Photosensitive compositions, films, filters, methods for manufacturing filters, solid-state imaging elements, and image display devices

Abstract

This invention provides a photosensitive composition comprising a colorant, a resin, a polymerizable compound, a photopolymerization initiator, a solvent, and compound A represented by formula (1). This invention also provides a film made using the photosensitive composition, a filter, a method for manufacturing the filter, a solid-state imaging element, and an image display device.

Description

Technical Field

[0001] This invention relates to a photosensitive composition containing a colorant. Furthermore, this invention relates to a film made using the photosensitive composition, a filter, a method for manufacturing the filter, a solid-state imaging element, and an image display device. Background Technology

[0002] In recent years, the widespread use of digital cameras and camera-equipped mobile phones has led to a significant increase in demand for solid-state imaging components such as charge-coupled device (CCD) image sensors. Color filters, as core devices in displays or optical components, are used. Color filters typically contain pixels of the three primary colors: red, green, and blue, and function to decompose transmitted light into these three primary colors.

[0003] The pixels of each color in the color filter are manufactured using a photosensitive composition containing color materials, and the pattern is formed by photolithography.

[0004] As described in Patent Document 1, this photosensitive composition uses a substance containing a colorant, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent.

[0005] Previous technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2022-063556

[0008] In recent years, the high resolution of solid-state imaging devices equipped with color filters and other light filters has also been developed. Therefore, research is underway on further miniaturization of pixel size for color filters and other light filters.

[0009] When pixels are formed by using a photosensitive composition and forming a pattern by methods such as photolithography, defects sometimes occur on the pixel surface during pixel formation. However, as the pixel size becomes smaller, there is a tendency for defects to easily occur on the pixel surface. Summary of the Invention

[0010] The technical problem to be solved by the invention

[0011] Therefore, the object of the present invention is to provide a photosensitive composition capable of suppressing the formation of defects in pixels. Furthermore, the object of the present invention is to provide a film, a filter, a method for manufacturing a filter, a solid-state imaging element, and an image display device.

[0012] means for solving technical problems

[0013] Based on the inventors' research, it was discovered that the above-mentioned objectives can be achieved through the photosensitive composition described later, thus completing the present invention. Therefore, the present invention provides the following.

[0014] <1> A photosensitive composition comprising a colorant, a resin, a polymerizable compound, a photopolymerization initiator, a solvent, and compound A represented by formula (1),

[0015] [Chemical Formula 1]

[0016]

[0017] In equation (1), R 1 and R 2 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 12 carbon atoms, a group containing an acid group with 1 to 6 carbon atoms, or a group containing an amino group with 1 to 6 carbon atoms. X 1 This indicates a straight-chain or branched alkylene group, where n represents an integer greater than or equal to 1. When n is 2 or greater, multiple X groups are represented. 1 They can be the same or different.

[0018] <2> According to the photosensitive composition described in <1>, wherein X of the above formula (1) 1 At least one of them is ethylene, R 1 and R 2 Each is independently an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0019] <3> According to the photosensitive composition described in <1>, wherein X of the above formula (1) 1 It is ethylene, R 1 and R 2 Each is independently an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0020] <4> The photosensitive composition according to any one of <1> to <3>, wherein R of formula (1) above... 1 and R 2 It is a hydrogen atom.

[0021] <5> The photosensitive composition according to any one of <1> to <4>, wherein the molecular weight of the compound A is 150 to 2000.

[0022] <6> The photosensitive composition according to any one of <1> to <5>, wherein the content of the above-mentioned compound A in the above-mentioned photosensitive composition is 0.01 to 5.0 by mass.

[0023] <7> The photosensitive composition according to any one of <1> to <6>, wherein the content of the colorant in the total solids component of the photosensitive composition is 55% by mass or more.

[0024] <8> A film obtained using any one of <1> to <7>.

[0025] <9> A filter having the membrane described in <8>.

[0026] <10> A method for manufacturing an optical device, comprising: a step of forming a composition layer on a support using any one of <1> to <7>; and a step of forming a pattern on the composition layer by photolithography.

[0027] <11> A solid-state imaging element having the film described in <8>.

[0028] <12> An image display device having the film described in <8>.

[0029] Invention Effects

[0030] According to the present invention, a photosensitive composition capable of suppressing the formation of defects in pixels can be provided. Furthermore, the present invention can provide a film, a filter, a method for manufacturing the filter, a solid-state imaging element, and an image display device. Attached Figure Description

[0031] Figure 1 This is a side sectional view showing one embodiment of the support.

[0032] Figure 2 From Figure 1 A top view taken directly above the support structure. Detailed Implementation

[0033] The present invention will now be described in detail.

[0034] In this specification, “~” is used to imply that the values ​​recorded before and after it are the lower and upper limits.

[0035] In the designation of groups (atomic groups) in this specification, the designations without substitution and without substitution include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl) but also alkyl groups with substituents (substituted alkyl).

[0036] In this specification, the term "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Furthermore, examples of light used in exposure include bright-line spectra of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other active light or radiation.

[0037] 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)acryloyl” means either or both of acryloyl and methacryloyl.

[0038] In this specification, in the structural formula, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0039] In this specification, the weight-average molecular weight and number-average molecular weight are converted values ​​of polystyrene determined by GPC (gel permeation chromatography).

[0040] In this specification, total solids content refers to the total mass of the components after removing the solvent from all components of the composition.

[0041] In this specification, pigment refers to a color material that is not easily soluble in solvents.

[0042] In this specification, the term "process" includes not only independent processes, but also processes that are not clearly distinguishable from other processes, as long as they achieve the desired effect.

[0043] <Photosensitive Composition>

[0044] The photosensitive composition of the present invention is characterized by containing a colorant, a resin, a polymerizable compound, a photopolymerization initiator, a solvent, and a compound A represented by formula (1).

[0045] The photosensitive composition of the present invention is able to form pixels in which the generation of defects is suppressed. The reason for achieving this effect is presumably due to the following reason. The reason is presumably that the photosensitive composition of the present invention, by containing compound A represented by formula (1), can impart appropriate softness to the film obtained by compound A represented by formula (1), thereby suppressing the generation of defects during development.

[0046] Furthermore, as the pigment content in the total solids of the photosensitive composition increases, there is a tendency for defects to easily form in the pixels when patterns are formed by photolithography. However, according to the photosensitive composition of the present invention, even if the pigment content in the total solids of the photosensitive composition is high, the generation of defects can be suppressed. Therefore, when using a photosensitive composition with a high pigment content in the total solids of the photosensitive composition and forming pixels by photolithography, the effects of the present invention can be more significantly achieved.

[0047] Furthermore, in recent years, techniques for forming pixels within regions defined by partitions on a support having partitions have been studied. However, when pixels are formed within regions defined by partitions, there is a tendency for defects to occur in the pixels compared to forming pixels on a support without partitions. But according to the photosensitive composition of the present invention, even when pixels are formed within regions defined by partitions on a support having partitions, the generation of defects can be suppressed. Therefore, when pixels are formed within regions defined by partitions, the photosensitive composition of the present invention can more significantly exert the effects of the present invention.

[0048] In addition, the photosensitive composition of the present invention further contains a compound A represented by formula (1) in addition to the colorant, resin, polymerizable compound, photopolymerization initiator and solvent. Thus, the photosensitive composition contains a substance of compound A represented by formula (1). For example, by treating pigments with compound A represented by formula (1) to produce processed pigments, the photosensitive composition contains processed pigments. As a result, it is different from the substance contained in the composition of compound A represented by formula (1).

[0049] The photosensitive composition of the present invention can preferably be used as a photosensitive composition for a filter. Examples of filters include color filters, infrared transmission filters, and infrared cutoff filters, with color filters being preferred.

[0050] As a color filter, an example is a filter having colored pixels that allow light of a specific wavelength to pass through. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The colored pixels of the color filter can be formed using a photosensitive composition containing colored pigments.

[0051] The maximum absorption wavelength of the infrared cutoff filter is preferably located 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, the transmittance of the infrared cutoff filter in all wavelength ranges from 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Furthermore, the transmittance at at least one location within the wavelength range of 700–1800 nm is preferably 20% or less. Furthermore, the ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at 550 nm (absorbance Amax / absorbance A550) is preferably 20–500, more preferably 50–500, even more preferably 70–450, and particularly preferably 100–400. The infrared cutoff filter can be formed using a photosensitive composition containing an infrared absorbing colorant.

[0052] An infrared transmission filter is a filter that allows at least a portion of infrared light to be transmitted. Preferably, an infrared transmission filter is a filter that blocks at least a portion of visible light while allowing at least a portion of infrared light to be transmitted. As an infrared transmission filter, a filter that satisfies the following spectral characteristics is preferred: 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. An infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).

[0053] (1): A filter with a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1500 nm.

[0054] (2): A filter with a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm.

[0055] (3): A filter with a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm.

[0056] (4): A filter with a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm.

[0057] (5): A filter with a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm.

[0058] The concentration of solid components 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, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0059] The components used in the photosensitive composition of the present invention will be described below.

[0060] <<Color>>

[0061] The photosensitive composition of the present invention contains a colorant. Examples of colorants include white colorants, black colorants, colored colorants, and infrared-absorbing colorants. In addition, in the present invention, the white colorant includes not only pure white, but also light gray (e.g., off-white, light gray, etc.) colorants that are close to white.

[0062] The colorant can be either a pigment or a dye. Pigments and dyes can be used together. The pigment can be either inorganic or organic, but organic pigments are preferred from the viewpoints of color variation, ease of dispersion, and safety. Pigment derivatives can also be used as the colorant. When using a pigment as the colorant, it is preferable to use both a pigment and a pigment derivative.

[0063] The average primary particle size of the pigment and pigment derivative is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. Furthermore, in this specification, the primary particle size of the pigment and pigment derivative can be determined by observing the primary particles of the pigment and pigment derivative using a transmission electron microscope and based on the obtained photographs. 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. Moreover, 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. The same applies to the average primary particle size of the pigment derivative.

[0064] The crystallite size, determined by the full width at half maximum (FWHM) of the peak of any crystal plane in the X-ray diffraction spectrum derived from the CuKα line of the pigment and pigment derivatives as the X-ray source, is preferably 0.1–100 nm, more preferably 0.5–50 nm, even more preferably 1–30 nm, and particularly preferably 5–25 nm.

[0065] The specific surface area of ​​pigments and pigment derivatives is preferably 1 to 300 m². 2 / g. The lower limit is preferably 10m. 2 / g or more, preferably 30m 2 / g or more. The upper limit is preferably 250m.2 / g or less, more preferably 200m 2 / g or less. The specific surface area can be determined according to the BET (Brunauer, Emmett and Teller) method and according to DIN 66131: determination of the specific surface area of ​​solids by gas adsorption.

[0066] The colorant contained in the photosensitive composition of the present invention preferably includes a colored colorant, more preferably including a colored colorant and a pigment derivative. Furthermore, the colored colorant preferably contains a pigment (colored pigment).

[0067] (color material)

[0068] As color materials, examples include those with extremely high absorption wavelengths in the range of 400–700 nm. Examples include green, red, yellow, purple, blue, and orange color materials.

[0069] Examples of red pigments include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, methylimine compounds, xaton compounds, quinacridone compounds, perylene compounds, and thioindole compounds, with diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds being preferred, and diketopyrrolopyrrole compounds being more preferred. Furthermore, the red pigment is preferably a pigment (red pigment), and more preferably a diketopyrrolopyrrole pigment.

[0070] As specific examples of red pigments, we can cite the CI (colorimetric index) values ​​for 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, 1 Red pigments in the following colors: 46, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297, etc. Furthermore, as a red pigment, compounds described in paragraph 0034 of International Patent Publication No. 2022 / 085485 and bromodione pyrrolopyrrole compounds described in Japanese Patent Application Publication No. 2020-085947 can also be used.

[0071] As a red pigment, CI Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, CI Pigment Red 254, 264, and 272 are more preferred, and CI Pigment Red 254 and 264 are even more preferred.

[0072] Examples of green colorants include phthalocyanine compounds and squaric acid cyanine compounds, with phthalocyanine compounds being preferred. Furthermore, the green colorant is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.

[0073] Specific examples of green pigments include CI pigments green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Furthermore, zinc halide phthalocyanine pigments with an average of 10-14 halogen atoms, 8-12 bromine atoms, and 2-5 chlorine atoms per molecule can also be used as green pigments. Specific examples include the compound described in International Publication No. 2015 / 118720. Additionally, compounds described in paragraph 0029 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Patent Application Publication No. 2020-070426, and diarylmethane compounds described in Japanese Patent Application Publication No. 2020-504758 can also be used as green pigments.

[0074] As a green pigment, CI pigment green 7, 36, 58, 62, and 63 are preferred.

[0075] Examples of orange colorants include diketopyrrole compounds and azo compounds. Pigments (orange pigments) are preferred as orange colorants. Specific examples of orange colorants include CI Pigment Orange 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.

[0076] Examples of yellow pigments include azo compounds, methylimine compounds, isoindolinite compounds, pteridine compounds, quinoline compounds, and perylene compounds. Pigments (yellow pigments) are preferred as yellow pigments. Specific examples of yellow pigments include CI pigments 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, and 12. Yellow pigments in the following digits: 0, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236, etc.

[0077] As a yellow pigment, nickel azobarbiturate complexes with the following structure can also be used.

[0078] [Chemical Formula 2]

[0079]

[0080] As a yellow pigment, compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485, methylene dyes described in Japanese Patent Application Publication No. 2019-073695, and methylene dyes described in Japanese Patent Application Publication No. 2019-073696 can be used.

[0081] Examples of purple pigments include oxazine compounds, quinacridone compounds, perylene compounds, and indigo compounds, with oxazine compounds being preferred. Pigments (purple pigments) are also preferred as purple pigments. Specific examples of purple pigments include CI pigments such as Purple 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0082] Examples of blue pigments include phthalocyanine compounds and squaric acid cyanine compounds, with phthalocyanine compounds being preferred. Pigments (blue pigments) are also preferred as blue pigments. Specific examples of blue pigments include CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Furthermore, aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue pigments. Specific examples include 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.

[0083] Colored pigments can also use dyes. There are no particular restrictions on the types of dyes used; well-known dyes can be used. Examples include pyrazole azo, aniline azo, triarylmethane, anthraquinone, anthraquinone, benzylene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethyl, xanthones, phthalocyanine, benzopyran, indigo, and pyrrole methylene dyes.

[0084] Pigment polymers can also be used in colored pigments. Pigment polymers are preferably dyes dissolved in a solvent. Furthermore, pigment polymers can be formed into particles. When the pigment polymer is in particle form, it is usually used in a dispersed state in a solvent. Particle-state pigment polymers can be obtained, for example, by emulsion polymerization; specific examples include the compound and manufacturing method described in Japanese Patent Application Publication No. 2015-214682. The pigment polymer has two or more pigment structures in one molecule, preferably three or more. There is no particular upper limit, and it can be set to 100 or less. The multiple pigment structures in one molecule can be the same pigment structure or different pigment structures. The weight-average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and further preferably 6000 or more. The upper limit is more preferably 30000 or less, and further preferably 20000 or less. The pigment polymers may also include 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, and International Publication No. 2016 / 031442.

