Resin compositions, films, optical filters, solid-state image sensors, and image display devices.

Abstract

Provided is a resin composition that exhibits an excellent pigment dispersibility. Also provided are a film, an optical filter, and a solid-state imaging element that use the resin composition. The resin composition comprises a pigment-containing colorant A, a resin B, and a solvent C. The resin B comprises a resin B1 that contains an acid anhydride group and a polymer chain comprising a repeat unit of at least one structure selected from polyether structures and polyester structures.

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a film, an optical filter, a solid-state image sensor, and an image display device. [Background technology]

[0002] In recent years, the demand for solid-state image sensors, such as charge-coupled (CCD) image sensors, has grown significantly due to the widespread use of digital cameras and camera-equipped mobile phones. Solid-state image sensors utilize films containing pigments, such as color filters. These color-containing films are manufactured using resin compositions containing pigments, resins, and solvents.

[0003] Patent Document 1 describes using a (meth)acrylic polymer (A2) having an anhydride group in one terminal region, which is obtained by polymerizing an ethylenically unsaturated monomer in the presence of a compound having two carboxyl groups and one or more thiol groups in the molecule, and by modifying the two carboxyl groups of (meth)acrylic polymer (A1) having two carboxyl groups in one terminal region with acid anhydride groups, as a pigment dispersant. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-090788 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In a resin composition containing a pigment, resin, and solvent, good dispersibility of the pigment is preferable. If the dispersibility of the pigment is insufficient, the pigment may aggregate and become coarse in the resin composition, or the viscosity of the resin composition may increase. Furthermore, even if the viscosity of the resin composition is low immediately after manufacturing, the viscosity may increase over time.

[0006] According to the study by the present inventors, it was found that the pigment dispersant described in Patent Document 1 has insufficient pigment dispersibility and there is room for further improvement.

[0007] Therefore, an object of the present invention is to provide a resin composition excellent in pigment dispersibility. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device using the resin composition.

Means for Solving the Problems

[0008] Examples of typical embodiments of the present invention are shown below. <1> A coloring material A containing a pigment, a resin B, and a solvent C, and the resin B contains a resin B1 including an acid anhydride group and a polymer chain including repeating units of at least one structure selected from a polyether structure and a polyester structure, the resin composition. <2> The resin composition according to <1>, wherein the acid anhydride group is a cyclic acid anhydride group. <3> The resin composition according to <1> or <2>, wherein the resin B1 is a resin represented by the formula (1);

Chemical formula

[0009] According to the present invention, it is possible to provide a resin composition with excellent pigment dispersibility. Furthermore, it is possible to provide a film, optical filter, solid-state image sensor, and image display device using the resin composition. [Modes for carrying out the invention]

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of light used for exposure include the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, (meth)allyl group represents allyl and methallyl, or either of them; (meth)acrylate represents acrylate and methacrylate, or either of them; (meth)acrylic represents acrylic and methacrylic, or either of them; and (meth)acryloyl represents acryloyl and methacryloyl, or either of them. In this specification, the weight-average molecular weight and number-average molecular weight are polystyrene-converted values ​​measured by GPC (gel permeation chromatography). In this specification, near-infrared light refers to light with a wavelength of 700 to 2500 nm. In this specification, total solids refers to the total mass of the components of the composition excluding the solvent. In this specification, the term "process" does not refer only to an independent process, but is also included in this term if the intended function of the process is achieved, even if it cannot be clearly distinguished from other processes. In this specification, "pigment" means a compound that is poorly soluble in solvents. In this specification, symbols preceding or following names (e.g., A) are terms used to distinguish components and do not limit the type, number, or hierarchy of components.

[0011] <Resin composition> The resin composition of the present invention is Colorant A containing pigment, Resin B and containing solvent C, The above resin B is characterized by comprising resin B1 which includes an acid anhydride group and a polymer chain which includes repeating units of at least one structure selected from a polyether structure and a polyester structure.

[0012] The resin composition of the present invention exhibits excellent pigment dispersibility. Although the detailed reasons for this effect are unknown, it is presumed to be due to the following: In the resin composition, the acid anhydride groups of resin B1 are adsorbed onto the surface of the pigment, and the polymer chains of resin B1 act as steric repulsive groups. Furthermore, since the polymer chains include repeating units of at least one structure selected from polyether and polyester structures, it is presumed that resin B1 has excellent affinity for solvents in the resin composition. For this reason, it is presumed that the resin composition of the present invention, by including resin B1, is able to be a resin composition with excellent pigment dispersibility.

[0013] The resin composition of the present invention is preferably used as a resin composition for optical filters. Examples of optical filters include color filters, near-infrared transmission filters, and near-infrared cut filters, with color filters being preferred. Furthermore, the resin composition of the present invention can be preferably used as a resin composition for solid-state image sensors, and more preferably as a resin composition for pixel formation of optical filters used in solid-state image sensors.

[0014] Examples of color filters include filters having colored pixels that transmit light of a specific wavelength, and it is preferable that the filter has at least one colored pixel selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels. Color filters can be formed using a resin composition containing a chromatic colorant.

[0015] Examples of near-infrared cut filters include filters whose maximum absorption wavelength is in the range of 700 to 1800 nm. The maximum absorption wavelength of the near-infrared cut filter is preferably in the range of 700 to 1300 nm, and more preferably in the range of 700 to 1100 nm. Furthermore, the transmittance of the near-infrared cut filter over the entire range of wavelengths 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 point in the range of wavelengths from 700 to 1800 nm is preferably 20% or less. In addition, the ratio of absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to absorbance A550 at a wavelength of 550 nm, which is absorbance Amax / absorbance A550, is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400. Near-infrared cut filters can be formed using a resin composition containing a near-infrared absorbing colorant.

[0016] A near-infrared transmission filter is a filter that transmits at least a portion of near-infrared light. Preferably, a near-infrared transmission filter is a filter that blocks at least a portion of visible light and transmits at least a portion of near-infrared light. Preferred near-infrared transmission filters include filters that satisfy spectral characteristics such as 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 1100 to 1300 nm. Preferably, a near-infrared transmission filter is a filter that satisfies any of the following spectral characteristics (1) to (5). (1) A filter having 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. (2) A filter having 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. (3) A filter having 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. (4) A filter having 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. (5) A filter having 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.

[0017] One preferred embodiment of the spectral properties of the resin composition of the present invention is that, when a film with a thickness of 5 μm is formed using the resin composition, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 360 to 700 nm is 50% or more. A resin composition satisfying such spectral properties can be preferably used as a resin composition for forming pixels in a color filter. Specifically, it can be preferably used as a resin composition for forming colored pixels selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels.

[0018] Resin compositions having the above spectral characteristics preferably contain chromatic pigments. For example, a resin composition containing a red pigment and a yellow pigment can preferably be used as a resin composition for forming red pixels. A resin composition containing a blue pigment and a purple pigment can preferably be used as a resin composition for forming blue pixels. A resin composition containing a green pigment can preferably be used as a resin composition for forming green or cyan pixels. When using a resin composition for forming green pixels, it is also preferable to include a yellow pigment in addition to the green pigment.