[0085] As a colored pigment, it is possible to use the triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, the xanthones compound described in Japanese Patent Application Publication No. 2020-117638, the phthalocyanine compound described in International Patent Publication No. 2020 / 174991, the isoindoline compound or its salt described in Japanese Patent Application Publication No. 2020-160279, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069442, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, and the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-00690. The compounds represented by Formula 1 as described in Publication No. 70, the compounds represented by Formula 1 as described in Korean Patent Publication No. 10-2020-0069067, the compounds represented by Formula 1 as described in Korean Patent Publication No. 10-2020-0069062, the zinc halide phthalocyanine pigment described in Japanese Patent No. 6809649, the isoindoline compound described in Japanese Unexamined Patent Publication No. 2020-180176, the phenothiazine compound described in Japanese Unexamined Patent Publication No. 2021-187913, the zinc halide phthalocyanine described in International Publication No. 2022 / 004261, and the zinc halide phthalocyanine described in International Publication No. 2021 / 250883. The colored pigment can be rotaxane, and the pigment skeleton can be used for cyclic structures of rotaxane, rod structures, or both. As a color pigment, it is also possible to use the quinoline compound represented by Formula 1 in Korean Patent Publication No. 10-2020-0030759, the polymer dye described in Korean Patent Publication No. 10-2020-0061793, the color pigment described in Japanese Patent Application Publication No. 2022-029701, the isoindoline compound described in International Patent Publication No. 2022 / 014635, the aluminum phthalocyanine compound described in International Patent Publication No. 2022 / 024926, the compound described in Japanese Patent Application Publication No. 2022-045895, the compound described in International Patent Publication No. 2022 / 050051, and the Japanese... The compounds described in Japanese Patent Application Publication No. 2020-090676, Japanese Patent Application Publication No. 2020-055956, Japanese Patent Application Publication No. 2021-031681, Japanese Patent Application Publication No. 2022-056354, U.S. Patent Application Publication No. 2021 / 0355327, International Patent Publication No. 2022 / 065357, Japanese Patent Application Publication No. 2020-045436, and Korean Patent Publication No. 10-2021-0146726.Compounds described in Japanese Patent Application Publication No. 2018-178039, compounds described in Chinese Patent Application Publication No. 113881244, compounds described in Chinese Patent Application Publication No. 113881245, compounds described in Chinese Patent Application Publication No. 113881246, compounds described in Japanese Patent Application Publication No. 2022-104822, compounds described in Japanese Patent Application Publication No. 2022-096701, compounds described in Japanese Patent Application Publication No. 2020-023652, and 80-80 of the Japan Colorant Association Journal (published in 2022). The green pigment described on page 4, the compound described in Japanese Patent Application Publication No. 2022-143135, the compound described in Japanese Patent Application Publication No. 2022-140287, the compound described in International Publication No. 2022 / 136308, the perylene compound described in Chinese Patent Application Publication No. 113061349, the cyan pigment described in Korean Patent Publication No. 10-2017-0018993, the isoindoline compound described in Japanese Patent Application Publication No. 2020-180176, the compound described in Japanese Patent Application Publication No. 2023-013209, and Japanese Patent Application Publication No. 2... The compounds described in Japanese Patent Application Publication No. 023-013166, the compounds described in International Patent Application Publication No. 2023 / 286526, the compounds described in Japanese Patent Application Publication No. 2021-155746, the compounds described in Japanese Patent Application Publication No. 2021-155747, the compounds described in Japanese Patent Application Publication No. 2021-155748, the compounds described in Japanese Patent Application Publication No. 2021-155749, the compounds described in International Patent Application Publication No. 2018 / 051876, the compounds described in Japanese Patent Application Publication No. 2020-083981, and the compounds described in Japanese Patent Application Publication No. 2023-05 The compounds described in Japanese Patent Application Publication No. 6463, the compounds described in Japanese Patent Application Publication No. 2023-515473, the dioxane compounds described in Japanese Patent Application Publication No. 2022-549530, the pigment preparations described in Japanese Patent Application Publication No. 2022-061494, the diketopyrrolopyrrole pigments described in Japanese Patent Application Publication No. 2023-057917, the diketopyrrolopyrrole compounds described in Japanese Patent Application Publication No. 2023-061273, the phthalocyanines described in Japanese Patent Application Publication No. 2023-519314, and the quinophthalones described in Japanese Patent Application Publication No. 2023-080419, etc.

[0086] Two or more colored pigments can also be used in combination. Furthermore, when two or more colored pigments are used in combination, black can be formed by combining two or more colored pigments. Examples of such combinations include the following (1) to (7). When the photosensitive composition contains two or more colored pigments and black is presented by combining two or more colored pigments, the photosensitive composition of the present invention can preferably be used as a photosensitive composition for forming an infrared transmission filter.

[0087] (1) A method containing red and blue pigments.

[0088] (2) A method containing red, blue and yellow pigments.

[0089] (3) A method containing red, blue, yellow and purple pigments.

[0090] (4) A method containing red, blue, yellow, purple and green pigments.

[0091] (5) A method containing red, blue, yellow and green pigments.

[0092] (6) A method containing red, blue and green pigments.

[0093] (7) Methods containing yellow and purple pigments.

[0094] (White pigment)

[0095] Examples of inorganic pigments that can be used as 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, and zinc sulfide. White pigments can be those described in paragraphs 0040 to 0043 of International Publication No. 2022 / 085485.

[0096] (Black pigment)

[0097] The use of a black colorant is not particularly limited, and any known colorant can be used. The black colorant can be either inorganic or organic. Pigments are preferred. Furthermore, in this specification, a black colorant refers to a colorant that exhibits absorption across the entire wavelength range of 400–700 nm.

[0098] Examples of inorganic black pigments include carbon black, titanium black, and graphite, with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black consists of black particles containing titanium atoms, and is preferably low-order titanium oxide or titanium oxynitride. The titanium black described in paragraph 0044 of International Publication No. 2022 / 085485 can be used. Zirconium nitride powder described in Japanese Patent Application Publication No. 2023-048173 can also be used as an inorganic black pigment.

[0099] Examples of organic black pigments include bisbenzofuranone compounds, methylimine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. The organic black pigment can be any compound described in paragraph 0166 of International Patent Publication No. 2022 / 065215. Furthermore, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016 to 0020 of Japanese Patent Application Publication No. 2017-226821, and black azo pigments described in Japanese Patent Application Publication No. 2022-121935 can also be used as organic black pigments.

[0100] The black pigments described in items 294-307 of the Journal of the Color Materials Association, Vol. 96, No. 9, 2023.

[0101] (Infrared absorbing color material)

[0102] The infrared absorbing colorant is preferably a compound that has a maximum absorption wavelength on the wavelength side longer than 700 nm. More preferably, it is a compound that has a maximum absorption wavelength in the range exceeding 700 nm and below 1800 nm; even more preferably, it is a compound that has a maximum absorption wavelength in the range exceeding 700 nm and below 1400 nm; even more preferably, it is a compound that has a maximum absorption wavelength in the range exceeding 700 nm and below 1200 nm; and particularly preferably, it is a compound that has a maximum absorption wavelength in the range exceeding 700 nm and below 1000 nm. Furthermore, the absorbance A of the infrared absorbing colorant at a wavelength of 500 nm... 1 Absorbance A at the wavelength of maximum absorption 2 The ratio A 1 / A 2 Preferably, the concentration is 0.08 or less, more preferably 0.04 or less. Furthermore, the infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.

[0103] Examples of infrared absorbing colorants 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, methylimine compounds, anthraquinone compounds, dibenzofuranone compounds, dithioene metal complexes, metal oxides, and metal borides. Specific examples include the compounds described in paragraph 0114 of International Publication No. 2022 / 065215. Furthermore, as an infrared absorbing colorant, compounds described in paragraph 0121 of International Publication No. 2022 / 065215, squaric acid compounds described in Japanese Patent Application Publication No. 2020-075959, copper complexes described in Korean Patent Publication No. 10-2019-0135217, ketone acid compounds described in Japanese Patent Application Publication No. 2021-195515, infrared absorbing pigments described in Japanese Patent Application Publication No. 2022-022070, and international publication No. 2019 / 0217 can also be used. The compounds described in Japanese Patent Application Publication No. 67, Japanese Patent Application Publication No. 2019-127549, Japanese Patent Application Publication No. 2022 / 059619, Japanese Patent Application Publication No. 2022-151682, Japanese Patent Application Publication No. 2022-188858, Japanese Patent Application Publication No. 2022-184710, Japanese Patent Application Publication No. 2022-189736, and Japanese Patent Application Publication No. 2023-004. The following compounds are described in Japanese Patent Publication No. 570, International Patent Publication No. 2019 / 230660, International Patent Publication No. 2020 / 218615, Japanese Patent Application Publication No. 2023-068643, Japanese Patent Application Publication No. 2023-052770, Korean Patent Publication No. 10-2022-0163680, and Japanese Patent Application Publication No. 2023-073064. Indigo monoboron complexes, phthalocyanine compounds described in Japanese Patent Application Publication No. 2023-066025, phthalocyanine compounds described in Japanese Patent Application Publication No. 2020-041127, indigo compounds described in Japanese Patent Application Publication No. 2023-073064, indigo compounds described in Korean Patent Publication No. 10-2023-0016355, squaric acid cyanine compounds described in International Patent Publication No. 2019 / 230570, and diimine compounds described in Japanese Patent Application Publication No. 2023-095824.

[0104] (Pigment derivatives)

[0105] As pigment derivatives, compounds that have pigment structures and acid or base groups can be cited.

[0106] Examples of pigment structures mentioned above include quinoline pigment structures, benzimidazolone pigment structures, benzisoindole pigment structures, benzothiazole pigment structures, imine pigment structures, squaric acid cyanine pigment structures, ketoneonium pigment structures, oxacyanine pigment structures, pyrrolopyrrole pigment structures, diketopyrrolopyrrole pigment structures, azo pigment structures, methylimine pigment structures, phthalocyanine pigment structures, naphthylphthalocyanine pigment structures, anthraquinone pigment structures, quinacridone pigment structures, dioxazine pigment structures, violane pigment structures, perylene pigment structures, thiazine indigo pigment structures, thioindoleline pigment structures, isoindoleline pigment structures, isoindoleline ketone pigment structures, quinophthalone pigment structures, dithiol pigment structures, triarylmethane pigment structures, and pyrrole methylene pigment structures.

[0107] Examples of acid groups found in pigment derivatives include carboxyl, sulfonyl, phosphate, borate, imide, and their salts. Examples of atoms or groups constituting salts include alkali metal ions (Li...). + Na + K + (etc.), alkaline earth metal ions (Ca 2+ Mg 2+ (etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, etc. As an imide acid group, -SO₂NHSO₂R is preferred. X1 -CONHSO2R X2 -CONHCOR X3 or -SO2NHCOR X4 More preferably -SO2NHSO2R X1 -CONHSO2R X2 or -SO2NHCOR X4 Further preferred is -SO2NHSO2R X1 or -CONHSO2R X2 R X1 ~R X4 Each can be represented independently as either alkyl or aryl. R X1 ~R X4 The alkyl and aryl groups represented may have substituents. Halogen atoms are preferred as substituents, and fluorine atoms are more preferred. R X1 ~R X4Each of the following is preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, more preferably an alkyl group containing a fluorine atom. The alkyl group containing a fluorine atom preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group containing a fluorine atom preferably has 6 to 20 carbon atoms, more preferably 6 to 12, and even more preferably 6.

[0108] Examples of bases found in pigment derivatives include amino, pyridyl 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, and phenoxide ions.

[0109] As an amino group, examples include those composed of -NR x11 R x12 The groups and cyclic amino groups are represented.

[0110] In the case of -NR x11 R x12 In the indicated group, R x11 and R x12 Each group independently represents a hydrogen atom, an alkyl group, or an aryl group, preferably an alkyl group. That is, the amino group is preferably a dialkylamino group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, preferably straight-chain or branched, and more preferably straight-chain. The alkyl group may have substituents. Examples of substituents include the substituent T described above. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have substituents. Examples of substituents include the substituent T described above.

[0111] Examples of cyclic amino groups include pyrrolidinyl, piperidinyl, piperazinyl, and morpholinyl. These groups can further have substituents.

[0112] The content of colorant in the total solids component of the photosensitive composition is preferably 50% by mass or more, more preferably 55% by mass or more.

[0113] The colorant used in the photosensitive composition of the present invention preferably contains a pigment, more preferably a pigment and a pigment derivative. Furthermore, the pigment is preferably a colored pigment. The pigment content in the colorant is preferably 20-100% by mass, more preferably 50-100% by mass, and even more preferably 70-100% by mass. The content of the pigment derivative relative to 100 parts by mass of pigment is preferably 1-30 parts by mass, more preferably 3-20 parts by mass. The total content of the pigment and pigment derivative in the colorant is preferably 25-100% by mass, more preferably 55-100% by mass, and even more preferably 75-100% by mass.

[0114] The photosensitive composition of the present invention may contain only one colorant or two or more colorants. When it contains two or more colorants, their total amount is preferably within the above-mentioned range.

[0115] <<Polymerizable Compounds>>

[0116] The photosensitive composition of the present invention contains a polymerizable compound. Examples of polymerizable compounds include compounds having groups containing olefinic unsaturated bonds. Examples of groups containing olefinic unsaturated bonds include vinyl, (meth)allyl, and (meth)acryloyl groups. The polymerizable compound is preferably a free radical polymerizable compound.

[0117] As a polymerizable compound, it can be any chemical form such as a monomer, prepolymer, or oligomer, but is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 2500. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.

[0118] From the viewpoint of the storage stability of the photosensitive composition, the number of groups containing olefinic unsaturated bonds (hereinafter referred to as the C=C value) of the polymeric compound is preferably 2 to 14 mmol / g. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and even more preferably 5 mmol / g or more. The upper limit is preferably 12 mmol / g or less, more preferably 10 mmol / g or less, and even more preferably 8 mmol / g or less. The C=C value of the polymeric compound is calculated by dividing the number of groups containing olefinic unsaturated bonds contained in one molecule of the polymeric compound by the molecular weight of the polymeric compound.

[0119] The polymerizable compound is preferably a compound containing three or more groups with olefinic unsaturated bonds, more preferably a compound containing 3 to 15 groups with olefinic unsaturated bonds, and even more preferably a compound containing 3 to 6 groups with olefinic unsaturated bonds. Furthermore, the polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples of polymerizable compounds include the compounds described in paragraphs 0075 to 0083 of International Patent Publication No. 2022 / 065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.

[0120] Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available, KAYARADD-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ESTER A-DPH-12E; SHIN-NAKAMURA CHEMICAL Co., Ltd.), and compounds with structures in which these (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (e.g., SR454 and SR499 commercially available from SARTOMER Company, Inc.). Furthermore, as polymerizable compounds, diglyceride EO (ethylene oxide) can also be used to modify (meth)acrylates (as a commercially available product, M-460; manufactured by TOAGOSEI CO.,LTD.), pentaerythritol tetraacrylate (manufactured by SHIN-NAKAMURA CHEMICAL Co.,Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co.,Ltd., KAYARADHDDA), 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 (Nippon Kayaku Co.,Ltd.). (Manufactured by KYOEISHA CHEMICAL 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.), ARONIXMT-3041, 3042 (manufactured by TOAGOSEI CO.,LTD., polymeric compounds containing amines), ARONIX M-510, 520 (manufactured by TOAGOSEI CO.,LTD.).The following are listed: Polymers with acidic groups (manufactured by Eternal Materials Co., Ltd., a polymer with hyperbranched structures); EBECRYL80 (a tetrafunctional monomer containing amines, manufactured by DAICEL-ALLNEX LTD.); EBECRYL7100 (a difunctional monomer containing amines, manufactured by DAICEL-ALLNEX LTD.); CN371NS (a difunctional monomer containing amines, manufactured by Arkema SA); HOA-MPL (2-acryloyloxyethyl-phthalic acid: manufactured by KYOEISHA CHEMICAL CO.,LTD.); HOA-MPE (2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid: manufactured by KYOEISHA CHEMICAL CO.,LTD.). Polymer compounds having dendritic or hyperbranched structures, as described in Japanese Patent Application Publication No. 2023-043479, and polymer compounds described in Japanese Patent Application Publication No. 2023-529984, etc.

[0121] The content of polymeric compounds in the total solids component of the photosensitive composition is preferably 1 to 30% by mass. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.

[0122] The photosensitive composition of the present invention may contain only one polymeric compound or two or more polymeric compounds. When containing two or more polymeric compounds, their total amount is preferably within the above-mentioned range.

[0123] <<Resin>>

[0124] The photosensitive composition of the present invention contains a resin. For example, the resin is incorporated for purposes such as dispersing pigments in the photosensitive composition or as an adhesive. Additionally, the resin primarily used for dispersing pigments in the photosensitive composition is also referred to as a dispersant. However, this use of the resin is only one example; the resin can also be used for purposes other than this.