[0019] Another preferred embodiment of the spectral properties of the resin composition of the present invention is one in which the spectral properties satisfy the ratio Amin / B, which is the ratio of the minimum absorbance Amin in the wavelength range of 400 to 640 nm to the absorbance B at a wavelength of 1500 nm, is 5 or more. Resin compositions that satisfy such spectral properties can be preferably used as resin compositions for forming near-infrared transmission filters. The value of Amin / B, which is the ratio of absorbances, is preferably 7.5 or more, more preferably 15 or more, and even more preferably 30 or more.

[0020] Here, the absorbance Aλ at wavelength λ is defined by the following equation (λ1). Aλ = -log(Tλ / 100) ... (λ1) Aλ is the absorbance at wavelength λ, and Tλ is the transmittance (%) at wavelength λ. In the present invention, the absorbance value may be the value measured in solution, or the value of a film formed using the composition. When measuring the absorbance of a film, it is preferable to apply the composition to a glass substrate by a method such as spin coating, and then measure the absorbance using the film obtained by drying it at 100°C for 120 seconds using a hot plate or the like.

[0021] The resin composition of the present invention preferably satisfies any of the following spectral characteristics (Ir1) to (Ir5). (Ir1): The value of A1 / B1, which is the ratio of the minimum absorbance A1 in the wavelength range of 400 to 640 nm to the maximum absorbance B1 in the wavelength range of 800 to 1500 nm, is 4.5 or greater, preferably 7.5 or greater, more preferably 15 or greater, and even more preferably 30 or greater. According to this embodiment, it is possible to form a film that can block light in the wavelength range of 400 to 640 nm and transmit light with a wavelength greater than 750 nm. (Ir2): The ratio of the minimum absorbance A2 in the wavelength range of 400 to 750 nm to the maximum absorbance B2 in the wavelength range of 900 to 1500 nm, A2 / B2, is 4.5 or greater, preferably 7.5 or greater, more preferably 15 or greater, and even more preferably 30 or greater. According to this embodiment, it is possible to form a film that blocks light in the wavelength range of 400 to 750 nm and transmits light with a wavelength greater than 850 nm. (Ir3): The value of A3 / B3, which is the ratio of the minimum absorbance A3 in the wavelength range of 400 to 830 nm to the maximum absorbance B3 in the wavelength range of 1000 to 1500 nm, is 4.5 or greater, preferably 7.5 or greater, more preferably 15 or greater, and even more preferably 30 or greater. According to this embodiment, it is possible to form a film that can block light in the wavelength range of 400 to 830 nm and transmit light with a wavelength greater than 950 nm. (Ir4): The ratio of the minimum absorbance A4 in the wavelength range of 400 to 950 nm to the maximum absorbance B4 in the wavelength range of 1100 to 1500 nm, A4 / B4, is 4.5 or greater, preferably 7.5 or greater, more preferably 15 or greater, and even more preferably 30 or greater. According to this embodiment, it is possible to form a film that can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1050 nm. (Ir5): The value of A5 / B5, which is the ratio of the minimum absorbance A5 in the wavelength range of 400 to 1050 nm to the maximum absorbance B5 in the wavelength range of 1200 to 1500 nm, is 4.5 or greater, preferably 7.5 or greater, more preferably 15 or greater, and even more preferably 30 or greater. According to this embodiment, it is possible to form a film that can block light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength exceeding 1150 nm.

[0022] The resin composition of the present invention can also be used as a resin composition for forming a light-shielding film. When the resin composition of the present invention is used as a resin composition for forming a light-shielding film, the resin composition of the present invention preferably contains a black colorant, and more preferably contains a black pigment. Furthermore, the content of the black pigment in the total solid content of the resin composition is preferably 65% ​​by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more.

[0023] When the resin composition of the present invention is used as a resin composition for forming a light-shielding film, the film formed using the resin composition preferably has an optical density (OD) of 2.5 or more per 1.5 μm of film thickness in the wavelength region of 400 to 1100 nm, and more preferably 3.0 or more. There is no particular upper limit, but generally 10 or less is preferred. In this specification, an optical density of 2.5 or more per 1.5 μm of film thickness in the wavelength region of 400 to 1100 nm means that the optical density is 2.5 or more per 1.5 μm of film thickness throughout the entire wavelength range of 400 to 1100 nm.

[0024] Furthermore, the reflectance of the above film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%. The lower limit is preferably 0% or higher. Reflectance is determined from the reflectance spectrum obtained by incident light with a wavelength of 400 to 1100 nm at an incident angle of 5° using the VAR unit of the V7200 (product name) spectrometer manufactured by JASCO Corporation. Specifically, the reflectance of the film is defined as the reflectance of light at the wavelength that shows the maximum reflectance in the range of 400 to 1100 nm.

[0025] The resin composition of the present invention is also preferably a resin composition for pattern formation by photolithography. According to this embodiment, pixels of a fine size can be easily formed. For this reason, it can be particularly preferably used as a resin composition for pixel formation of optical filters used in solid-state image sensors. For example, a resin composition containing a component having an ethylenically unsaturated bond-containing group (for example, a resin having an ethylenically unsaturated bond-containing group or a monomer having an ethylenically unsaturated bond-containing group) and a photopolymerization initiator can be preferably used as a resin composition for pattern formation by photolithography. The resin composition for pattern formation by photolithography may further preferably contain an alkali-soluble resin.

[0026] The following describes each component used in the resin composition of the present invention.

[0027] <Colorant A> The resin composition of the present invention contains a colorant A (hereinafter referred to as "colorant"). Examples of colorants include white colorants, black colorants, chromatic colorants, and near-infrared absorbing colorants. In this invention, the white colorant includes not only pure white but also light gray colorants that are close to white (e.g., off-white, light gray, etc.).

[0028] The colorant preferably includes at least one selected from the group consisting of chromatic colorants, black colorants, and near-infrared absorbing colorants, more preferably includes at least one selected from the group consisting of chromatic colorants and black colorants, and even more preferably includes a black colorant.

[0029] Furthermore, the colorant may preferably include two or more chromatic colorants and a near-infrared absorbing colorant. Alternatively, a combination of two or more chromatic colorants may be used to form black. Furthermore, the colorant may preferably include a black colorant and a near-infrared absorbing colorant. According to these embodiments, the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared transmission filter. For combinations of colorants that form black using a combination of two or more chromatic colorants, please refer to Japanese Patent Publication No. 2013-077009, Japanese Patent Publication No. 2014-130338, International Publication No. 2015 / 166779, etc.

[0030] The colorant used in the colored composition of the present invention contains a pigment. The pigment may be either an inorganic pigment or an organic pigment.

[0031] The crystallite size of the organic pigment is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm. The crystallite size can be determined from the full width at half maximum of the diffraction angle peak using an X-ray diffractometer, and is calculated using Scherrer's formula. The crystallite size of the organic pigment can be adjusted by known methods such as adjusting the manufacturing conditions or grinding after manufacturing. Any grinding method that can adjust the crystallite size is acceptable, but dry grinding and wet grinding are examples. Dry grinding is preferred because it does not require solvent removal and there is a low concern about re-aggregation. Examples of dry grinding methods include impact crushing using a hammer crusher, jet grinding using a jet mill, and ball mills and rod mills. Known dry grinding equipment can be used, and equipment from Nippon Coke Industries, Kurimoto Iron Works, Ashizawa Fine Tech, and Sugino Machine can be used.

[0032] (Chromatic color materials) Examples of chromatic colorants include those having a maximum absorption wavelength in the range of 400 to 700 nm. Examples include yellow colorants, orange colorants, red colorants, green colorants, purple colorants, and blue colorants. From the viewpoint of heat resistance, chromatic colorants are preferably pigments (chromatic pigments), more preferably red pigments, yellow pigments, and blue pigments, and even more preferably red pigments and blue pigments.

[0033] The average primary particle size of the chromatic pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. If the average primary particle size of the chromatic pigment is within the above range, the dispersion stability of the chromatic pigment in the resin composition is good. In this specification, the average primary particle size of the pigment is the number-average particle size calculated by arithmetic mean of the number-based particle size measured by the dynamic light scattering method in accordance with JIS 8826:2005. Examples of measuring devices include a dynamic light scattering particle size distribution analyzer (Horiba, Ltd., LB-500).

[0034] Specific examples of chromatic pigments include the following:

[0035] CI Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,1 37, 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 (methine-based), 233 (quinoline-based), 234 (aminoketone-based), 235 (aminoketone-based), 236 (aminoketone-based), etc. (all yellow pigments), 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, 73, etc. (all are orange pigments) CI Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149 ,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 (xanthene-based, Organo Ultramarine, Bluish Red), 295 (monoazo-based), 296 (diazo-based), 297 (aminoketone-based), etc. (all are red pigments), CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine-based), 65 (phthalocyanine-based), 66 (phthalocyanine-based), etc. (all are green pigments). CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane-based), 61 (xanthene-based), etc. (all are purple pigments) CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo type), 88 (methine type), etc. (all are blue pigments).

[0036] Among these chromatic pigments, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 272, CI Pigment Red 122, and CI Pigment Red 177 are preferred as red pigments because they readily form films whose spectral properties do not easily change even after heating to high temperatures (e.g., 300°C or higher). Furthermore, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16 are preferred as blue pigments.

[0037] Furthermore, as a green pigment, zinc halide phthalocyanine pigments can be used, which have an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule. A specific example is the compound described in International Publication No. 2015 / 118720. In addition, as a green pigment, compounds described in Chinese Patent Application No. 106909027, phthalocyanine compounds having a phosphate ester as a ligand as described in International Publication No. 2012 / 102395, phthalocyanine compounds described in Japanese Patent Publication No. 2019-008014, phthalocyanine compounds described in Japanese Patent Publication No. 2018-180023, and compounds described in Japanese Patent Publication No. 2019-038958 can also be used.

[0038] Furthermore, aluminum phthalocyanine compounds containing a phosphorus atom can also be used as a blue pigment. Specific examples include the compounds described in paragraphs 0022 to 0030 of Japanese Patent Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Publication No. 2011-157478.

[0039] Furthermore, as a yellow pigment, the compounds described in Japanese Patent Publication No. 2017-201003, Japanese Patent Publication No. 2017-197719, Japanese Patent Publication No. 2017-171912 (paragraphs 0011-0062, 0137-0276), Japanese Patent Publication No. 2017-171913 (paragraphs 0010-0062, 0138-0295), Japanese Patent Publication No. 2017-171914 (paragraphs 0011-0062, 0139-0190), and Japanese Patent Publication No. 2017-171915 (paragraphs 0010-0065, 0142-0222) The following are examples of the following compounds: quinophthalone compounds described in paragraphs 0011-0034 of JP 2013-054339, quinophthalone compounds described in paragraphs 0013-0058 of JP 2014-026228, isoindoline compounds described in JP 2018-062644, quinophthalone compounds described in JP 2018-203798, quinophthalone compounds described in JP 2018-062578, quinophthalone compounds described in Japanese Patent No. 6432076, quinophthalone compounds described in JP 2018-155881, and JP 2018-1117 Quinophthalone compounds described in Japanese Patent Publication No. 57, Quinophthalone compounds described in Japanese Patent Publication No. 2018-040835, Quinophthalone compounds described in Japanese Patent Publication No. 2017-197640, Quinophthalone compounds described in Japanese Patent Publication No. 2016-145282, Quinophthalone compounds described in Japanese Patent Publication No. 2014-085565, Quinophthalone compounds described in Japanese Patent Publication No. 2014-021139, Quinophthalone compounds described in Japanese Patent Publication No. 2013-209614, Quinophthalone compounds described in Japanese Patent Publication No. 2013-209435, Quinophthalone compounds described in Japanese Patent Publication No. 2013-181015 Quinophthalone compounds, quinophthalone compounds described in Japanese Patent Publication No. 2013-061622, quinophthalone compounds described in Japanese Patent Publication No. 2013-032486, quinophthalone compounds described in Japanese Patent Publication No. 2012-226110, quinophthalone compounds described in Japanese Patent Publication No. 2008-074987, quinophthalone compounds described in Japanese Patent Publication No. 2008-081565, quinophthalone compounds described in Japanese Patent Publication No. 2008-074986, quinophthalone compounds described in Japanese Patent Publication No. 2008-074985, quinophthalone compounds described in Japanese Patent Publication No. 2008-050420,The following compounds can also be used: the quinophthalone compound described in Japanese Patent Publication No. 2008-031281, the quinophthalone compound described in Japanese Patent Publication No. 48-032765, the quinophthalone compound described in Japanese Patent Publication No. 2019-008014, the quinophthalone compound described in Japanese Patent Publication No. 6607427, the compound described in Korean Published Patent No. 10-2014-0034963, the compound described in Japanese Patent Publication No. 2017-095706, the compound described in Taiwan Patent Application Publication No. 201920495, the compound described in Japanese Patent Publication No. 6607427, the quinophthalone dimer described in Japanese Patent Publication No. 2020-033521, the compound represented by the following formula (QP1), and the compound represented by the following formula (QP2). Furthermore, polymerized versions of these compounds are also preferably used from the viewpoint of improving color value. [ka]

[0040] In formula (QP1), X 1 ~X 16 Each of these independently represents a hydrogen atom or a halogen atom, Z 1 represents an alkylene group having 1 to 3 carbon atoms. A specific example of a compound represented by formula (QP1) is the compound described in paragraph 0016 of Japanese Patent Publication No. 6443711. [ka]

[0041] In formula (QP2), Y 1 ~Y 3 Each of these independently represents a halogen atom. n and m are integers from 0 to 6, and p is an integer from 0 to 5. (n+m) is 1 or greater. Specific examples of compounds represented by formula (QP2) include those described in paragraphs 0047 to 0048 of Japanese Patent Publication No. 6432077.