[0125] The weight-average molecular weight (Mw) of the resin is preferably between 3,000 and 2,000,000. The upper limit is preferably below 1,000,000, more preferably below 500,000. The lower limit is preferably above 4,000, more preferably above 5,000.

[0126] Examples of resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, olefin-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyaryl ether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Furthermore, as a resin, the resins described in paragraphs 0091 to 0099 of International Publication No. 2022 / 065215, the end-capped polyisocyanate resins described in Japanese Patent Application Publication No. 2016-222891, the resins described in Japanese Patent Application Publication No. 2020-122052, the resins described in Japanese Patent Application Publication No. 2020-111656, the resins described in Japanese Patent Application Publication No. 2020-139021, the resins described in Japanese Patent Application Publication No. 2017-138503 containing structural units having a ring structure in the main chain and biphenyl structural units having a side chain, the resins described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373, and the alkali-soluble resins described in Japanese Patent Application Publication No. 2020-186325 can also be used. The resin represented by Formula 1 as described in Korean Patent Publication No. 10-2020-0078339, the copolymer containing epoxy and acid groups as described in International Publication No. 2022 / 030445, the resin described in Japanese Patent Application Publication No. 2018-135514, the copolymer described in Japanese Patent Application Publication No. 2020-041046, the resin described in Japanese Patent Application Publication No. 2023-033156, the resin described in Japanese Patent Application Publication No. 2023-030386, the resin described in Japanese Patent Application Publication No. 2023-027753, the resin described in Japanese Patent Application Publication No. 2020-139021, the resin described in Japanese Patent Application Publication No. 2023-074038, and the resin described in Japanese Patent Application Publication No. 2023-079666.

[0127] As the resin, a resin having acid groups is preferred. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, and phenolic hydroxyl groups.

[0128] The acid value of the resin containing acid groups is preferably 30 to 500 mg KOH / g. The lower limit is preferably 40 mg KOH / g or more, more preferably 50 mg KOH / g or more. The upper limit is preferably 400 mg KOH / g or less, more preferably 300 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. The weight-average molecular weight (Mw) of the resin containing acid groups is preferably 5000 to 100000, more preferably 5000 to 50000. The number-average molecular weight (Mn) of the resin containing acid groups is preferably 1000 to 20000.

[0129] The resin containing acid groups preferably contains repeating units with acid groups on their side chains. More preferably, among all repeating units in the resin, it contains 5 to 70 mol% of repeating units with acid groups on their side chains. The upper limit of the content of repeating units with acid groups on their side chains is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units with acid groups on their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.

[0130] Regarding resins containing acid groups, for example, reference can be made to paragraphs 0558 to 0571 of Japanese Patent Application Publication No. 2012-208494 (corresponding to paragraphs 0685 to 0700 of U.S. Patent Application Publication No. 2012 / 0235099) and paragraphs 0076 to 0099 of Japanese Patent Application Publication No. 2012-198408, the contents of which are incorporated herein by reference. Furthermore, commercially available resins containing acid groups can also be used. Moreover, there are no particular limitations on the method for introducing acid groups into the resin; for example, the method described in Japanese Patent No. 6349629 can be cited. Additionally, as a method for introducing acid groups into the resin, a method of introducing acid groups by reacting an acid anhydride with a hydroxyl group generated in the ring-opening reaction of an epoxy group can also be cited.

[0131] The photosensitive composition of the present invention preferably contains a resin having a base group. The resin having a base group is preferably a resin containing repeating units having a base group on the side chain, more preferably a copolymer having repeating units having a base group on the side chain and repeating units without a base group, and even more preferably a block copolymer having repeating units having a base group on the side chain and repeating units without a base group. The resin having a base group can also be used as a dispersant. The amine value of the resin having a base group is preferably 5 to 300 mg KOH / g. The lower limit is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more. The upper limit is preferably 200 mg KOH / g or less, more preferably 100 mg KOH / g or less.

[0132] Commercially available resins containing alkali groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by BYK-Chemie GmbH), and Solsperse. Models 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan Limited), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), etc. Furthermore, the resins containing base groups can also include the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Application Publication No. 2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of Japanese Patent Application Publication No. 2018-156021, and the vinyl resins containing base groups described in paragraphs 0150 to 0153 of Japanese Patent Application Publication No. 2019-184763, all of which are incorporated herein by reference.

[0133] The photosensitive composition of the present invention preferably contains both an acidic resin and a basic resin. This further improves the storage stability of the photosensitive composition. When both an acidic resin and a basic resin are used, the content of the basic resin is preferably 20 to 500 parts by weight, more preferably 30 to 300 parts by weight, and even more preferably 50 to 200 parts by weight, relative to 100 parts by weight of the acidic resin.

[0134] As the resin, a resin having aromatic carboxyl groups is preferred. In a resin having aromatic carboxyl groups, the aromatic carboxyl groups may be contained in the main chain of the repeating unit or in the side chain of the repeating unit. It is preferable that the aromatic carboxyl groups are contained in the main chain of the repeating unit. Furthermore, in this specification, an aromatic carboxyl group refers to a group in which one or more carboxyl groups are bonded to an aromatic ring. In an aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2. Examples of resins having aromatic carboxyl groups include those described in paragraphs 0082 to 0107 of International Publication No. 2021 / 166858.

[0135] As the resin, a resin having crosslinking groups is preferred. Examples of crosslinking groups include (meth)acryloyl, epoxy, and oxetyl. When a resin having crosslinking groups is used, the content of the resin having crosslinking groups in the resin contained in the photosensitive composition is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0136] The photosensitive composition of the present invention preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). An acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups exceeds the amount of base groups. When the total amount of acid groups and base groups is set to 100 mol%, a resin in which the amount of acid groups is 70 mol% or more is preferred. The acid groups in the acidic dispersant (acidic resin) are preferably carboxyl groups. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mg KOH / g. Similarly, a basic dispersant (basic resin) refers to a resin in which the amount of base groups exceeds the amount of acid groups. When the total amount of acid groups and base groups is set to 100 mol%, a resin in which the amount of base groups exceeds 50 mol% is preferred. The base groups in the basic dispersant are preferably amino groups.

[0137] Grafted resins are preferred as dispersants. For details regarding grafted resins, please refer to paragraphs 0025 to 0094 of Japanese Patent Application Publication No. 2012-255128, which are incorporated herein by reference.

[0138] The resin used as a dispersant is preferably a resin having aromatic carboxyl groups. Examples of resins having aromatic carboxyl groups include the resins described above.

[0139] The resin used as a dispersant is preferably a polyimide-based dispersant containing a nitrogen atom at least once in the main chain and side chains. As a polyimide-based dispersant, a resin having a main chain and side chains, and having a basic nitrogen atom at least once in the main chain and side chains, is preferred. The main chain contains a partial structure with functional groups having a pKa of 14 or less, and the side chains have 40 to 10,000 atoms. There are no particular limitations as long as the basic nitrogen atom is a nitrogen atom exhibiting basicity. For information on polyimide-based dispersants, please refer to paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, which is incorporated herein by reference.

[0140] The resin used as a dispersant is preferably a resin with a structure in which multiple polymer chains are bonded to the core. Examples of such resins include dendritic polymers (including star polymers). Specific examples of dendritic polymers include polymers C-1 to C-31 as described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0141] The resin used as a dispersant is preferably a resin containing repeating units with olefinically unsaturated groups on the side chains. The content of repeating units with olefinically unsaturated groups on the side chains is preferably 10 mol% or more, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol% of all repeating units in the resin.

[0142] As a dispersant, the resin described in Japanese Patent Application Publication No. 2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent Publication No. 6432077, the polyethyleneimine with polyester side chains described in International Publication No. 2016 / 104803, the block copolymers described in International Publication No. 2019 / 125940, the block polymers with acrylamide structural units described in Japanese Patent Application Publication No. 2020-066687, the block polymers with acrylamide structural units described in Japanese Patent Application Publication No. 2020-066688, and the dispersant described in International Publication No. 2016 / 104803, etc., can also be used.

[0143] Dispersants are also available as commercially available products. Specific examples include the DISPERBYK series manufactured by BYK-Chemie GmbH, the SOLSPERSE series manufactured by Lubrizol Japan Limited, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Inc. Furthermore, the products described in paragraph 0129 of Japanese Patent Application Publication No. 2012-137564 and paragraph 0235 of Japanese Patent Application Publication No. 2017-194662 can also be used as dispersants.

[0144] The resin content in the total solids component of the photosensitive composition is preferably 1 to 60% by mass. 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 particularly preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less.

[0145] The content of resins containing acid groups in the total solids component of the photosensitive composition is preferably 1 to 60% by mass. 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 particularly preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less.

[0146] The resin content is preferably 100 to 1000 parts by weight relative to 100 parts by weight of the polymerizable compound. The lower limit is preferably 150 parts by weight or more, more preferably 200 parts by weight or more. The upper limit is preferably 600 parts by weight or less, more preferably 500 parts by weight or less.

[0147] The photosensitive composition of the present invention may contain only one type of resin or two or more types of resin. When it contains two or more types of resin, it is preferable that their total amount is within the above-mentioned range.

[0148] <<Photopolymerization Initiator>>

[0149] The photosensitive composition of the present invention contains a photopolymerization initiator. There are no particular limitations on the photopolymerization initiator, and it can be appropriately selected from known photopolymerization initiators. For example, compounds that are photosensitizing to light in the ultraviolet to visible regions are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0150] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, and α-amino ketone compounds. From the viewpoint of exposure sensitivity, photopolymerization initiators are preferably trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds. More preferably, they are compounds selected from oxime compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and acylphosphine compounds. Oxime compounds are even more preferred. Furthermore, as photopolymerization initiators, examples include the compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, and MATERIAL STAGE 37-60p, vol. 19, No.The peroxide-based photopolymerization initiator described in 3, 2019; the photopolymerization initiator described in International Publication No. 2018 / 221177; the photopolymerization initiator described in International Publication No. 2018 / 110179; the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-043864; the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-044030; the peroxide-based initiator described in Japanese Patent Application Publication No. 2019-167313; the oxazolyl-based aminoacetophenone initiator described in Japanese Patent Application Publication No. 2020-055992; and the photopolymerization initiator described in Japanese Patent Application Publication No. 2013-190459. The oxime-based photopolymerization initiators described herein, the polymers described in Japanese Patent Application Publication No. 2020-172619, the compounds represented by formula 1 described in International Patent Application Publication No. 2020 / 152120, the compounds described in Japanese Patent Application Publication No. 2021-181406, the photopolymerization initiators described in Japanese Patent Application Publication No. 2022-013379, the compounds represented by formula (1) described in Japanese Patent Application Publication No. 2022-015747, the fluorinated fluorene oxime ester-based photoinitiators described in Japanese Patent Application Publication No. 2021-507058, the initiators described in Chinese Patent Application Publication No. 110764367, and Japanese Patent Application Publication No. 2 The initiator described in Japanese Patent Application Publication No. 022-518535, the initiator described in International Publication No. 2021 / 175855, the compound described in Japanese Patent Application Publication No. 2022-078550, the compound described in Korean Patent Publication No. 10-2017-0087330, the compound described in International Publication No. 2022 / 075452, the oxime ester compound described in Chinese Patent Application Publication No. 110066225, the compound described in Korean Patent Publication No. 10-2022-0076157, and the compound having a triarylamine or N-arylcarbazole skeleton in International Publication No. 2019 / 01311 The compounds described in paragraphs 0042 to 0062 of Patent No. 2, the oxime ester-based photopolymerization initiator described in Japanese Patent No. 7219378, the photopolymerization initiator described in Korean Patent Publication No. 10-2021-0146174, the photopolymerization initiator described in International Patent Publication No. 2019 / 013112, the photopolymerization initiator described in Japanese Unexamined Patent Application Publication No. 2023-033731, the initiator described in Japanese Unexamined Patent Application Publication No. 2022-515524, the initiator described in Japanese Unexamined Patent Application Publication No. 2023-517304, and the initiator described in Chinese Patent Application Publication No. 114149517, etc.

[0151] In addition, as a photopolymerization initiator, the compound described in Taiwan Patent Application Publication No. 202200534 can be cited.

[0152] Specific examples of hexaaryl biimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole, etc.

[0153] 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 B.V.), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (both manufactured by BASF).

[0154] Examples of oxime compounds include those described in paragraph 0142 of International Publication No. 2022 / 085485, those described in Japanese Patent No. 5430746, those described in Japanese Patent No. 5647738, those represented by general formula (1) or described in paragraphs 0022 to 0024 of Japanese Patent Application Publication No. 2021-173858, and those represented by general formula (1) or described in paragraphs 0117 to 0120 of Japanese Patent Application Publication No. 2021-170089. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), etc. As commercially available products, examples include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR-PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, and TR-PBG-B (all manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), and ADEKAOPTOMER N-1919 (ADEKA...). The photopolymerization initiator 2, manufactured by CORPORATION and disclosed in Japanese Patent Application Publication No. 2012-014052, is used. Furthermore, as the oxime compound, a colorless compound or a compound with high transparency and resistance to discoloration is preferred. Commercially available examples include ADEKA ARKLS NCI-730, NCI-831, NCI-831E, and NCI-930 (all manufactured by ADEKA CORPORATION).

[0155] As photopolymerization initiators, oxime compounds having a fluorene ring, oxime compounds having at least one benzene ring in a carbazole ring forming a naphthalene ring skeleton, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds having a hydroxyl substituent bonded to a carbazole skeleton, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485 can also be used.

[0156] Compounds represented by formula (OX-1) can also be used as photopolymerization initiators.

[0157] [Chemical Formula 3]

[0158]

[0159] In equation (OX-1), X 1a It indicates that it contains at least one divalent linker selected from the group consisting of aromatic rings and heterocycles.

[0160] R 1a Represents a hydrogen atom or an acyl group.

[0161] R 2a Indicates alkyl or aryl.

[0162] R 3a and R 4a Each can be used independently to represent a hydrogen atom or an alkyl group.

[0163] Alk 1 and Alk 2 Each can be used independently to represent an alkyl group.

[0164] R 3a With R 4a They can bond together to form a ring.

[0165] Alk 1 With Alk 2 They can bond together to form a ring.

[0166] n represents 0 or 1.

[0167] X as in equation (OX-1) 1a Examples of divalent linking groups include divalent aromatic cyclic groups, divalent heterocyclic groups, divalent groups that bond two or more aromatic rings via single bonds or linking groups, divalent groups that bond two or more heterocyclic rings via single bonds or linking groups, and divalent groups that bond aromatic rings and heterocyclic rings via single bonds or linking groups. Examples of linking groups for bonding aromatic rings to each other, heterocyclic groups to each other, or aromatic rings to heterocyclic rings include -CH2-, -O-, -CO-, -S-, and -NR. x - and groups formed by combining them, etc. Rx It represents a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic group.

[0168] X in equation (OX-1) 1a Preferably, it is a group represented by any one of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8), and even more preferably a group represented by formula (X-2) or formula (X-6).

[0169] [Chemical Formula 4]

[0170]

[0171] In the formula R X1 ~R X9 Each group independently represents a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic group, with * indicating a bond.

[0172] R X1 ~R X9 The alkyl group represented preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups.

[0173] R X1 ~R X9 The alkenyl group preferably has 2 to 15 carbon atoms, more preferably 2 to 10. The alkenyl group can be straight-chain, branched, or cyclic. The alkenyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups.

[0174] R X1 ~R X9 The number of carbon atoms in the represented alkynyl group is preferably 2 to 15, more preferably 2 to 10. The alkynyl group can be straight-chain, branched, or cyclic. The alkynyl group can have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups.

[0175] R X1 ~R X9 The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heterocyclic groups.

[0176] R X1 ~R X9The heterocyclic group represented is preferably a 5-membered or 6-membered ring. The heteroatoms in the heterocyclic group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0177] R in equation (OX-1) 1a It represents a hydrogen atom or an acyl group, preferably an acyl group.