[0042] As red pigments, diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure described in Japanese Patent Publication No. 2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 102399, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 117965, naphthol azo compounds described in Japanese Patent Publication No. 2012-229344, compounds described in Japanese Patent No. 6516119, compounds described in Japanese Patent No. 6525101, etc., can also be used. Furthermore, as red pigments, compounds having a structure in which an aromatic hydrocarbon group into which an oxygen atom, sulfur atom, or nitrogen atom is bonded to an aromatic hydrocarbon ring is bonded to a diketopyrrolopyrrole skeleton can also be used. Such compounds are preferably those represented by formula (DPP1), and more preferably those represented by formula (DPP2). [ka]

[0043] In the above formula, R 11 and R 13 Each of these independently represents a substituent, R 12 and R 14 Each of the following independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and n11 and n13 each independently represent an integer from 0 to 4, X 12 and X 14 Each of these independently represents an oxygen atom, a sulfur atom, or a nitrogen atom, and X 12 If it is an oxygen atom or a sulfur atom, then m12 represents 1, and X 12 If it is a nitrogen atom, then m12 represents 2, and X 14 If it is an oxygen atom or a sulfur atom, then m14 represents 1, and X 14 If it is a nitrogen atom, then m14 represents 2. 11 and R 13Preferred examples of substituents represented by include alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, amide groups, cyano groups, nitro groups, trifluoromethyl groups, sulfoxide groups, and sulfo groups.

[0044] Regarding the diffraction angles that various pigments preferably possess, refer to the descriptions in Japanese Patent Publication No. 6561862, Japanese Patent Publication No. 6413872, and Japanese Patent Publication No. 6281345, the contents of which are incorporated herein by reference.

[0045] Examples of chromatic dyes include pyrazole azo compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazoleazomethine compounds, xanthene compounds, phthalocyanine compounds, benzopyran compounds, indigo compounds, and pyromethene compounds.

[0046] Furthermore, the chromatic colorants include thiazole compounds described in JP 2012-158649, azo compounds described in JP 2011-184493, azo compounds described in JP 2011-145540, triarylmethane dye polymers described in Korean Published Patent No. 10-2020-0028160, xanthene compounds described in JP 2020-117638, phthalocyanine compounds described in International Publication No. 2020 / 174991, isoindoline compounds described in JP 2020-160279 or their salts, and Korean Published Patent No. 10-2020-00 The following compounds can be used: the compound represented by formula 1 described in Japanese Patent Publication No. 69442, the compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069730, the compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069070, the compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069067, the compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069062, the zinc halide phthalocyanine pigment described in Japanese Patent No. 6809649, and the isoindoline compound described in Japanese Patent Publication No. 2020-180176. In addition, the chromatic colorant may be a rotaxane, and the pigment skeleton may be used in a cyclic structure of the rotaxane, in a rod-shaped structure, or in both structures.

[0047] Two or more chromatic colorants may be used in combination. Furthermore, when two or more chromatic colorants are used in combination, the combination of two or more chromatic colorants may form black. Examples of such combinations include the following embodiments (1) to (7). When the resin composition contains two or more chromatic colorants and exhibits black color through a combination of two or more chromatic colorants, the resin composition of the present invention can be preferably used as a resin composition for forming near-infrared transmission filters. (1) An embodiment containing a red colorant and a blue colorant. (2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant. (3) A form containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant. (4) An embodiment containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant. (5) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant. (6) An embodiment containing a red colorant, a blue colorant, and a green colorant. (7) An embodiment containing a yellow colorant and a purple colorant.

[0048] (white color material) Examples of white colorants include inorganic pigments (white pigments) such as titanium dioxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. White pigments are preferably particles containing titanium atoms, with titanium dioxide being more preferred. Furthermore, white pigments are preferably particles with a refractive index of 2.10 or higher for light at a wavelength of 589 nm. The aforementioned refractive index is preferably between 2.10 and 3.00, and more preferably between 2.50 and 2.75.

[0049] Additionally, the white pigment can be titanium dioxide as described in "Titanium Dioxide: Physical Properties and Applied Technologies" by Manabu Seino, pages 13-45, published June 25, 1991, by Gihodo Publishing.

[0050] White pigments may consist not only of a single inorganic substance but also of particles compounded with other materials. For example, it is preferable to use particles having voids or other materials inside, particles with many inorganic particles attached to a core particle, or core-shell composite particles consisting of a core particle made of polymer particles and a shell layer made of inorganic nanoparticles. As for the core-shell composite particles consisting of a core particle made of polymer particles and a shell layer made of inorganic nanoparticles, for example, the description in paragraphs 0012 to 0042 of Japanese Patent Application Publication No. 2015-047520 can be referenced, and this content is incorporated herein.

[0051] White pigments can also be made using hollow inorganic particles. Hollow inorganic particles are inorganic particles with a structure that has a cavity inside, and are defined as inorganic particles that have a cavity surrounded by an outer shell. Examples of hollow inorganic particles include those described in Japanese Patent Publication No. 2011-075786, International Publication No. 2013 / 061621, and Japanese Patent Publication No. 2015-164881, and the contents of these publications are incorporated herein by reference.

[0052] (Black coloring agent) The black colorant is not particularly limited, and known materials can be used. In this specification, the term "black colorant" refers to a colorant that exhibits absorption over the entire wavelength range of 400 to 700 nm. The black colorant is preferably a black pigment. Among these, the black pigment is preferably a black pigment that conforms to the evaluation criterion Z described below. First, a composition is prepared containing a black pigment, a transparent resin matrix (such as acrylic resin), and a solvent, with the black pigment content being 60% by mass relative to the total solids. The obtained composition is applied to a glass substrate so that the thickness of the cured film after drying is 1 μm, and a cured film is formed. The light-shielding properties of the cured film after drying are evaluated using a spectrophotometer (such as Hitachi UV-3600). If the maximum transmittance of the cured film after drying at wavelengths of 400 to 700 nm is less than 10%, the black pigment can be determined to be a black pigment that conforms to evaluation criterion Z. For the black pigment, it is more preferable that the maximum transmittance of the cured film after drying at a wavelength of 400-700 nm is less than 8% according to evaluation criterion Z, and even more preferable that it is less than 5%.

[0053] The average primary particle size of the black pigment is preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. The above average primary particle size is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 20 nm or more, from the viewpoint of superior handling properties.