[0178] R 1a The acyl group represented is preferably composed of -C(O)-R 101 The group indicated by R. 101 It represents an aryl or heterocyclic group, preferably an aryl group.

[0179] R 101 The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heterocyclic groups. 101 The aryl group represented is preferably phenyl, methylphenyl, or naphthyl, more preferably methylphenyl or naphthyl.

[0180] R 101 The heterocyclic group represented is preferably a 5-membered or 6-membered ring. The heteroatoms in the heterocyclic group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0181] R in equation (OX-1) 2a The group is alkyl or aryl, and alkyl is preferred for its high reactivity in generating free radicals.

[0182] R 2a The alkyl group represented preferably has 1 to 15 carbon atoms, more preferably 1 to 10, even more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, more preferably straight-chain. The alkyl group may have substituents, but is preferably unsubstituted. 2a The alkyl group represented is preferably an unsubstituted straight-chain or branched alkyl group, more preferably an unsubstituted straight-chain alkyl group.

[0183] R 2a The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents, but is preferably an unsubstituted aryl group.

[0184] R in equation (OX-1) 3a and R4a Each can be represented independently as a hydrogen atom or an alkyl group, preferably a hydrogen atom.

[0185] R 3a and R 4a The alkyl group represented preferably has 1 to 15 carbon atoms, more preferably 1 to 10, even more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, and more preferably straight-chain. The alkyl group may have substituents, but is preferably unsubstituted.

[0186] R 3a With R 4a They can bond together to form a ring. The formed ring is preferably a 5-membered or 6-membered ring, more preferably a 5-membered or 6-membered aliphatic hydrocarbon ring.

[0187] Alk of formula (OX-1) 1 and Alk 2 Alkyl groups are represented independently. The number of carbon atoms in an alkyl group is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, and even more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, more preferably straight-chain. The alkyl group may have substituents, but is preferably unsubstituted.

[0188] Alk 1 With Alk 2 They can bond together to form a ring, preferably a ring. The formed ring is preferably a 5-membered or 6-membered ring, more preferably a 5-membered or 6-membered aliphatic hydrocarbon ring, and even more preferably a cyclopentane ring or a cyclohexane ring.

[0189] In formula (OX-1), n ​​represents 0 or 1, preferably 0.

[0190] Specific examples of compounds represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of Japanese Patent Application Publication No. 2012-113104 and the compounds described in paragraph 0041 of Japanese Patent Application Publication No. 2012-189997.

[0191] Compounds represented by formula (OX-2) can also be used as photopolymerization initiators.

[0192] [Chemical Formula 5]

[0193]

[0194] In equation (OX-2), R 1b and R 2b Each substituent is represented independently, R 3b ~R 7bEach can be used independently to represent a hydrogen atom or a substituent, Ar 1b This indicates an aromatic cyclic or heterocyclic group that can have substituents, and n represents 0 or 1.

[0195] As R 1b and R 2b Examples of substituents include alkyl and aryl groups, with alkyl groups being preferred. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl, alkenyl, ynyl, and heterocyclic groups. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl, alkenyl, ynyl, and heterocyclic groups.

[0196] As R 3b ~R 7b Examples of substituents include halogen atoms, alkyl groups, and aryl groups. Examples of alkyl and aryl groups include the groups mentioned above.

[0197] R 3b ~R 7b Hydrogen atoms are preferred.

[0198] Ar 1b Ar indicates an aromatic cyclic or heterocyclic group that can have substituents. 1b Preferably, it is an aromatic cyclic group that can have substituents. The aromatic cyclic group is preferably a benzene cyclic group or a naphthyl cyclic group, more preferably a benzene cyclic group. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, nitro groups, and acyl groups, with acyl groups being preferred. Examples of acyl groups include the aforementioned acyl groups.

[0199] Compounds represented by formula (OX-3) can also be used as photopolymerization initiators.

[0200] [Chemical Formula 6]

[0201]

[0202] In formula (OX-3), Ar 1c This indicates a (k+m+1) valence aromatic cyclic group or a (k+m+1) valence heterocyclic group.

[0203] Ar 2c This indicates a (k+2) valence aromatic cyclic group or a (k+2) valence heterocyclic group.

[0204] R 1c ~R 3c Substituents are represented independently.

[0205] L 1c Indicates a single key or CR 11c R 12c R 11c and R 12c Each can independently represent a hydrogen atom, alkyl group, or aryl group.

[0206] X 1c It can represent -CH2-, -O-, or -S-.

[0207] k represents 0 or 1, m represents an integer from 0 to 4, and n represents 0 or 1.

[0208] As R 1c and R 2c Examples of substituents include alkyl and aryl groups, with alkyl groups being preferred. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl, alkenyl, ynyl, and heterocyclic groups. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl, alkenyl, ynyl, and heterocyclic groups.

[0209] R 2c Preferably, it is an alkyl group having a branched or cyclic structure.

[0210] As R 3c Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and acyl groups, with acyl groups being preferred. Examples of acyl groups include the aforementioned acyl groups.

[0211] L 1c Indicates a single key or CR 11c R 12c R 11c and R 12c Each can be independently represented by a hydrogen atom, alkyl group, or aryl group. R 11c and R 12c The meanings of alkyl and aryl groups in R are related to the meanings of R. 1c and R 2c The alkyl and aryl groups in this context have the same meaning. When k is 1, L 1c Single bonds are preferred.

[0212] X 1c It can be represented as -CH2-, -O-, or -S-, preferably -O- or -S-.

[0213] Ar 1cThis indicates a (k+m+1) valent aromatic cyclic group or a (k+m+1) valent heterocyclic group, preferably a (k+m+1) valent aromatic cyclic group. The aromatic cyclic group is preferably a benzene cyclic group or a naphthyl cyclic group, more preferably a benzene cyclic group.

[0214] Ar 2c The term represents a (k+2) valent aromatic cyclic group or a (k+2) valent heterocyclic group, preferably a (k+2) valent aromatic cyclic group. The aromatic cyclic group is preferably a benzene cyclic group or a naphthyl cyclic group, more preferably a benzene cyclic group.

[0215] k represents 0 or 1, preferably 0.

[0216] m represents an integer from 0 to 4, preferably 0 or 1, and more preferably 1.

[0217] n represents 0 or 1, preferably 0.

[0218] The following are specific examples of oxime compounds that are preferably used in this invention, but the invention is not limited to these.

[0219] [Chemical Formula 7]

[0220]

[0221] [Chemical Formula 8]

[0222]

[0223] [Chemical Formula 9]

[0224]

[0225] [Chemical Formula 10]

[0226]

[0227] [Chemical Formula 11]

[0228]

[0229] The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350–500 nm, more preferably a compound having a maximum absorption wavelength in the range of 360–480 nm. Furthermore, from the viewpoint of sensitivity, the oxime compound preferably has a high molar absorptivity at wavelengths of 365 nm or 405 nm, more preferably 1,000–300,000, even more preferably 2,000–300,000, and particularly preferably 5,000–200,000. The molar absorptivity of the compound can be determined using known methods. For example, it is preferably determined using a spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0230] As photopolymerization initiators, it is also preferred to use Irgacure OXE01 (manufactured by BASF) and / or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins BV) in combination.

[0231] 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, in the case of using compounds with asymmetric structures, crystallinity decreases while solubility in solvents and the like increases, making it less prone to precipitation over time, thereby improving the storage stability of the photosensitive composition. Specific examples of photoradical polymerization initiators with two or more functionalities include the compound described in paragraph 0148 of International Publication No. 2022 / 065215.

[0232] The content of the photopolymerization initiator in the total solids component of the photosensitive composition is preferably 0.1% to 20% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less. In the photosensitive composition of the present invention, only one photopolymerization initiator may be used, or two or more photopolymerization initiators may be used. When two or more are used, their combined amount is preferably within the above-mentioned range.

[0233] <<Specific Compounds>>

[0234] The photosensitive composition of the present invention contains compound A (hereinafter also referred to as a specific compound) represented by formula (1).

[0235] [Chemical Formula 12]

[0236]

[0237] In equation (1), R 1 and R 2 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 12 carbon atoms, a group containing an acid group with 1 to 6 carbon atoms, or a group containing an amino group with 1 to 6 carbon atoms. X 1 This indicates a straight-chain or branched alkylene group, where n represents an integer greater than or equal to 1. When n is 2 or greater, multiple X groups are represented. 1 They can be the same or different.

[0238] R 1 and R 2 The alkyl group represented preferably has 1 to 3 carbon atoms, more preferably 1 or 2. The alkyl group is preferably methyl or ethyl, and methyl is more preferred from the perspective of being able to form pixels where the generation of defects is further suppressed.

[0239] R 1 and R 2 The aryl group representing 6 to 12 carbon atoms is preferably phenyl or naphthyl, more preferably phenyl.

[0240] Regarding R 1 and R 2 The acid group containing 1 to 6 carbon atoms can be exemplified by carboxyl, sulfonyl, and phosphate groups.

[0241] Regarding R 1 and R 2 The amino group represented by the group containing 1 to 6 carbon atoms, such as -NRa, can be cited as an example. 1 Ra 2 The group indicated. Ra 1 and Ra 2 Alkyl groups, which can be represented independently by 1 to 3 hydrogen atoms or carbon atoms respectively.

[0242] Based on the reasoning that the generation of defects can be further suppressed in pixels, R 1 and R 2 Each is preferably an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. Furthermore, in addition to the effects described above, R is preferred because it allows the photosensitive composition to have good sensitivity during exposure. 1 and R 2 One of them is a hydrogen atom and the other is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably R. 1 and R 2 It is a hydrogen atom. Furthermore, from the viewpoint of radioactivity, R... 1 and R 2 At least one of them is preferably an alkyl group, more preferably a methyl group.

[0243] X 1 The term refers to a straight-chain or branched alkylene group, preferably a straight-chain alkylene group. The alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 3. 1 Ethylene is preferred.

[0244] When n is 2 or more, there are multiple X 1 They can be the same or different, but being the same is preferred. X is preferred. 1 At least one of them is ethylene, more preferably X 1 It is ethylene.

[0245] In equation (1), n ​​represents an integer greater than or equal to 1. The upper limit of n is preferably 500 or less, more preferably 50 or less, and even more preferably 15 or less. The lower limit of n is preferably 2 or more, more preferably 4 or more.

[0246] The molecular weight of the specific compound is preferably 100 to 30,000, more preferably 100 to 10,000, and even more preferably 100 to 5,000. From the perspective of further suppressing the formation of pixels with defects, 150 to 2,000 is particularly preferred. The upper limit of the molecular weight is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. Furthermore, in this specification, the molecular weight of the specific compound refers to the value calculated from the structural formula when the molecular weight can be calculated from the structural formula, and the number-average molecular weight when it is difficult to calculate from the structural formula. The number-average molecular weight of the specific compound is a polystyrene conversion value determined by GPC (gel permeation chromatography).

[0247] The boiling point of the specific compound is preferably 150°C to 1000°C, more preferably 250°C to 900°C, and even more preferably 300°C to 800°C. From the perspective of being able to form pixels where the generation of defects is further suppressed, it is particularly preferred to be 320°C to 700°C.

[0248] Specific examples of particular compounds include polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 1000, polyethylene glycol 20000, polyethylene glycol monomethyl ether 550, polyethylene glycol dimethyl ether 550, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene glycol 400, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, diethylene glycol monophenyl ether, (2-butoxyethoxy)acetic acid, and 2-[2-(2-aminoethoxy)ethoxy]ethanol.

[0249] The content of the specific compound in the photosensitive composition is preferably 0.01 to 5.0% by mass. The upper limit is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less. The lower limit is preferably 0.05% by mass or more. Only one specific compound may be used, or two or more specific compounds may be used. When two or more specific compounds are used, their combined amount is preferably within the above-mentioned range.

[0250] <<Solvent>>

[0251] The photosensitive composition of the present invention contains a solvent. Examples of solvents include organic solvents. The type of solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. 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 preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol. Monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-dimethyldiacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (as an alternative name, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropanol, 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 by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less).

[0252] The metal content of the organic solvent is preferably low. For example, the metal content of the organic solvent is preferably below 10 parts per billion (ppb). Organic solvents with a metal content 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).

[0253] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) or filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0254] Organic solvents can contain isomers (compounds with the same number of atoms but different structures). Furthermore, they can contain only one isomer or multiple isomers.

[0255] The peroxide content in the organic solvent is preferably below 0.8 mmol / L, and more preferably substantially free of peroxides.

[0256] The solvent content in the photosensitive composition is preferably 10-95% by mass, more preferably 20-90% by mass, and even more preferably 30-90% by mass.

[0257] From an environmental perspective, the photosensitive composition of the present invention preferably contains substantially no environmentally restricted substances. Furthermore, in the present invention, "substantially no environmentally restricted substances" means that the content of environmentally restricted substances in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are registered as environmentally restricted substances under REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, PRTR (Pollutant Release and Transfer Register) law, and VOC (Volatile Organic Compounds) restrictions, and their usage and processing methods are strictly limited. These compounds are sometimes used as solvents in the various components used in the manufacture of the photosensitive composition, and sometimes they are mixed into the photosensitive composition as residual solvents. From the perspective of human safety and the environment, it is preferable to minimize these substances as much as possible. One method for reducing environmentally restricted substances is to heat and depressurize the system to a temperature above the boiling point of the substance, and then distill it off within the system to reduce its concentration. Furthermore, when distilling off small amounts of environmentally restricted substances, azeotropic distillation with a solvent having a boiling point similar to the solvent can improve efficiency. Additionally, when the substance contains compounds with free radical polymerization potential, depressurized distillation can be performed by adding polymerization inhibitors to suppress free radical polymerization reactions during depressurized distillation, which could lead to intermolecular crosslinking. These distillation removal methods can be performed at any stage, including the raw material stage, the product stage (e.g., a polymerized resin solution or a multifunctional monomer solution), or the stage where these compounds are mixed to form a photosensitive composition.

[0258] <<Ionic Compounds>>

[0259] The photosensitive composition of the present invention can contain the cationic CX. + With anion CZ - Salts (hereinafter also referred to as ionic compounds).

[0260] The specific absorbance of the ionic compound, expressed by formula (Aλ), is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less. The specific absorbance, expressed by formula (Aλ), is an indicator of the degree to which the ionic compound absorbs light in the visible region. The lower the specific absorbance, the lower the absorption of light in the visible region. The lower limit of the specific absorbance is not limited. When setting the lower limit of the specific absorbance, it is sufficient that the specific absorbance expressed by formula (Aλ) is within the range of 0.001 or more.

[0261] E 1 =A 1 / (c 1 ×l 1 )……(Aλ)

[0262] In formula (Aλ), E 1 This indicates the specific absorbance of ionic compounds at their maximum absorption wavelength within the range of 400–700 nm.

[0263] A 1 This indicates the absorbance of ionic compounds at their maximum absorption wavelength within the range of 400–700 nm.

[0264] l 1 The length of the groove (cell length) is expressed in cm.

[0265] c 1 The concentration of ionic compounds in a solution is expressed in mg / ml.

[0266] In equation (Aλ), "A" 1 The absorbance indicated is determined by the following method. The test sample is prepared using an ionic compound and a solvent sufficient to dissolve the ionic compound. If the ionic compound is sufficiently soluble in methanol, methanol is used as the solvent. If the ionic compound is not sufficiently soluble in methanol, cyclohexanone is used as the solvent. The absorbance of the above test sample is measured at 25°C (room temperature) using a trough with a path length of 1 cm.

[0267] The molecular weight of the ionic compound is preferably 80 to 5000. The upper limit is preferably 3000 or less, more preferably 2000 or less, even more preferably 1500 or less, and particularly preferably 1210 or less. The lower limit is preferably 100 or more, more preferably 200 or more.

[0268] CZ, an anion in ionic compounds -Examples of suitable anions include imide anions, methylated anions, borate anions, phosphorus-containing anions, and sulfonic acid anions. Imitide anions, methylated anions, or borate anions are preferred, and imide anions or borate anions are even more preferred. Furthermore, the anion CZ... - It is also preferred to contain anion selected from at least one of fluorine and sulfur atoms.