[0054] The black pigment may be an inorganic pigment (inorganic black pigment) or an organic pigment (organic black pigment). However, an inorganic black pigment is preferable because it results in a film with superior lightfastness.

[0055] Generally, black pigments tend to have lower dispersibility in resin compositions than other pigments. In particular, inorganic black pigments tend to have lower dispersibility in resin compositions. According to the resin composition of the present invention, even if it contains a black pigment, it is possible to make a resin composition with excellent pigment dispersibility, and therefore the effects of the present invention are particularly evident when using a black pigment (especially an inorganic black pigment).

[0056] As for the inorganic black pigment, there are no particular limitations as long as it has light-shielding properties and contains particles of an inorganic compound; however, known inorganic pigments can be used.

[0057] Examples of inorganic black pigments include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), yttrium (Y), aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag). Among these, metal oxides, metal nitrides, or metal oxynitrides containing one or more metal elements selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V), yttrium (Y), aluminum (Al), and iron (Fe) are preferred. In other words, inorganic black pigments may contain two or more metal atoms. The above-mentioned metal oxides, metal nitrides, and metal oxynitrides may also include particles containing other metal atoms. For example, metal nitride-containing particles may also be used, which may further contain atoms selected from groups 13 to 17 of the periodic table (preferably oxygen atoms and / or sulfur atoms). Furthermore, the above-mentioned metal oxides, metal nitrides, and metal oxynitrides may be coated with inorganic and / or organic materials. Examples of the inorganic substances mentioned above include metal atoms contained in the inorganic black pigment. Examples of the above-mentioned organic substances include organic substances having hydrophobic groups, and silane compounds are preferred.

[0058] The method for producing the above-mentioned metal nitrides, metal oxides, or metal oxynitrides is not particularly limited as long as it yields a black pigment with the desired physical properties, but known production methods such as gas-phase reaction methods can be used. Examples of gas-phase reaction methods include electric furnace methods and thermal plasma methods, but thermal plasma methods are preferred because they involve less impurity contamination, easily produce uniform particle sizes, and have high productivity. The above-mentioned metal nitrides, metal oxides, or metal oxynitrides may be subjected to surface modification treatment. For example, they may be surface modified with a surface treatment agent that combines a silicone group and an alkyl group. Examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0059] Examples of inorganic black pigments include zirconium nitride containing yttrium. The particle size (average primary particle diameter) of yttrium-containing zirconium nitride is preferably 10 to 100 nm, as this suppresses a decrease in light-shielding properties at a wavelength of 550 nm (visible light). The average primary particle diameter of yttrium-containing zirconium nitride powder can be measured by converting the measured specific surface area to a spherical shape. The yttrium is contained in a solid solution state within the zirconium nitride powder. In the spectral transmission spectrum of a 50 ppm dispersion of zirconium nitride powder containing yttrium, when X1 is the light transmittance at a wavelength of 550 nm and X2 is the light transmittance at a wavelength of 365 nm, X1 is preferably 7.5% or less, more preferably 6.5% or less. X2 is preferably 25% or more, more preferably 26% or more. The ratio of X2 to X1 (X2 / X1) is preferably 3.5 or greater, and more preferably 4.0 or greater.

[0060] The yttrium content is preferably 1.0 to 12.0% by mass, and more preferably 2.0 to 11.0% by mass, relative to the total mass of zirconium nitride and yttrium, in order to suppress the decrease in light-shielding properties at a wavelength of 550 nm (visible light). The above content can be measured by ICP (inductively coupled plasma) emission spectrometry.

[0061] Examples of zirconium nitride containing yttrium and methods for producing the same include those described in Japanese Patent Publication No. 2020-180036, the contents of which are incorporated herein by reference.

[0062] Examples of inorganic black pigments include zirconium nitride containing aluminum. Among the aluminum-containing zirconium nitrides, zirconium nitride coated with alumina is preferred. Coating the zirconium nitride with alumina improves its moisture resistance. The volume resistivity of alumina-coated zirconium nitride is 1 × 10⁻⁶ 6 Preferably Ω·cm or more, 1 × 10 7 A value of Ω·cm or greater is preferable. The volume resistivity of zirconium nitride coated with alumina can be determined as follows: Zirconium nitride coated with alumina is placed in a pressure vessel and compressed at 5-10 MPa to form a compacted powder, and the resistance of this compacted powder is measured with a digital multimeter. The volume resistivity (Ω·cm) of the powder is then obtained by multiplying the obtained resistance value by the thickness of the compacted powder and a resistivity correction factor (RCF) that is referenced based on the apparatus shape and the thickness of the compacted powder. The amount of alumina coating is preferably 1.5 to 9% by mass, and more preferably 3 to 7% by mass, relative to 100% by mass of zirconium nitride. The isoelectric point of zirconium nitride coated with alumina is preferably 5.7 or higher, and more preferably 5.8 or higher. The "isoelectric point of alumina-coated zirconium nitride" refers to the pH at which, when the pH of a dispersion of alumina-coated zirconium nitride is changed, the overall charge per particle becomes zero, and the powder does not move even when a voltage is applied to the dispersion. In other words, inorganic nitride powders, such as zirconium nitride powder, exhibit a large change in zeta potential when the pH changes, and have an isoelectric point at a certain pH where the surface potential (zeta potential) becomes zero and no electrophoresis is observed. The "zeta potential" refers to the potential of the slip surface at which liquid flow begins in an electrical double layer, which is an electrical double structure formed in a dispersion when ions with opposite polarity charges are attracted to a powder with a certain polarity charge. This zeta potential can be measured, for example, using a zeta potential meter (model: DT1202) manufactured by Dispersion Technology, as follows. This device uses the colloidal oscillation current method for measurement. The dispersion is placed in a container and sandwiched between a pair of electrodes, and a predetermined voltage is applied to these electrodes, causing the powder in the dispersion to move. As a result, polarization occurs between the charged particles and the counterions around them, generating an electric field called the colloidal oscillation potential, which can be detected as an electric current. This current is the colloidal vibrational current. The zeta potential can be determined from the measured colloidal vibrational current using Smoluchowski's equation and the coupled total theory. The pH at which the zeta potential becomes zero is the isoelectric point of the powder.

[0063] Zirconium nitride L coated with alumina * The value is preferably 13 or less. * "Value" refers to CIE1976L * a * b * This is the lightness index in the color space (measurement light source C: color temperature 6774K). (CIE1976L) * a * b * The color space was created by the International Commission on Illumination (CIE) in 1976 by converting the CIEXYZ color system. This is a color space defined such that a certain distance within the color system results in approximately equal perceptual step differences across all color regions. Furthermore, the lightness index L * value, a * Value and b * The value is CIE1976L * a * b * It is a quantity defined in a Cartesian coordinate system within a color space, and is expressed by equations (1) to (3). L * =116(Y / Y0) 1 / 3 -16 (1) a * =500[(X / X0) 1 / 3 -(Y / Y0) 1 / 3 (2) b * =200[(Y / Y0) 1 / 3 -(Z / Z0) 1 / 3 (3) However, X / X0, Y / Y0, and Z / Z0 > 0.008856, where X, Y, and Z are the tristimulus values ​​of the object's color. Also, X0, Y 0、 Z0 is the tristimulus value of the light source that illuminates the object's color, and is normalized to Y0=100. Also, the lightness index L of zirconium nitride coated with alumina. * The value is determined, for example, using a spectrophotometer (model: SE7700) manufactured by Nippon Denshoku Industries Co., Ltd. L * If the value is 13 or less, the blackness is sufficient, and the desired color tone is obtained as a black pigment.