[0269] From the perspective of the storage stability of photosensitive compositions, the anion CZ of ionic compounds - The pKa of the conjugate acid is preferably 0 or less, more preferably -5 or less, even more preferably -8 or less, even more preferably -10 or less, and particularly preferably -10.5 or less. The lower limit is not particularly limited, but can be set to -20 or more, or -18 or more. The pKa of the conjugate acid can be determined, for example, by the method described in J.Org.Chem. 2011, 76, 391-395.

[0270] In ionic compounds, CX is used as a cation. + As long as the anions CZ can cancel each other out - The structure of the charge is sufficient.

[0271] From the ease of reducing with anion CZ - Based on the reason of ionic bond energy, cation CX + The molecular weight is preferably 2 to 500, more preferably 2 to 200, and even more preferably 6 to 90.

[0272] As a cation CX + Preferably, it is a cation of a monomeric metal atom, a carbocation, an ammonium cation, a phosphonium cation, or a sulfonium cation, more preferably a cation of a monomeric metal atom or an ammonium cation. Furthermore, cation CX is also preferred. + It consists of divalent or higher cations. This method allows for the formation of more robust films and more effective suppression of defects in the developed film.

[0273] Specific examples of ionic compounds include the following compounds.

[0274] [Chemical Formula 13]

[0275]

[0276] [Chemical Formula 14]

[0277]

[0278] [Chemical Formula 15]

[0279]

[0280] The content of ionic compounds in the total solids component of the photosensitive composition is preferably 0.1% to 15% by mass. The upper limit is preferably 12% by mass or less, more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Only one type of ionic compound may be used, or two or more types may be used. When two or more types are used, their combined amount is preferably within the above-mentioned range.

[0281] <<Polyalkylimine>>

[0282] The photosensitive composition of the present invention may also contain polyalkylene imides. Polyalkylene imides can be used, for example, as dispersing agents for pigments. Dispersing agents are materials used to improve the dispersibility of pigments and other colorants in a photosensitive composition. Polyalkylene imides are polymers formed by ring-opening polymerization of alkylene imides. Polyalkylene imides are preferably polymers having branched structures containing primary, secondary, and tertiary amino groups, respectively. The number of carbon atoms in the alkylene imide is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0283] The molecular weight of the polyalkylene imide is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, and particularly preferably 2,000 or less. Furthermore, regarding the molecular weight of the polyalkylene imide, when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imide 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 elevation method is used. Furthermore, when the boiling point elevation method is also not feasible or difficult to determine, the number-average molecular weight value determined by the viscosity method is used. Furthermore, when the viscosity method is also not feasible or difficult to determine, the number-average molecular weight value from the polystyrene conversion value determined by GPC (gel permeation chromatography) is used.

[0284] The amine value of the polyalkylene imide is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.

[0285] Specific examples of alkylene imides include ethyleneimine, propyleneimine, 1,2-buteneimine, and 2,3-buteneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. Polyalkylene imides are particularly preferred to be polyethyleneimine. Furthermore, relative to the total amount of primary, secondary, and tertiary amino groups, polyethyleneimine preferably contains 10 mol% or more of primary amino groups, more preferably 20 mol% or more of primary amino groups, and even more preferably 30 mol% or more of primary amino groups. 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.).

[0286] The content of polyalkylene imide in the total solids component 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 even more 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 even more preferably 3% by mass or less. Furthermore, the content of polyalkylene imide relative to 100 parts by mass of pigment is preferably 0.5 to 20 parts by mass. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one type of polyalkylene imide may be used, or two or more types may be used. When two or more types are used, their combined amount is preferably within the above-mentioned range.

[0287] <<Compounds with cyclic ether groups>>

[0288] The photosensitive composition of the present invention can contain a compound having a cyclic ether group. Examples of cyclic ether groups include epoxy groups, oxacyclobutyl groups, etc. The epoxy group can be an alicyclic epoxy group. Furthermore, an alicyclic epoxy group refers to a monovalent functional group having a cyclic structure formed by the fusion of an epoxy ring and a saturated hydrocarbon ring. The compound having a cyclic ether group is preferably 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 preferably compounds having two or more epoxy groups. Epoxy compounds are preferably compounds having 1 to 100 epoxy groups per molecule. The upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups contained in the epoxy compound is preferably two or more.

[0289] As compounds having cyclic ether groups, 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), Japanese Patent Application Publication No. 2017-179172, cyclohexane-type epoxy resins described in Japanese Patent Application Publication No. 2021-195421, and cyclohexane-type epoxy resins described in Japanese Patent Application Publication No. 2021-195422 can also be used.

[0290] Compounds having cyclic ether groups can be low molecular weight compounds (e.g., molecular weight less than 2000, and further, less than 1000) or macromolecules (e.g., molecular weight 1000 or more, and in the case of polymers, weight-average molecular weight 1000 or more). The weight-average molecular weight of compounds having cyclic ether groups is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight-average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

[0291] Commercially available examples of compounds containing cyclic ether groups include 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, polymers containing epoxy groups).

[0292] The content of compounds having cyclic ether groups in the total solids component of the photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less. 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, their combined amount is preferably within the above-mentioned range.

[0293] <<Curing Accelerator>>

[0294] The photosensitive composition of the present invention can contain a curing accelerator. Examples of curing accelerators include thiol compounds, hydroxymethyl compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, alkali-generating agents, isocyanate compounds, alkoxysilane compounds, and onium salt compounds. Specific examples of curing accelerators include compounds described in paragraph 0164 of International Publication No. 2022 / 085485 and compounds described in Japanese Patent Application Publication No. 2021-181406. The content of the curing accelerator in the total solids component of the photosensitive composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.

[0295] <<Ultraviolet Absorber>>

[0296] The photosensitive composition of the present invention can contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, amino diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds, indole compounds, triazine compounds, and benzoyl compounds. Specific examples of such compounds include those described in International Patent Publication No. 2022 / 085485, paragraph 0179; reactive triazine ultraviolet absorbers described in Japanese Patent Application Publication No. 2021-178918; ultraviolet absorbers described in Japanese Patent Application Publication No. 2022-007884; compounds described in Korean Patent Publication No. 10-2022-0014454; and compounds described in Japanese Patent Application Publication No. 2023-013321. The content of the ultraviolet absorber in the total solids component of the photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. One type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that their combined dosage is within the range mentioned above.

[0297] <<Polymerization Inhibitor>>

[0298] The photosensitive composition of the present invention can contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-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 component of the photosensitive composition is preferably 0.0001 to 5% by mass. There may be only one type of polymerization inhibitor, or there may be two or more types. When there are two or more types, the total amount is preferably within the above range.

[0299] <<Silane Coupling Agents>>

[0300] The photosensitive composition of the present invention can contain a silane coupling agent. Examples of silane coupling agents include silane compounds having a hydrolyzable group, preferably silane compounds having a hydrolyzable group and other functional groups. A hydrolyzable group refers to a substituent that can form a siloxane bond by directly bonding with a silicon atom and by at least one of a hydrolysis reaction and a fusion reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, etc., preferably alkoxy groups. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Furthermore, examples of functional groups other than the hydrolyzable group include vinyl, (meth)allyl, (meth)acryloyl, mercapto, epoxy, oxetyl, amino, urea, sulfide group, isocyanate group, phenyl, etc., preferably amino, (meth)acryloyl, and epoxy groups. Specific examples of silane coupling agents include the compounds described in paragraph 0177 of International Patent Publication No. 2022 / 085485 and the compounds described in Japanese Patent Application Publication No. 2019-183020. The content of the silane coupling agent in the total solids component of the photosensitive composition is preferably 0.1 to 15% by mass. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. There may be only one type of silane coupling agent, or there may be two or more types. When there are two or more types, the total amount is preferably within the above range.

[0301] <<Surfactants>>

[0302] The photosensitizing composition of the present invention can contain a surfactant. Various surfactants, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants, can be used as surfactants. The surfactant is preferably a silicone surfactant or a fluorinated surfactant, and more preferably a silicone surfactant. Regarding surfactants, reference can be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, the contents of which are incorporated herein by reference.

[0303] As a fluorinated surfactant, the compounds described in paragraphs 0167 to 0173 of International Publication No. 2022 / 085485 can be used.

[0304] As a nonionic surfactant, the compound described in paragraph 0174 of International Publication No. 2022 / 085485 can be cited as an example.

[0305] Examples of silicone-based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Co., Ltd.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, and BYK-UV3510 (manufactured by BYK Chemie GmbH). Furthermore, silicone surfactants can also use compounds with the following structures.

[0306] [Chemical Formula 16]

[0307]

[0308] The surfactant content in the total solids component of the photosensitive composition is preferably 0.001% to 5.0% by mass, more preferably 0.005% to 3.0% by mass. There may be only one type of surfactant or two or more types. When there are two or more types, the total amount is preferably within the above range.

[0309] <<Antioxidants>>

[0310] The photosensitive composition of the present invention can contain an antioxidant. Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, and sulfur antioxidants. Examples of hindered phenolic compounds are examples of phenolic antioxidants. Phenolic antioxidants are preferably compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Antioxidants are also preferably compounds having a phenolic group and a phosphite group within the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxophosphatahept-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphatahept-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, and tris(2,4-di-tert-butylphenyl) phosphite. Commercially available antioxidants include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STABAO-330 (all manufactured by ADEKA CORPORATION), and JP-650 (manufactured by JOHOKU CHEMICAL CO., LTD.). The antioxidants may also be compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, compounds described in International Publication No. 2017 / 006600, compounds described in International Publication No. 2017 / 164024, and compounds described in Korean Patent Publication No. 10-2019-0059371. The antioxidant content in the total solids component of the photosensitive composition is preferably 0.01-20% by mass, more preferably 0.3-15% by mass. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, their combined amount is preferably within the above-mentioned range.

[0311] <<Other Ingredients>>

[0312] The photosensitizing composition of the present invention may, as needed, contain sensitizers, plasticizers, and other additives (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peel accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately including these components, film properties and other characteristics can be adjusted. These components can be compounds described in paragraph 0182 of International Publication No. 2022 / 085485.

[0313] To adjust the refractive index of the obtained film, the photosensitive composition of the present invention may contain a metal oxide. Examples of metal oxides include TiO2, ZrO2, Al2O3, and SiO2. The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. Furthermore, the core may be hollow.

[0314] The photosensitizing composition of the present invention may contain a lightfastness modifier. Examples of lightfastness modifiers include compounds described in paragraph 0183 of International Publication No. 2022 / 085485.

[0315] The photosensitive composition of the present invention is preferably substantially free of terephthalates. Here, "substantially free" means that the content of terephthalates in the total amount of the photosensitive composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably 0.

[0316] From an environmental perspective, the melamine content in the photosensitive composition of the present invention is preferably less than 10,000 ppm by mass.

[0317] The free metal content of the photosensitive composition of the present invention is preferably 100 ppm or less, more preferably 50 ppm or less. Furthermore, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Methods for reducing free metals or halogens in the photosensitive composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchanged resins.

[0318] From an environmental perspective, the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts, is sometimes restricted. In the photosensitive composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acids (especially perfluoroalkyl sulfonic acids with 6 to 8 carbon atoms in the perfluoroalkyl group) and their salts, and perfluoroalkyl carboxylic acids (especially perfluoroalkyl carboxylic acids with 6 to 8 carbon atoms in the perfluoroalkyl group) and their salts, relative to the total solids content of the photosensitive composition, is preferably in the range of 0.01 ppb to 1000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb. The photosensitive composition of the present invention may be substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. For example, by using compounds that can replace perfluoroalkyl sulfonic acids and their salts, and compounds that can replace perfluoroalkyl carboxylic acids and their salts, a photosensitive composition substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts, can be selected. As alternatives to the restricted compounds, examples include compounds excluded from the restrictions due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the foregoing does not preclude the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts. The photosensitive compositions of the present invention may contain perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts, within the maximum permissible range.

[0319] The photosensitive composition of the present invention typically has a water content of 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably in the range of 0.1 to 1.0% by mass. The water content can be determined using the Karl Fischer method.

[0320] The photosensitive composition of the present invention can be used to adjust the viscosity for purposes such as adjusting the film surface (flatness, etc.) and film thickness. The viscosity value can be appropriately selected as needed, but for example, at 25°C, it is preferably 0.3 mPa·s to 50 mPa·s, more preferably 0.5 mPa·s to 20 mPa·s. As a method for measuring viscosity, for example, a cone-plate viscometer can be used, and the measurement can be performed at a temperature adjusted to 25°C.

[0321] <<Containment Container>>

[0322] There are no particular limitations on the container for the photosensitive composition, and any known container can be used. Furthermore, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can be used as the container.

[0323] <Preparation Method of Photosensitive Composition>

[0324] The photosensitive composition of the present invention can be prepared by mixing the components. When preparing the photosensitive composition, all components can be simultaneously dissolved and / or dispersed in a solvent, or, as needed, each component can be appropriately prepared as a solution or dispersion of two or more parts, which are then mixed during use (coating) to prepare the photosensitive composition.

[0325] Furthermore, the preparation of the photosensitive composition preferably includes a process for dispersing the pigment. Examples of mechanical forces used for pigment dispersion in this process include compression, extrusion, impact, shearing, and cavitation. Specific examples of these processes include bead milling, grinding, roller milling, ball milling, paint stirring, microjet milling, high-speed impeller milling, sand milling, jet mixing, high-pressure wet micronization, and ultrasonic dispersion. In the grinding of pigments in bead milling, it is preferable to perform the process under conditions that improve grinding efficiency by using small-diameter beads and increasing the bead filling rate. After grinding, it is preferable to remove coarse particles by filtration, centrifugation, or other methods. Furthermore, regarding the manufacturing process and dispersing machine for disperse pigments, the processes and dispersing machines described in "Complete Collection of Dispersion Technology, published by JOHOKIKO CO.,LTD., July 15, 2005" or "Comprehensive Data Collection on Dispersion Technology and Practical Industrial Applications Centered on Suspension (Solid / Liquid Dispersion Systems), published by the Business Development Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Application Publication No. 2015-157893, are preferred. In the manufacturing process of disperse pigments, particle refinement can be achieved through a salt milling process. The materials, equipment, and processing conditions used in the salt milling process can be referenced, for example, in Japanese Patent Application Publication Nos. 2015-194521 and 2012-046629. Examples of materials for the beads used for dispersion include zirconium dioxide, agate, quartz, titanium dioxide, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Furthermore, the beads can also be made from inorganic compounds with a Mohs hardness of 2 or higher. The photosensitive composition may contain 1 to 10,000 ppm of the aforementioned beads.

[0326] When preparing a photosensitive composition, it is preferable to use a filter to filter the photosensitive composition in order to remove impurities or reduce defects. Examples of filters and filtration methods used for filtration include those described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485.

[0327] <Membrane>

[0328] The film of the present invention is a film obtained from the photosensitive composition of the present invention described above. The film of the present invention can be used in filters such as color filters, infrared transmission filters, and infrared cutoff filters.

[0329] The film thickness of the membrane of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0330] When the film of the present invention is used as a color filter, the film preferably has a green, red, blue, cyan, magenta, or yellow hue. Furthermore, the film of the present invention can preferably be used as a colored pixel in a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

[0331] <Filter>

[0332] The film of the present invention can be used in filters. Examples of filters include color filters, infrared cut-off filters, and infrared transmission filters, with color filters being preferred. Color filters preferably have the film of the present invention as their pixels, and more preferably have the film of the present invention as their colored pixels.

[0333] A protective layer can also be provided on the surface of the membrane of the present invention in the filter. By providing a protective layer, various functions such as oxidation resistance, low reflectivity, hydrophilicity / hydrophobicity, and shielding of light of specific wavelengths (ultraviolet, infrared, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of methods for forming the protective layer include methods of forming by coating a resin composition for forming a protective layer, chemical vapor deposition, and methods of attaching a pre-formed resin with an adhesive. Examples of components constituting the protective layer include (meth)acrylic resin, olefin-thiol resin, polycarbonate resin, polyether resin, polyaryl ester resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyaryl ether phosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, polyurethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluoropolymer resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al₂O₃, Mo, SiO₂, Si₂N₄, etc., and more than two of these components may be contained. For example, in the case of a protective layer intended to block oxidation, the protective layer preferably contains polyol resin, SiO₂, and Si₂N₄. Furthermore, in the case of a protective layer intended to reduce reflectivity, the protective layer preferably contains (meth)acrylic resin and fluoropolymer resin.

[0334] When a protective layer is formed by coating a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the coating method for the resin composition. Known organic solvents (e.g., propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used as the organic solvent contained in the resin composition. When a protective layer is formed by chemical vapor deposition (CVD), known CVD methods (thermochemical vapor deposition, plasma-enhanced chemical vapor deposition, photochemical vapor deposition) can be used as the CVD method.

[0335] Depending on the requirements, the protective layer may also contain additives such as organic / inorganic microparticles, absorbers of specific wavelengths of light (e.g., ultraviolet, infrared, etc.), refractive index modifiers, antioxidants, adhesives, and surfactants. Examples of organic / inorganic microparticles include, for instance, polymeric microparticles (e.g., silicone resin microparticles, polystyrene microparticles, melamine resin microparticles), titanium dioxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known absorbers can be used for the specific wavelengths of light. The content of these additives can be appropriately adjusted, but is preferably 0.1–70% by mass relative to the total mass of the protective layer, more preferably 1–60% by mass.

[0336] As a protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Publication No. 2017-151176 may also be used.

[0337] Filters can also have the following structure: pixels are embedded in spaces separated by partitions, for example, in a grid pattern.

[0338] <Method for manufacturing filters>

[0339] A method for manufacturing a filter using the photosensitive composition of the present invention will be described. The method for manufacturing the filter includes: a step of forming a composition layer on a support using the photosensitive composition of the present invention; and a step of forming a pattern on the composition layer by photolithography.

[0340] The pattern formation method using photolithography preferably includes a step of exposing the above-mentioned composition layer in a patterned manner, and a step of developing and removing the unexposed portions of the composition layer.

[0341] In the process of forming the composition layer, the photosensitive composition of the present invention is used to form the composition layer on a support. There are no particular limitations on the support, and it can be appropriately selected according to the application. Examples include glass substrates and silicon substrates, with silicon substrates being preferred. Furthermore, charge-coupled devices (CCDs), complementary metal-oxide-semiconductor (CMOS) films, transparent conductive films, etc., can also be formed on the silicon substrate. Sometimes, a black matrix 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, the surface contact angle of the base layer is preferably 20 to 70°. And when measured with water, it is preferably 30 to 80°.

[0342] The support can also be a support with partitions. Figure 1 This is a side sectional view showing one embodiment of a support structure with partitions. Figure 2 This is a top view taken directly above the support. Figure 1 In this context, a partition wall 11 is formed on the surface of the support 10. Furthermore, as... Figure 2 As shown, multiple regions, divided by partition walls 11, are provided on the surface of the support 10. Additionally, in Figure 2 In this structure, partition walls 11 are formed in a grid pattern on the surface of the support 10. The shape of the regions on the support 10 divided by the partition walls 11 (hereinafter also referred to as the shape of the openings of the partition walls) is square, but the shape of the openings of the partition walls 11 is not particularly limited; for example, it can be rectangular, circular, elliptical, or polygonal. Furthermore, in... Figure 1 In this design, the partition 11 is columnar, but its shape is not limited to columnar; it can be either a regular cone or an inverted cone. Furthermore, the width of the partition can be a shape that gradually expands or contracts from the support side towards the front end. Specifically, a regular cone shape refers to a partition whose width continuously contracts from the support side towards the front end, an inverted cone shape refers to a partition whose width continuously expands from the support side towards the front end, and a columnar shape refers to a partition whose width is approximately the same on both the support side and the front end side.

[0343] The width W1 of the partition 11 is preferably 20 to 500 nm. The lower limit is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The upper limit is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.

[0344] The thickness (height) H1 of the partition 11 is preferably 200 nm or more, more preferably 300 nm or more, and even more preferably 400 nm or more. The upper limit is preferably less than 200% of the pixel thickness, more preferably less than 150% of the pixel thickness, and even more preferably substantially the same as the pixel thickness.

[0345] The height-to-width ratio (height / width) of the partition 11 is preferably 1 to 100, more preferably 5 to 50, and even more preferably 5 to 30.

[0346] In addition, in this specification, the thickness of the partition refers to the longitudinal length of the partition, and the width of the partition refers to the transverse length of the partition.

[0347] The spacing W3 of the partitions 11 disposed on the support 10 is preferably 400 to 1200 nm. The lower limit of the spacing W3 is preferably 450 nm or more, more preferably 500 nm or more. The upper limit of the spacing W3 is preferably 1000 nm or less, more preferably 900 nm or less, and even more preferably 800 nm or less. In addition, in this specification, the spacing of the partitions refers to the total value of the width W1 of the partition and the width W2 of the partition opening 12 (the distance between the opposing surfaces of the partitions).

[0348] The width W2 of the partition opening 12 is preferably 300 to 1100 nm. The lower limit is preferably 400 nm or more, more preferably 450 nm or more. The upper limit is preferably 1000 nm or less, more preferably 900 nm or less. The width W2 of the partition opening 12 corresponds to the width of the pixel formed between the partitions. As long as the width W2 of the partition opening 12 is within the above-mentioned range, it is possible to reduce the size of the solid-state imaging element or increase its resolution.

[0349] There are no particular limitations on the material of the partition 11. For example, organic materials such as siloxane resin and fluororesin, or inorganic particles such as silica particles and magnesium fluoride can be used. From the perspective of improving the strength of the partition, the partition 11 preferably contains silica particles.

[0350] The partition 11 can be formed using methods known in the past. For example, the partition can be formed as follows.

[0351] First, a partition material layer is formed on the support. The partition material layer can be formed, for example, by coating a composition containing inorganic particles such as silica particles (a partition material forming composition) onto the support and then curing it. Examples of such compositions include those described in paragraphs 0012-0077 and 0093-0105 of International Publication No. 2019 / 017280 and those described in paragraphs 0089-0091 of International Publication No. 2019 / 111748, which are incorporated herein by reference.

[0352] The partition material layer can also be formed by depositing inorganic materials such as silicon dioxide on the support through chemical vapor deposition (CVD), vacuum vapor deposition or sputtering.

[0353] Next, a resist pattern is formed on the partition material layer using a mask with a pattern corresponding to the shape of the partition.

[0354] Next, using the resist pattern as a mask, the spacer material layer is etched to form a pattern. Examples of etching methods include dry etching and wet etching. Dry etching can be performed under the conditions described in paragraphs 0128 to 0133 of Japanese Patent Application Publication No. 2016-014856. Then, the resist pattern is peeled off from the spacer material layer. Spacers can be formed in this manner.

[0355] Although not illustrated, a base layer can be provided on the surfaces of the partition 11 and the support 10. By providing the base layer, the adhesion between the pixel and the partition can be improved. Furthermore, it can suppress the diffusion of components from the pixel into the partition and also improve the strength of the partition. Various inorganic or organic materials can be used as the material for the base layer. For example, examples of organic materials include acrylic resin, polystyrene resin, polyimide resin, and organic SOG (Spin On Glass) resin. Furthermore, compositions containing compounds (having groups with olefinic unsaturated bonds) can also be used to form the base layer. Additionally, organosilane compounds such as 1,1,1,3,3,3-hexamethyldisilazane can also be used to form the base layer. Examples of groups containing olefinic unsaturated bonds include vinyl, (meth)allyl, (meth)acryloyl, and styryl, with (meth)allyl and (meth)acryloyl being preferred. The compound having groups containing olefinic unsaturated bonds can be a monomer or a polymer or other resin. Examples of inorganic materials include silicon dioxide and aluminum oxide. The substrate layer can be formed using conventionally known methods. When forming a substrate layer composed of organic materials, for example, a composition containing organic materials (a substrate layer composition) can be coated onto the partition wall and dried. When forming a substrate layer composed of inorganic materials, for example, the inorganic material constituting the substrate layer can be formed into a film on the surface of the partition wall by vapor deposition methods such as chemical vapor deposition (CVD), vacuum vapor deposition, or sputtering.

[0356] When forming the composition layer, known methods can be used as the coating method for the photosensitive composition. Examples include drop casting; slot coating; spraying; roller coating; spin coating; cast coating; both slot and spin coating; pre-wetting (e.g., the method described in Japanese Patent Application Publication No. 2009-145395); inkjet printing (e.g., on-demand, piezoelectric, thermal), nozzle ejection, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, and various other printing methods; transfer methods using molds, etc.; and nanoimprinting. Furthermore, the coating method described in paragraph 0207 of International Publication No. 2022 / 085485 can also be used.

[0357] The composition layer formed on the support can be dried (pre-baked). When the film is manufactured by a low-temperature process, pre-baking may not be necessary. When pre-baking is performed, the pre-baking temperature is preferably below 150°C, more preferably below 120°C, and even more preferably below 110°C. The lower limit can be set to 50°C or higher, or 80°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a heating plate, oven, or the like.

[0358] Next, the composition layer is exposed in a pattern (exposure process). For example, using a stepper or scanning exposure machine, the composition layer is exposed through a mask with a specified mask pattern, thereby enabling patterned exposure. This allows the exposed portion to be cured.

[0359] Examples of radiation (light) that can be used during exposure include gamma rays and i-rays. Furthermore, light with wavelengths of 150–300 nm can also be used. Examples of light with wavelengths of 150–300 nm include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. Excimer lasers with wavelengths of 150–300 nm are preferred. Moreover, long-wavelength light sources with wavelengths of 300 nm or higher can also be used during exposure.

[0360] In the exposure process, it is preferable to irradiate the composition layer with light of wavelength 150-300 nm (preferably excimer laser light of wavelength 150-300 nm) to expose it in a patterned manner.

[0361] During exposure, light can be applied continuously or in pulses (pulse exposure). Pulse exposure is an exposure method that involves repeatedly applying and pausing light for short periods (e.g., less than milliseconds).

[0362] The irradiation dose (exposure dose) is preferably 0.03 to 2.5 J / cm. 2 More preferably, it is 0.05–1.0 J / cm³. 2 Regarding the oxygen concentration during exposure, it can be appropriately selected. Besides exposure under atmospheric conditions, it can also be performed in low-oxygen environments with an oxygen concentration below 19% by volume (e.g., 15% by volume, 5% by volume, or virtually oxygen-free), or in high-oxygen environments with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). Furthermore, the exposure illuminance can be appropriately set, typically from 1000 W / m². 2 ~100000W / m 2 (For example, 5000W / m) 2 15000W / m 2 Or 35000W / m 2 The range of oxygen concentration and illuminance can be selected. These conditions can be appropriately combined; for example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m² can be set. 2 Oxygen concentration 35% by volume and illuminance 20000 W / m² 2 wait.

[0363] Next, the unexposed portions of the composition layer are removed by development to form a pattern (pixel). The unexposed portions of the composition layer can be removed by developing a developer. As a result, the unexposed portions of the composition layer from the exposure process dissolve in the developer, leaving only the photocured portion. The temperature of the developer is preferably, for example, 20–30°C. The development time is preferably 20–180 seconds. Furthermore, to improve residue removal, the process of repeatedly discarding the developer every 60 seconds and then supplying fresh developer can be repeated multiple times.

[0364] Developers may include organic solvents, alkaline developers, etc., and alkaline developers are preferred. Regarding the developer and the post-development cleaning (rinsing) method, the developer or cleaning method described in paragraph 0214 of International Publication No. 2022 / 085485 may be used.

[0365] After development, and following drying, it is preferable to perform additional exposure treatment or heat treatment (post-baking). Additional exposure treatment or post-baking is a curing treatment after development to ensure complete curing. The heating temperature during post-baking is preferably 100–300°C, more preferably 200–270°C. The developed film can be post-baked continuously or intermittently using heating means such as hot plates, convection ovens (hot air circulating dryers), or high-frequency heaters to achieve the above conditions. When performing additional exposure treatment, the light used for exposure is preferably light with a wavelength of 400 nm or less. Furthermore, the additional exposure treatment can also be performed using the method described in Korean Patent Publication No. 10-2017-0122130.

[0366] Solid-state imaging element

[0367] The solid-state imaging element of the present invention has the film of the present invention as described above. As for the structure of the solid-state imaging element, there are no particular limitations as long as it has the film of the present invention and functions as a solid-state imaging element; for example, the following structures can be cited.

[0368] The solid-state imaging element has the following structure: On a substrate, there are multiple 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, and a transmission electrode made of polysilicon, etc. A light-shielding film with openings only for the light-receiving portions of the photodiodes is present on the photodiodes and the transmission electrode. A device protective film made of silicon nitride, etc., is formed on the light-shielding film to cover the entire light-shielding film and the light-receiving portions of the photodiodes. A color filter is present on the device protective film. Furthermore, it can have a structure with a light-concentrating mechanism (e.g., a microlens, etc. hereinafter the same) on the device protective film and on the underside (closer to the substrate) of the color filter, or a structure with a light-concentrating mechanism on the color filter itself. The color filter can also have a structure in which each colored pixel is embedded in a space divided by partitions, for example, in a grid pattern. In this case, the partitions are preferably of a low refractive index relative to each colored pixel. Examples of camera devices with this 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 in digital cameras or electronic devices with camera functions (such as mobile phones), but also as vehicle cameras or surveillance cameras.

[0369] <Image display device>

[0370] The image display device of the present invention includes the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescent display devices. Definitions of image display devices and detailed descriptions of various image display devices are provided, for example, in "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Publishing Co., Ltd., 1989). Furthermore, liquid crystal display devices are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994). There are no particular limitations on the liquid crystal display devices to which the present invention can be applied; for example, liquid crystal display devices of the various types described in "Next-Generation Liquid Crystal Display Technology" can be applied.

[0371] Example

[0372] The present invention will be described in more detail below with examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Furthermore, in the structural formulas shown below, Et represents ethyl and iPr represents isopropyl.

[0373] <Preparation of Dispersions>

[0374] The mixture obtained by mixing the materials listed in the table below was mixed and dispersed for 3 hours using a bead mill (using zirconia beads with a diameter of 0.1 mm). Then, it was dispersed using a NANO-3000-10 high-pressure disperser (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism at a flow rate of 500 g / min under a pressure of 2000 MPa. This dispersion process was repeated 10 times to obtain the various dispersions.

[0375] [Table 1]

[0376]

[0377] The details of the materials represented by abbreviations in the table above are as follows.

[0378] (pigment)

[0379] PG7: CI Pigment Green 7 (phthalocyanine compound, green pigment)

[0380] PG36: CI Pigment Green 36 (Heliogen Green L 9362, manufactured by Sun Chemical, phthalocyanine compound, green pigment)

[0381] PG58: CI Pigment Green 58 (phthalocyanine compound, green pigment)

[0382] PY139: CI Pigment Yellow 139 (isoindoline compound, yellow pigment)

[0383] PY139A: CI Pigment Yellow 139 (Paliotol Yellow L 2140 HD, manufactured by Sun Chemical, isoindoline compound, yellow pigment)

[0384] PY150: CI Pigment Yellow 150 (azo compound, yellow pigment)

[0385] PY185: CI Pigment Yellow 185 (Palitol Yellow L 1155, manufactured by Sun Chemical, isoindoline compound, yellow pigment)

[0386] PR254: CI Pigment Red 254 (diketopyrrolopyrrole compound, red pigment)

[0387] PR254A: CI Pigment Red 254 (Irgazin Red K 3842, manufactured by Sun Chemical, a diketopyrrolopyrrole compound, a red pigment)

[0388] PR264: CI Pigment Red 264 (Irgazin Rubine K 4082, manufactured by Sun Chemical, a diketopyrrolopyrrole compound, a red pigment)

[0389] PR272: CI Pigment Red 272 (diketopyrrolopyrrole compound, red pigment)

[0390] PB15:4:CI Pigment Blue 15:4 (Phalothiocyanate compound, blue pigment)

[0391] PB15:6: CI Pigment Blue 15:6 (Heliogen Blue D 6700 T, manufactured by Sun Chemical, phthalocyanine compound, blue pigment)

[0392] PV2: CI Pigment Violet 2 (purple pigment)

[0393] PV2A: CI Pigment Violet 2 (Fanal Violet D 5460, manufactured by Sun Chemical, purple pigment)

[0394] PV19: CI Pigment Violet 19 (Purple Pigment)

[0395] PV19A: CI Pigment Violet 19 (Cinqueasia Violet K5350, manufactured by Sun Chemical, purple pigment)

[0396] PV19B: CI Pigment Violet 19 (Fastogen Super Red 7100Y, manufactured by Sun Chemical, purple pigment)

[0397] PV23: CI Pigment Violet 23 (Dioxazine compound, purple pigment)

[0398] PV23A: CI Pigment Violet 23 (Pigmosol AGRO Violet 5890, manufactured by Sun Chemical, dioxazine compound, purple pigment)

[0399] PV37: CI Pigment Violet 37 (Chromophthal Violet K 5700, manufactured by Sun Chemical, a purple pigment)

[0400] (dye)

[0401] Dye-1: A dye with the following structure (xanthine compound, purple dye).