[0064] The BET specific surface area of ​​zirconium nitride coated with alumina is 20 m². 2 A value of 1000mg or more is preferable. The upper limit is 1000mg. 2It is preferable that the amount is less than or equal to / g. The BET specific surface area is determined, for example, by using a specific surface area measuring device (model: SA1100) manufactured by Shibata Scientific Co., Ltd. to adsorb gas molecules (e.g., nitrogen gas) with a known adsorption area onto the surface of the above powder (black pigment), and then determining the amount of adsorption. However, by applying the BET formula (an formula that shows the relationship between the adsorption equilibrium pressure and the amount of adsorption at a constant temperature when the adsorption equilibrium state is reached at a constant temperature) to the information of the process in which gas molecules adsorbed on the surface of zirconium nitride coated with alumina transition from adsorption in the first layer to multilayer adsorption, the amount of gas molecules in only one layer can be measured, and the specific surface area can be measured accurately. 2 If the amount is 1 / g or more, the decrease in coloring power (color development) can be suppressed.

[0065] Examples of alumina-coated zirconium nitride and methods for producing the same include those described in Japanese Patent Publication No. 2020-158377, the details of which are incorporated herein by reference.

[0066] In particular, nitrides or oxynitrides of one or more metals selected from the group consisting of titanium, vanadium, zirconium, niobium, and iron are more preferred because they can suppress the occurrence of undercuts when forming a light-shielding film, and nitrides or oxynitrides of zirconium or titanium (titanium black) are even more preferred.

[0067] Titanium black is a black particle containing titanium oxynitride. Titanium black can be surface-modified as needed for purposes such as improving dispersibility and suppressing aggregation. Titanium black can be coated with silicon dioxide, titanium dioxide, germanium dioxide, aluminum dioxide, magnesium dioxide, or zirconium dioxide, and can also be treated with water-repellent substances as described in Japanese Patent Publication No. 2007-302836.

[0068] Methods for producing titanium black include a method of reducing a mixture of titanium dioxide and metallic titanium by heating it in a reducing atmosphere (Japanese Patent Publication No. 49-005432), a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a hydrogen-containing reducing atmosphere (Japanese Patent Publication No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Publication No. 60-065069, Japanese Patent Publication No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Publication No. 61-201610).

[0069] The particle size of titanium black is not particularly limited, but 10-45 nm is preferred, and 12-20 nm is more preferred. The specific surface area of ​​titanium black is not particularly limited, but in order for the water repellency after surface treatment with a water repellent to achieve the desired performance, the value measured by the BET (Brunauer, Emmett, Teller) method is 5-150 m². 2 It is preferable that the value be / g, and 20-100m 2 It is more preferable that it be / g.

[0070] Examples of Titanium Black include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (product names, manufactured by Mitsubishi Materials Corporation), Tilack D (product name, manufactured by Akaho Chemicals Co., Ltd.), and MT-150A (product name, manufactured by Teika Co., Ltd.).

[0071] The resin composition of the present invention may also preferably contain titanium black as a dispersion containing titanium black and Si atoms. In this embodiment, titanium black is contained as a dispersion in the resin composition. The content ratio of Si atoms to Ti atoms in the dispersion (Si / Ti) is preferably 0.05 to 0.5 by mass, and more preferably 0.07 to 0.4. Here, the above dispersion includes both titanium black in the state of primary particles and titanium black in the state of aggregates (secondary particles). Furthermore, if the Si / Ti ratio of the dispersed material is above a predetermined value, when the composition layer using the dispersed material is patterned by photolithography or the like, residue is less likely to remain in the removal area. Conversely, if the Si / Ti ratio of the dispersed material is below a predetermined value, the light-shielding ability tends to be good.

[0072] To change the Si / Ti ratio of the dispersed material (for example, to 0.05 or higher), the following methods can be used. First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and this mixture is reduced at a high temperature (for example, 850-1000°C) to obtain a dispersed material mainly composed of titanium black particles and containing Si and Ti. Titanium black with adjusted Si / Ti can be produced, for example, by the method described in paragraphs 0005 and 0016-0021 of Japanese Patent Application Publication No. 2008-266045. The Si / Ti content ratio in the dispersion can be measured, for example, using the method(2-1) or method(2-3) described in paragraphs 0054-0056 of International Publication No. 2011 / 049090.

[0073] In a dispersion containing titanium black and Si atoms, the titanium black can be the one described above. In addition, in this dispersion, one or more black pigments, such as composite oxides of multiple metals selected from Cu, Fe, Mn, V, and Ni, cobalt oxide, iron oxide, carbon black, and aniline black, may be used in combination with titanium black to adjust dispersibility, colorability, etc. In this case, it is preferable that the dispersion consisting of titanium black accounts for 50% by mass or more of the total dispersion.

[0074] Carbon black is another example of an inorganic black pigment. Examples of carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black. Carbon black can be produced using known methods such as the oil furnace process, or it can be a commercially available product. Specific examples of commercially available carbon black include inorganic black pigments such as CI Pigment Black 7.

[0075] As the carbon black, surface-treated carbon black is preferred. Surface treatment can modify the surface state of the carbon black particles and improve their dispersion stability in the composition. Examples of surface treatments include resin coating, surface treatment introducing acidic groups, and surface treatment with a silane coupling agent.

[0076] As the carbon black, carbon black coated with resin is preferred. By coating the surface of the carbon black particles with an insulating resin, the light-shielding and insulating properties of the film can be improved. Furthermore, the reliability of image display devices can be improved by reducing leakage current, etc. For this reason, it is suitable for applications where the film requires insulating properties. Examples of coating resins include epoxy resins, polyamides, polyamide-imides, novolac resins, phenolic resins, urea resins, melamine resins, polyurethanes, diallyl phthalate resins, alkylbenzene resins, polystyrene, polycarbonate, polybutylene terephthalate, and modified polyphenylene oxide. The content of the coating resin is preferably 0.1 to 40% by mass, and more preferably 0.5 to 30% by mass, relative to the total amount of carbon black and coating resin, in order to obtain superior light-shielding and insulating properties.

[0077] The crystallite size of the inorganic black pigment is preferably 10 nm or larger, and more preferably 20 nm or larger. The upper limit is preferably 60 nm or smaller, more preferably 50 nm or smaller, and even more preferably 40 nm or smaller. By setting the crystallite size of the inorganic black pigment within the above range, the transmitted light of the film exhibits a bluish-purple color with a peak wavelength of 400 nm or less, thereby improving light transmittance in the ultraviolet region. Because it exhibits superior transmittance in the ultraviolet region (especially i-rays (365 nm)) compared to conventional light-shielding materials, photocuring or photodissolution proceeds sufficiently to the bottom of the film, improving sensitivity. When the crystallite size is 10 nm or larger, the particle surface is less susceptible to oxidation, and the decrease in light-shielding properties is suppressed. When the crystallite size is 60 nm or smaller, the shift of the transmission peak to longer wavelengths when a colored film is formed is suppressed, which suppresses the decrease in light transmittance in the ultraviolet region, as well as the decrease in light-shielding properties in the visible light region.

[0078] The crystallite size can be determined, for example, by the following method. It can be calculated from the full width at half maximum of the X-ray diffraction peaks originating from the (111) plane in the X-ray diffraction spectrum when CuKα is used as the X-ray source. For example, when CuKα radiation is used as the X-ray source for zirconia compound particles containing zirconium nitride, zirconium oxide, and / or zirconium oxynitride, the X-ray diffraction spectra are as follows: In the case of zirconium nitride, a peak originating from the (111) plane is observed around the diffraction angle 2θ = 33.5~34.0°. In the case of zirconium oxide, a peak originating from the (011) plane is observed around the diffraction angle 2θ = 30.3°, and a peak originating from the (-111) plane is observed around the diffraction angle 2θ = 28.2°. In the case of zirconium oxynitride, a peak originating from the (211) plane is observed around 2θ = 33.4°. The crystallite size can then be calculated from the full width at half maximum of these X-ray diffraction peaks using Scherrer's equation shown in equation (4) below. Crystallite size (nm) = Kλ / βcosθ (4) β = √(β e 2 -β O 2 ) (5) In equation (4), K represents the constant 0.9. λ represents 0.15406 (nm). β is the value expressed in equation (5) above. θ is as described above. In equation (5), β eβ represents the full width at half maximum of the diffraction peak. O This represents the correction value for the full width at half maximum (0.12°). However, β, β e and β O It is calculated in radians. The X-ray diffraction spectrum is measured using wide-angle X-ray diffraction with the X-ray source being CuKα. For example, the RU-200R manufactured by Rigakusha can be used as an X-ray diffractometer. The measurement conditions are as follows: output power of 50kV / 200mA, slit system of 1°-1°-0.15mm-0.45mm, measurement step (2θ) of 0.02°, and scan speed of 2° / min. Furthermore, examples of the diffraction peak values ​​mentioned above include those shown in paragraphs 0027 to 0028 of Japanese Patent Publication No. 2009-091205, and these contents are incorporated herein by reference.

[0079] One method for achieving the crystallite size within the above range is to adjust the crystal growth conditions during particle synthesis by gas-phase reaction. For example, in the thermal plasma method, the crystallite size can be easily adjusted to the above range by adjusting the cooling time and cooling rate after the particles have been vaporized.

[0080] Examples of inorganic black pigments include zirconium as described in Japanese Patent Publication No. 2017-222559, International Publication No. 2019 / 130772, International Publication No. 2019 / 059359, and Japanese Patent Publication No. 2009-091205, the contents of which are incorporated herein by reference.

[0081] As for the organic black pigment used as a black pigment, there are no particular limitations as long as it has light-shielding properties and contains organic compounds as particles; however, known organic black pigments can be used. Examples of organic black pigments include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds or perylene compounds being preferred.

[0082] Examples of bisbenzofuranone compounds include those described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, and Japanese Patent Publication No. 2012-515234. Bisbenzofuranone compounds are available from BASF under the trade name "Irgaphor Black". Examples of perylene compounds include those described in Japanese Patent Publication No. 62-001753 and Japanese Patent Publication No. 63-026784. Perylene compounds are available as CIPigment Black 21, 30, 31, 32, 33 and 34.

[0083] The colorant used in the resin composition of the present invention may consist only of the black colorant described above, or it may further contain a chromatic colorant. According to this embodiment, a resin composition that can form a film with excellent light-shielding properties in the visible light region is easily obtained. When a black colorant and a chromatic colorant are used in combination as colorants, the mass ratio of the two is preferably black colorant:chromatic colorant = 100:10 to 300, and more preferably 100:20 to 200. Furthermore, it is preferable to use a black pigment as the black colorant, and a chromatic pigment as the chromatic colorant.

[0084] Preferred combinations of black pigments and chromatic pigments include, for example, the following: (A-1) An embodiment containing an organic black colorant and a blue colorant. (A-2) An embodiment containing an organic black colorant, a blue colorant, and a yellow colorant. (A-3) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant, and a red colorant. (A-4) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant, and a purple colorant.

[0085] In the embodiment (A-1) described above, the mass ratio of the organic black pigment to the blue pigment is preferably 100:1 to 70, more preferably 100:5 to 60, and even more preferably 100:10 to 50. In the aspect of (A-2) above, the mass ratio of the organic black colorant, blue colorant, and yellow colorant is preferably organic black colorant: blue colorant: yellow colorant = 100:10 to 90:10 to 90, more preferably 100:15 to 85:15 to 80, and even more preferably 100:20 to 80:20 to 70. In the aspect of (A-3) above, the mass ratio of the organic black colorant, blue colorant, yellow colorant, and red colorant is preferably organic black colorant: blue colorant: yellow colorant: red colorant = 100:20 to 150:1 to 60:10 to 100, more preferably 100:30 to 130:5 to 50:20 to 90, and even more preferably 100:40 to 120:10 to 40:30 to 80. In the aspect of (A-4) above, the mass ratio of the organic black colorant, blue colorant, yellow colorant, and purple colorant is preferably organic black colorant: blue colorant: yellow colorant: purple colorant = 100:20 to 150:1 to 60:10 to 100, more preferably 100:30 to 130:5 to 50:20 to 90, and even more preferably 100:40 to 120:10 to 40:30 to 80.

[0086] (Near-infrared absorbing colorant) The near-infrared absorbing colorant is preferably a pigment, more preferably an organic pigment. Also, the near-infrared absorbing colorant preferably has a maximum absorption wavelength in the range exceeding 700 nm and not exceeding 1400 nm. Further, the maximum absorption wavelength of the near-infrared absorbing colorant is preferably 1200 nm or less, more preferably 1000 nm or less, and even more preferably 950 nm or less. Also, the near-infrared absorbing colorant has an absorbance A at a wavelength of 550 nm 550 and an absorbance A at the maximum absorption wavelength max and the ratio of A 550 / A maxIt is preferable that the ratio is 0.1 or less, more preferably 0.05 or less, even more preferably 0.03 or less, and particularly preferably 0.02 or less. There is no particular lower limit, but for example it can be 0.0001 or more, or 0.0005 or more. If the above-mentioned ratio of absorbances is within the above range, a near-infrared absorbing colorant with excellent visible light transparency and near-infrared shielding properties can be obtained. In this invention, the maximum absorption wavelength of the near-infrared absorbing colorant and the absorbance values ​​at each wavelength are values ​​obtained from the absorption spectrum of a film formed using a resin composition containing the near-infrared absorbing colorant.