[0402] [Chemical Formula 17]

[0403]

[0404] (Pigment derivatives)

[0405] Syn-1: Compounds with the following structures

[0406] [Chemical Formula 18]

[0407]

[0408] Syn-2: A compound with the following structure

[0409] [Chemical Formula 19]

[0410]

[0411] Syn-3: A compound with the following structure

[0412] [Chemical Formula 20]

[0413]

[0414] Syn-4: A compound with the following structure

[0415] [Chemical Formula 21]

[0416]

[0417] (Dispersant)

[0418] B-1: A 30% by mass solution of propylene glycol monomethyl ether acetate (PGMEA) of the following resin structure (the values ​​on the main chain are the molar ratio of structural units, and the values ​​on the side chains are the number of structural units. Weight average molecular weight 20000, acid value 48.7 mgKOH / g).

[0419] [Chemical Formula 22]

[0420]

[0421] B-2: A 30% PGMEA solution of the polymer (acid value 28 mg KOH / g, amine value 72.4 mg KOH / g, weight average molecular weight 5000) obtained by reacting 5 parts by mass of compound b-1, 5 parts by mass of compound b-2 and 90 parts by mass of compound b-3.

[0422] [Chemical Formula 23]

[0423]

[0424] Resin B-2 has the structure shown below.

[0425] [Chemical Formula 24]

[0426]

[0427] B-3: A 30% PGMEA solution of the following resin structure (the values ​​on the main chain are the molar ratio of structural units, and the values ​​on the side chains are the number of structural units. Weight-average molecular weight 20000, acid value 70.1 mgKOH / g).

[0428] [Chemical Formula 25]

[0429]

[0430] B-4: A 30% PGMEA solution of Prysur A212C (manufactured by DKS Co., Ltd., acid value 100-120 mg KOH / g).

[0431] CB-1: A 30% by mass PGMEA solution of a resin with the following structure (weight average molecular weight 10000).

[0432] [Chemical Formula 26]

[0433]

[0434] (solvent)

[0435] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0436] S-2: Cyclopentanone

[0437] S-3: Cyclohexanone

[0438] <Preparation of Photosensitive Compositions>

[0439] The materials listed in the table below were mixed and stirred according to the mass parts listed in the table below, and then filtered through a 0.45 μm nylon filter (manufactured by Nihon Pall Ltd.) to produce a photosensitive composition. In the table below, the content of specific compounds in the photosensitive composition is recorded in the "Specific Compound Concentration (mass %)" column, and the content of colorants (total content of pigments, dyes, and pigment derivatives) in the total solids composition of the photosensitive composition is recorded in the "Colorant Concentration (mass %)" column. Furthermore, the total solids composition of the photosensitive composition refers to the total mass of the components after removing the solvent.

[0440] [Table 2]

[0441]

[0442] [Table 3]

[0443]

[0444] [Table 4]

[0445]

[0446] [Table 5]

[0447]

[0448] [Table 6]

[0449]

[0450] [Table 7]

[0451]

[0452] The details of the materials represented by abbreviations in the table indicating the formulation of the above-mentioned photosensitive composition are as follows.

[0453] (Dispersion)

[0454] Dispersions R-2, R-5 to R-10, B-1, G-1, CG-1: The above-mentioned dispersions R-2, R-5 to R-10, B-1, G-1, CG-1

[0455] (Adhesive resin)

[0456] C-1: A 30% by mass solution of propylene glycol monomethyl ether acetate (PGMEA) of the following resin structure (the values ​​on the main chain are the molar ratio of structural units. Weight-average molecular weight 11000, acid value 69 mg KOH / g).

[0457] [Chemical Formula 27]

[0458]

[0459] C-2: A 30% by mass solution of propylene glycol monomethyl ether acetate (PGMEA) of the following resin structure (the values ​​indicated on the main chain are the molar ratio of structural units. Weight-average molecular weight 11000, acid value 195.4 mgKOH / g).

[0460] [Chemical Formula 28]

[0461]

[0462] C-3: A 30% PGMEA solution of the following resin structure (the values ​​on the main chain are the molar ratio of structural units, and the values ​​on the side chains are the number of structural units. Weight-average molecular weight 20000, acid value 94.7 mgKOH / g, C=C value: neutral / salt = 0.62 / 0.12 (mmol / g)).

[0463] [Chemical Formula 29]

[0464]

[0465] CC-1: A 30% by mass PGMEA solution of a resin with the following structure (weight average molecular weight 20000).

[0466] [Chemical Formula 30]

[0467]

[0468] (polymerizable monomers (polymerizable compounds))

[0469] M-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a compound containing olefinic unsaturated groups)

[0470] M-2: NK Ester A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., a compound containing olefinic unsaturated groups)

[0471] M-3: M-305 (manufactured by TOAGOSEI CO.,LTD., a compound containing olefinically unsaturated groups)

[0472] M-4: M-350 (manufactured by TOAGOSEI CO.,LTD., a compound containing olefinically unsaturated groups)

[0473] CM-1: NK Ester A-DPH-12ET (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., a compound containing olefinic unsaturated groups)

[0474] (Photopolymerization initiator)

[0475] I-1~I-3, CI-1: Compounds with the following structures

[0476] [Chemical Formula 31]

[0477]

[0478] (Polymerization inhibitor)

[0479] In-1: p-Methoxyphenol

[0480] (additive)

[0481] A-1: Compounds with the following structure (molecular weight 2300, compounds with cyclic ether groups)

[0482] A-2~A-6: Compounds with the following structures

[0483] [Chemical Formula 32]

[0484]

[0485] (Specific compound)

[0486] P-1: Polyethylene glycol 200 (a compound with the following structure, number average molecular weight 200).

[0487] P-2: Polyethylene glycol 400 (a compound with the following structure, number average molecular weight 400).

[0488] P-3: Polyethylene glycol 1000 (a compound with the following structure, number average molecular weight 1000).

[0489] P-4: Polyethylene glycol 20000 (a compound with the following structure, number average molecular weight 20000).

[0490] P-5: Polyethylene glycol monomethyl ether 550 (a compound with the following structure, number average molecular weight 550).

[0491] P-6: Polyethylene glycol dimethyl ether 550 (a compound with the following structure, number average molecular weight 550).

[0492] P-7: Diethylene glycol monoethyl ether (a compound with the following structure, molecular weight 134)

[0493] P-8: Triethylene glycol monoethyl ether (a compound with the following structure, molecular weight 178).

[0494] P-9: Ethylene glycol monobutyl ether (a compound with the following structure, molecular weight 118).

[0495] P-10: Triethylene glycol monobutyl ether (a compound with the following structure, molecular weight 206).

[0496] P-11: (2-Butoxyethoxy)acetic acid (a compound with the following structure, molecular weight 176)

[0497] P-12: 2-[2-(2-aminoethoxy)ethoxy]ethanol (a compound with the following structure, molecular weight 149)

[0498] [Chemical Formula 33]

[0499]

[0500] (surfactant)

[0501] W-1: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0502] (solvent)

[0503] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0504] S-3: Cyclohexanone

[0505] <Evaluation>

[0506] (Pixel defects)

[0507] On an 8-inch diameter silicon wafer (substrate A) or a support (substrate B) with partitions spaced 1.0 μm apart in a grid pattern, a substrate composition (CT-4000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied by spin coating to achieve a film thickness of 0.1 μm. The substrate layer was then formed by heating at 220°C for 1 hour using a hot plate. Using a spin coater (manufactured by MIKASA CO., LTD.), various photosensitive compositions were applied to the silicon wafer with the substrate layer to achieve a pre-baked film thickness of 0.6 μm, thus forming a coating film. Next, the wafer was heated at 100°C for 2 minutes using a hot plate. Then, an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at 1000 mJ / cm². 2 Exposure was performed through a 1.0 μm square Bayer pattern mask. Next, a 60-second spin-dip development was performed at 23°C using a 0.3% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. Afterwards, the image was rinsed by a spin spray and further washed with pure water to form pixels. The silicon wafer with the pixels formed was diced, and platinum was deposited. Cross-sectional scanning electron microscopy (SEM) images of the pixels were obtained using a scanning electron microscope (manufactured by Hitachi High-Tech Corporation). 100 pixels were extracted from the obtained surface SEM images, and the number of pixels with defects larger than 0.1 μm observed on the pixel surface was measured. Pixel defects were evaluated according to the following evaluation criteria. Note that "-" in the table indicates no evaluation was performed. That is, the evaluation of pixel defects in substrate B was performed only for Examples 1-10, 55-57, and Comparative Example 1.

[0508] -Evaluation Criteria-

[0509] 5: Out of 100 pixels, the number of pixels with defects larger than 0.1 μm was 0.

[0510] 4: Among 100 pixels, the number of pixels with defects larger than 0.1 μm is more than 1 and less than 5.

[0511] 3: Among 100 pixels, the number of pixels with defects larger than 0.1 μm is 5 or more but less than 10.

[0512] 2: Among 100 pixels, the number of pixels with defects larger than 0.1 μm is more than 10 and less than 50.

[0513] 1: Among 100 pixels, the number of pixels with defects larger than 0.1μm is observed to be 50 or more.

[0514] (Sensitivity)

[0515] On an 8-inch diameter silicon wafer, a substrate composition (CT-4000, manufactured by FUJIFILME Electronic Materials Co., LTD.) was spin-coated to achieve a film thickness of 0.1 μm, and then heated at 220°C for 1 hour using a hot plate to form the substrate layer. Using a spin coater (MIKASA CO., LTD.), various photosensitive compositions were coated onto the silicon wafer with this substrate layer to achieve a pre-baked film thickness of 0.6 μm, thus forming the coating. Next, it was heated at 100°C for 2 minutes using a hot plate (pre-baking). Then, exposure was performed using an i-line stepper exposure unit FPA-3000i5+ (manufactured by Canon Inc.) through a 1.0 μm square Bayer pattern mask. Next, a spin-dip development was performed at 23°C for 60 seconds using a 0.3% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. Afterwards, the wafer was rinsed by a spin spray and further washed with pure water to form pixels. The upper surface of the silicon wafer with the aforementioned pixels was observed using a scanning electron microscope (SEM), and the pixel linewidth was evaluated according to the evaluation criteria below. Note that "-" in the table indicates that no evaluation was performed.

[0516] -Evaluation Criteria-

[0517] 5: The exposure amount to achieve a linewidth of 1.0μm is less than 100mJ.

[0518] 4: The exposure amount to achieve a linewidth of 1.0μm is 100mJ or more but less than 300mJ.

[0519] 3: The exposure amount to achieve a linewidth of 1.0μm is 300mJ or more but less than 1000mJ.

[0520] 2: The exposure amount to achieve a linewidth of 1.0μm is above 1000mJ and less than 2000mJ.

[0521] 1: The exposure amount to achieve a linewidth of 1.0μm is above 2000mJ.

[0522] (Reproducible)

[0523] A substrate composition (CT-4000, manufactured by FUJIFILME Electronic Materials Co., LTD.) was spin-coated onto an 8-inch diameter glass wafer to achieve a film thickness of 0.1 μm, and then heated at 220°C for 1 hour using a hot plate to form a substrate layer. Using a spin coater (manufactured by MIKASA CO., LTD.), various photosensitive compositions were coated onto a silicon wafer with this substrate layer to achieve a pre-baked film thickness of 0.6 μm, thus forming a coating. Next, a spin-dip development was performed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. Afterwards, rinsing with a rotating spray and washing with pure water were performed to obtain a developed glass wafer. The maximum absorbance difference (ΔAbs) between the developed glass wafer and the uncoated glass wafer with a substrate layer was measured in the 400–700 nm range, and the developability was evaluated according to the following criteria. A smaller ΔAbs indicates better developability. Additionally, "-" in the table indicates that no evaluation was conducted.

[0524] -Evaluation Criteria-

[0525] 5: ΔAbs is below 0.01

[0526] 4: ΔAbs exceeds 0.01 but is below 0.02

[0527] 3: ΔAbs exceeds 0.02 but is below 0.03

[0528] 2: ΔAbs exceeds 0.03 but is below 0.04

[0529] 1: ΔAbs exceeds 0.04

[0530] [Table 8]

[0531]

[0532] [Table 9]

[0533]

[0534] As shown in the table above, the embodiments are able to suppress the generation of pixel defects.

[0535] (Examples 1001-1048)

[0536] The dispersion R-2 in Examples 1-16 was replaced with dispersion R-1, R-3 or R-4. Otherwise, the photosensitive composition was manufactured in the same manner as in Examples 1-16, and the evaluation results were carried out under the same conditions, and the same evaluation results as in the examples were obtained.

[0537] (Examples 3001-3096)

[0538] The dispersion B-1 in Examples 23-38 was replaced with dispersions B-2, B-3, B-4, B-5, B-6, or B-7. Otherwise, the photosensitive compositions were manufactured in the same manner as in Examples 23-38, and the evaluation results were carried out under the same conditions, obtaining the same evaluation results as in the examples.

[0539] (Examples 5001 to 5160)

[0540] The dispersion G-1 in Examples 39-54 was replaced with dispersions G-2, G-3, G-4, G-5, G-6, G-7, G-8, G-9, G-10 or G-11. Otherwise, the photosensitive compositions were manufactured in the same manner as in Examples 39-54, and the results of each evaluation were carried out under the same conditions, and the same evaluation results were obtained.

[0541] <Preparation of the Composition for Use in the Partition>

[0542] (Compositions 1-3, 6-8 for adjacent rooms)

[0543] The components were mixed to achieve the compositions shown in the table below (the blending amounts are parts by mass), and filtered using a DFA4201NIEY (0.45 μm nylon filter) manufactured by Nihon Pall Ltd. to produce partition wall compositions 1 to 3, 6 to 8.

[0544] [Table 10]

[0545]

[0546] The raw materials listed in the table above are as follows.

[0547] (Silica particle solution)

[0548] P1: This is a silica particle solution prepared by adding 3.0 g of trimethylmethoxysilane as a hydrophobicating agent to 100.0 g of a propylene glycol monomethyl ether acetate solution (silica particle concentration 20% by mass) containing the following silica particles (beaded silica), and reacting at 20°C for 6 hours. The silica particles have the following shape: multiple spherical silica particles with an average particle size of 15 nm are connected in a beaded manner by silica containing metal oxides (connecting material). Furthermore, in silica particle solution P1, the average particle size of the spherical silica was calculated by averaging the number of equivalent circle diameters in the projected images of the spherical portions of 50 spherical silica particles measured using transmission electron microscopy (TEM). Additionally, the presence of silica particles (multiple spherical silica particles connected in a beaded manner) in silica particle solution P1 was investigated by TEM observation.

[0549] P2: Thrulya 4110 (manufactured by JGC Catalysts and Chemicals Ltd., a solution of silica particles (hollow silica particles) with an average particle size of 60 nm. The solid content concentration converted from SiO2 is 20% by mass).

[0550] P3: A silica particle solution prepared by the following method.

[0551] 100 g of silica sol with an average particle size of 5 nm and a SiO2 concentration of 20% by mass was mixed with 1900 g of pure water to prepare a reaction mother liquor, which was then heated to 80 °C. The pH of this reaction mother liquor was 10.5. 9000 g of a sodium silicate aqueous solution (1.17% by mass as SiO2) and 9000 g of a sodium aluminate aqueous solution (0.83% by mass as Al2O3) were simultaneously added to the mother liquor. During this process, the temperature of the reaction solution was maintained at 80 °C. After the addition of sodium silicate and sodium aluminate, the pH of the reaction solution immediately rose to 12.5 and then remained almost unchanged. After the addition was complete, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a primary particle dispersion of SiO2·Al2O3 with a solid content of 20% by mass. Next, 500g of the SiO2·Al2O3 primary particle dispersion was collected, and 1700g of pure water was added. The mixture was heated to 98°C, and while maintaining this temperature, 50400g of sodium sulfate (0.5% by mass) was added. Then, 3000g of sodium silicate aqueous solution (1.17% by mass as SiO2) and 9000g of sodium aluminate aqueous solution (0.5% by mass as Al2O3) were added to obtain a composite oxide particle dispersion. This dispersion was then washed with an ultrafiltration membrane to obtain a composite oxide particle dispersion with a solid content concentration of 13% by mass. 1125g of pure water was added to 500g of this composite oxide particle dispersion, and concentrated hydrochloric acid (35.5%) was added dropwise to adjust the pH to 1.0, followed by a dealumination treatment. Next, while adding 10L of hydrochloric acid aqueous solution with pH 3 and 5L of pure water, the dissolved aluminum salt was separated by ultrafiltration membrane and washed to obtain a dispersion of silica-based microparticles (1) with a solid content concentration of 20% by mass. 500g of pure water, 1750g of ethanol, and 626g of 28% ammonia were added to 1500g of the aqueous dispersion of silica-based microparticles (1), and the resulting mixture was heated to 35°C. Then, 104g of ethyl silicate (SiO2 28% by mass) was added. Next, while adding 5L of pure water, the mixture was washed by ultrafiltration membrane to prepare a dispersion of silica-based microparticles (2) with a solid content concentration of 20% by mass. Next, the dispersion of silica-based microparticles (2) was subjected to hydrothermal treatment again at 200°C for 11 hours, and then while adding 5L of pure water, the mixture was washed by ultrafiltration membrane to adjust the solid content concentration to 20% by mass. Then, using an ultrafiltration membrane, the dispersion medium of the dispersion was replaced with propylene glycol monomethyl ether, thereby preparing an organosol with a solid content of 20% by mass. This organosol is an organosol dispersed with hollow silica particles with an average particle size of 23 nm (hereinafter referred to as "hollow silica sol A").Prepare 200g of hollow silica sol A (20% by mass concentration of solid silica). Replace the solvent with methanol using an ultrafiltration membrane to prepare 100g of an organosol with a SiO2 content of 20% by mass (water content relative to SiO2 content of 0.5% by mass). Add a 28% ammonia solution to bring the ammonia content to 100 ppm by mass relative to the 100g organosol, and mix thoroughly. Then, add 4g of silane methacrylate (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.) (equivalent to 20 parts by mass relative to 100 parts by mass of SiO2) to prepare a reaction solution (water content relative to SiO2 content of 0.6% by mass). Heat the solution to 50°C and stir while heating at 50°C for 15 hours. After heating, the reaction solution was cooled to room temperature and cleaned with an ultrafiltration membrane to prepare silica particle liquid P3, which consists of hollow microparticles coated with SiO2 at a concentration of 20% by mass.

[0552] (surfactant)

[0553] W-11: A compound with the following structure (a silicone-based nonionic surfactant, a methanol-modified silicone compound. Weight-average molecular weight = 3000, kinematic viscosity at 25°C = 45 mm). 2 / s)

[0554] [Chemical Formula 34]

[0555]

[0556] W-12: Compounds with the following structures

[0557] [Chemical Formula 35]

[0558]

[0559] (Silane coupling agent)

[0560] SC-1: Additive A-5 mentioned above

[0561] (solvent)

[0562] S-11: 1,4-Butanediol diacetate

[0563] S-12: Propylene glycol monomethyl ether acetate

[0564] S-13: Propylene glycol monomethyl ether

[0565] S-14: Methanol

[0566] S-15: Ethanol

[0567] S-16: Water

[0568] S-17: Compounds with the following structures

[0569] [Chemical Formula 36]

[0570]

[0571] S-18: 1-Propanol

[0572] S-19: 2-Propanol

[0573] (Composition 4 for adjacent rooms)

[0574] 300 g of cation exchange resin powder (WK-40, Mitsubishi Chemical Corporation.) was added to 1000 g of an aqueous solution containing 40% by mass of tetrapropylammonium hydroxide (TPAOH, manufactured by Lion Corporation). The mixture was stirred at 100 rpm for 1 hour at room temperature, and the added cation exchange resin powder was removed by filtration. Next, 2100 g of anion exchange resin powder (SAT-10, manufactured by Mitsubishi Chemical Corporation.) was added, and the mixture was stirred at 100 rpm for 1 hour at room temperature. The added anion exchange resin powder was then removed by filtration. The obtained aqueous solution of tetrapropylammonium hydroxide (TPAOH) was adjusted to a concentration of 10% by mass by adding ultrapure water. The amounts of alkali metal compounds (sodium (Na) and potassium (K)) and halogen compounds (bromine (Br) and chlorine (Cl)) contained in the aqueous solution as impurities were determined by atomic absorption spectrometry (AAS method, Hitachi, Ltd. Zeeman polarized atomic absorption spectrophotometer Z-5710) and ion chromatography (Dionex Corporation 2020i), respectively. Furthermore, the content of impurities was also determined by adding ultrapure water to the aqueous solution of tetrapropylammonium hydroxide (commercially available) before the above ion exchange treatment to adjust the concentration to 10% by mass. As a result, compared with the impurities in the aqueous solution before ion exchange treatment (sodium 50 ppm, potassium 2500 ppm, bromine 2250 ppm, and chlorine 13 ppm on an elemental basis), the impurities in the aqueous solution after ion exchange treatment (sodium 10 ppb or less (detection limit), potassium 10 ppb or less (detection limit), bromine 1 ppm or less (chlorine 1 ppm) on an elemental basis) were found to be less than 10 ppb (detection limit), bromine 1 ppm or less (detection limit), and chlorine 1 ppm or less (detection limit). Next, tetraethyl orthosilicate (TEOS, manufactured by TAMA CHEMICALS CO.,LTD.), methyltrimethoxysilane (MTMS, manufactured by Shin-Etsu Chemical Co.,Ltd.), and 99.5% ethanol (ETOH, manufactured by FUJIFILM Wako Pure Chemical Corporation) were mixed, and the mixture was maintained at 20°C and stirred at 150 rpm for 30 minutes. These mixed solutions were added dropwise over 10 minutes with a highly purified aqueous solution of tetrapropylammonium hydroxide (containing 10% by mass of TPAOH), and then stirred at 200 rpm for 1 hour at 20°C.Subsequently, the silica-based coating-forming components (TEOS and MTMS) were hydrolyzed for 20 hours while being heated to 50°C and stirred at 200 rpm. Next, the ethanol in the mixed solution containing the hydrolysate of the silica-based coating-forming components was replaced with propylene glycol monopropyl ether using a rotary evaporator. The concentration of the silicon compound composed of the hydrolysate of tetraethyl orthosilicate (TEOS) and methyltrimethoxysilane (MTMS) was adjusted to obtain a liquid composition containing 12% by mass of this compound based on SiO2 conversion. This liquid composition was used as composition 4 for partition walls.

[0575] (Composition 5 for use next door)

[0576] In a 500 ml three-necked flask, a mixture of 0.05 g (0.4 mmol) of methyltrimethoxysilane (KBM-13: manufactured by Shin-Etsu Chemical Co., Ltd.), 0.66 g (3.0 mmol) of trifluoropropyltrimethoxysilane (KBM-7103: manufactured by Shin-Etsu Chemical Co., Ltd.), 0.10 g (0.4 mmol) of trimethoxysilylpropylsuccinic anhydride (KBM-967: manufactured by Shin-Etsu Chemical Co., Ltd.), 7.97 g (34 mmol) of γ-acryloyloxypropyltrimethoxysilane (KBM-5103: manufactured by Shin-Etsu Chemical Co., Ltd.), and 224.37 g of 15.6% by mass silica particles in an isopropanol dispersion (IPA-ST-UP: Nissan Chemical) was prepared. (Manufactured by Corporation), and 163.93 g of ethylene glycol mono-tert-butyl ether was added. An aqueous solution of phosphoric acid, obtained by dissolving 0.088 g of phosphoric acid in 4.09 g of water, was added over 3 minutes with stirring at room temperature. The flask was then immersed in an oil bath at 40°C and stirred for 60 minutes, after which the oil bath temperature was raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and it was then heated and stirred for another 2 hours (internal temperature 100–110°C) to obtain partition wall composition 4. The obtained partition wall composition 4 had a solids concentration of 24.3% by mass, and the contents of polysiloxane and silica particles in the solids were 15% by mass and 85% by mass, respectively.

[0577] <Preparation of the composition for base layer formation>

[0578] (Composition 1 for basement formation)

[0579] Composition 1 for substrate formation was prepared by mixing 0.1 parts by weight of resin A (weight average molecular weight 20,000, the values ​​indicated on the main chain are the mass ratio of repeating units), 0.01 parts by weight of epoxy compound (the above-mentioned additive A-1), 0.01 parts by weight of surfactant (KF-6000, manufactured by Shin-Etsu Chemical Co., Ltd.), and 99.88 parts by weight of propylene glycol monomethyl ether acetate.

[0580] [Chemical Formula 37]

[0581]

[0582] (Composition 2 for base layer formation)

[0583] Composition 2 for substrate formation was prepared by mixing 0.7 parts by weight of resin (CYCLOMER P(ACA)230AA, manufactured by DAICEL-ALLNEX LTD.), 0.8 parts by weight of surfactant (KF-6000, manufactured by Shin-Etsu Chemical Co., Ltd.), and 98.5 parts by weight of propylene glycol monomethyl ether acetate.

[0584] (Composition 3 for basement formation)

[0585] Composition 3 for substrate formation was prepared by mixing 0.3 parts by weight of the above-mentioned resin A, 0.02 parts by weight of the polymerizable compound (KAYARAD DPHA, manufactured by NipponKayaku Co., Ltd.), 0.01 parts by weight of the surfactant (KF-6000, manufactured by Shin-Etsu Chemical Co., Ltd.), and 99.67 parts by weight of propylene glycol monomethyl ether acetate.

[0586] <Preparation of Lens Material Composition>

[0587] (Lens material composition 1)

[0588] Lens material composition 1 was prepared by mixing 10 parts by weight of a resin with the following structure (weight average molecular weight 19,000, the values ​​indicated on the main chain are the molar ratio of repeating units), 0.01 parts by weight of a surfactant (FTERGENT DFX-18, manufactured by Neos Corporation), 51.4 parts by weight of propylene glycol monomethyl ether acetate, and 22.0 parts by weight of propylene glycol monomethyl ether.

[0589] [Chemical Formula 38]

[0590]

[0591] <Manufacturing of Solid State Imaging Components>

[0592] As a support, an 8-inch (20.32 cm) diameter silicon wafer with silicon photodiodes formed on it was used. After drying any one of the spacer compositions 1 to 8, it was spin-coated onto the surface of the silicon wafer on the side with the silicon photodiodes formed, to achieve a film thickness of 350 nm. Then, it was heated at 100°C for 120 seconds and then at 200°C for 300 seconds using a hot plate to form the film. In addition, when spacer composition 5 was used, an additional treatment of heating at 300°C for 10 minutes was performed to form the film. Under the conditions described in paragraphs 0128 to 0133 of Japanese Patent Application Publication No. 2016-014856, these films were patterned by dry etching to form a lattice-shaped spacer with a spacing of 0.7 μm.

[0593] On the surface of the silicon wafer and the spacers on which these spacers are formed, any one of the substrate layer compositions 1 to 3 prepared above is applied by spin coating, and heated at 100°C for 2 minutes and then at 230°C for 2 minutes using a heating plate, thereby forming a substrate layer with a film thickness of 10 nm on the surface of the silicon wafer and the spacers.

[0594] Next, a pixel-forming composition of the first color is spin-coated onto the surface of the silicon wafer with partitions. Then, the surface is heated to 100°C for 2 minutes using a hot plate to form the first color composition layer. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), through a mask with a Bayer pattern, at 150 mJ / cm²... 2 The composition layer was exposed to the specified exposure level. Next, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used, and the composition layer was subjected to a spin-dip development at 23°C for 60 seconds. Afterwards, a rinsing process using a rotating spray, a water rinse using pure water, and then heating at 220°C for 5 minutes using a hot plate were performed to form pixels of the first color in the spacer-divided areas on the silicon wafer. The second and third color pixel forming compositions were also developed and exposed using the same method as the first color pixel forming composition, and pixels of the second and third colors were sequentially formed in the spacer-divided areas on the silicon wafer to form a filter. Furthermore, the first color pixel forming composition used the photosensitive composition of Example 1. The second color pixel forming composition used the photosensitive composition of Example 39. The third color pixel forming composition used the photosensitive composition of Example 23.

[0595] Next, the lens material composition 1 was coated onto the filter using a spin coating method. Then, the filter was heated at 100°C for 2 minutes using a heating plate, followed by heating at 200°C for 5 minutes using a heating plate, thereby forming a lens material composition layer with a film thickness of 1.2 μm. Subsequently, using a known etching transfer method, the lens material composition layer was processed to a height of 400 nm from the top to the bottom of the lens, thereby forming a microlens to manufacture a solid-state imaging element.

[0596] The spacer compositions 1 to 8 used in the manufacture of solid-state imaging elements can also be used as metamaterials, low-refractive-index materials for metasurfaces, low-refractive-index materials for optical components or color filters containing metasurfaces, and low-refractive-index materials for anti-reflective layers.

[0597] Symbol Explanation

[0598] 10-Support body, 11-Blocking wall.

Claims

1. A photosensitive composition comprising a colorant, a resin, a polymerizable compound, a photopolymerization initiator, a solvent, and a compound A represented by formula (1), In equation (1), R 1 and R 2 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 12 carbon atoms, a group containing an acid group with 1 to 6 carbon atoms, or a group containing an amino group with 1 to 6 carbon atoms. X 1 This indicates a straight-chain or branched alkylene group, where n represents an integer greater than or equal to 1. When n is 2 or greater, multiple X groups are represented. 1 Choose either the same or different.

2. The photosensitizing composition according to claim 1, wherein, X in equation (1) 1 At least one of them is ethylene, R 1 and R 2 Each is independently an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

3. The photosensitizing composition according to claim 1, wherein, X in equation (1) 1 It is ethylene, R 1 and R 2 Each is independently an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

4. The photosensitive composition according to any one of claims 1 to 3, wherein, R in equation (1) 1 and R 2 It is a hydrogen atom.

5. The photosensitive composition according to any one of claims 1 to 3, wherein, The molecular weight of compound A is 150 to 2000.

6. The photosensitive composition according to any one of claims 1 to 3, wherein, The content of compound A in the photosensitive composition is 0.01% to 5.0% by mass.

7. The photosensitive composition according to any one of claims 1 to 3, wherein, The content of the colorant in the total solids component of the photosensitive composition is 55% by mass or more.

8. A film obtained using the photosensitive composition according to any one of claims 1 to 3.

9. A filter having the membrane of claim 8.

10. A method for manufacturing a filter, comprising: The process of forming a composition layer on a support using the photosensitive composition according to any one of claims 1 to 3; And the process of forming a pattern on the composition layer by photolithography.

11. A solid-state imaging element having the membrane of claim 8.

12. An image display device having the membrane of claim 8.

Images