[0087] There are no particular limitations on the near-infrared absorbing colorants, but examples include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, crokonium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, and dithiolene metal complexes. Examples of pyrrolopyrrole compounds include those described in paragraphs 0016 to 0058 of Japanese Patent Publication No. 2009-263614, those described in paragraphs 0037 to 0052 of Japanese Patent Publication No. 2011-068731, and those described in paragraphs 0010 to 0033 of International Publication No. 2015 / 166873. Examples of squarylium compounds include the compounds described in paragraphs 0044 to 0049 of Japanese Patent Publication No. 2011-208101, the compounds described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, the compounds described in paragraph 0040 of International Publication No. 2016 / 181987, the compounds described in Japanese Patent Publication No. 2015-176046, and the compounds described in paragraph 0072 of International Publication No. 2016 / 190162. Examples include compounds, compounds described in paragraphs 0196 to 0228 of Japanese Patent Publication No. 2016-074649, compounds described in paragraph 0124 of Japanese Patent Publication No. 2017-067963, compounds described in International Publication No. 2017 / 135359, compounds described in Japanese Patent Publication No. 2017-114956, compounds described in Japanese Patent No. 6197940, and compounds described in International Publication No. 2016 / 120166. Examples of cyanine compounds include those described in paragraphs 0044 to 0045 of Japanese Patent Publication No. 2009-108267, those described in paragraphs 0026 to 0030 of Japanese Patent Publication No. 2002-194040, those described in Japanese Patent Publication No. 2015-172004, those described in Japanese Patent Publication No. 2015-172102, those described in Japanese Patent Publication No. 2008-088426, those described in paragraph 0090 of International Publication No. 2016 / 190162, and those described in Japanese Patent Publication No. 2017-031394. Examples of croconium compounds include those described in Japanese Patent Publication No. 2017-082029.Examples of iminium compounds include the compounds described in Japanese Patent Publication No. 2008-528706, Japanese Patent Application Publication No. 2012-012399, Japanese Patent Application Publication No. 2007-092060, and the compounds described in paragraphs 0048 to 0063 of International Publication No. 2018 / 043564. Examples of phthalocyanine compounds include the compounds described in paragraph 0093 of Japanese Patent Application Publication No. 2012-077153, oxytitanium phthalocyanine described in Japanese Patent Application Publication No. 2006-343631, the compounds described in paragraphs 0013 to 0029 of Japanese Patent Application Publication No. 2013-195480, the vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, and the compounds described in International Publication No. 2020 / 071470. Examples of naphthalocyanine compounds include those described in paragraph 0093 of Japanese Patent Publication No. 2012-077153. Examples of dithiolene metal complexes include those described in Japanese Patent Publication No. 5733804.

[0088] Furthermore, as near-infrared absorbing colorants, the following are used: the squarylium compound described in Japanese Patent Publication No. 2017-197437, the squarylium compound described in Japanese Patent Publication No. 2017-025311, the squarylium compound described in International Publication No. 2016 / 154782, the squarylium compound described in Japanese Patent No. 5884953, the squarylium compound described in Japanese Patent No. 6036689, and the squarylium compound described in Japanese Patent No. 5810604. The squarylium compounds described in International Publication No. 2017 / 213047, paragraphs 0090-0107, the pyrrole ring-containing compounds described in Japanese Patent Publication No. 2018-054760, paragraphs 0019-0075, the pyrrole ring-containing compounds described in Japanese Patent Publication No. 2018-040955, paragraphs 0078-0082, and paragraphs 0043-006 of Japanese Patent Publication No. 2018-002773. The pyrrole ring-containing compounds described in 9, the squarylium compounds having an aromatic ring at the amide α position described in paragraphs 0024 to 0086 of JP 2018-041047, the amide-linked squarylium compounds described in JP 2017-179131, the compounds having a pyrrole-bis-type squarylium skeleton or crokonium skeleton described in JP 2017-141215, the dihydrocarbazole-bis-type squarylium compounds described in JP 2017-082029, the asymmetric-type compounds described in paragraphs 0027 to 0114 of JP 2017-068120, the pyrrole ring-containing compounds (carbazole type) described in JP 2017-067963, the phthalocyanine compounds described in Japanese Patent No. 6251530, the squarylium compounds described in JP 2020-075959, Copper complexes, etc., as described in Korean Published Patent No. 10-2019-0135217 can also be used.

[0089] The colorant content in the total solids of the resin composition is preferably 20 to 90% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less. Furthermore, the pigment content in the total solids of the resin composition is preferably 20 to 90% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less. Furthermore, the dye content in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0090] A preferred embodiment of the resin composition of the present invention is one in which the colorant contained in the resin composition contains a black pigment, and the content of the black pigment in the total solid content of the resin composition is 65% by mass or more. According to this embodiment, a film with excellent light-shielding properties can be formed. In this embodiment, the content of the black pigment in the total solid content of the resin composition is preferably 70% by mass or more, and more preferably 75% by mass or more. The upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less. Furthermore, the content of the black pigment in the colorant is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and particularly preferably 100% by mass.

[0091] <Resin B> (Specific resin) The resin composition of the present invention comprises resin B (hereinafter also referred to as "resin"). The resin contained in the resin composition comprises resin B1 (hereinafter also referred to as "specific resin") which comprises an acid anhydride group and a polymer chain containing repeating units of at least one structure selected from a polyether structure and a polyester structure.

[0092] The specific resin preferably has acid anhydride groups at its ends. The number of acid anhydride groups in the specific resin is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1, because it can further improve the dispersibility of the pigment.

[0093] The acid anhydride group possessed by the specific resin is preferably a cyclic acid anhydride group because it can further improve the dispersibility of the pigment.

[0094] The acid anhydride group possessed by the specific resin is preferably a group represented by any one of Formula (RAH-1) to Formula (RAH-7), and more preferably a group represented by Formula (RAH-4).

Chemical formula

[0095] r2, r3, r4, r6 and r7 are each independently preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0. r5 is preferably 0 or 1, and even more preferably 0.

[0096] R AH1 ~R AH11 Examples of the substituents represented by include the substituents T described below, and are preferably a halogen atom, a carboxy group, an alkyl group or a hydroxy group, and more preferably a carboxy group.

[0097] The polymer chain of a particular resin may contain at least one selected from ethylenically unsaturated bond-containing groups, epoxy groups, and oxetanyl groups. These groups are preferably located at the ends of the polymer chain. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

[0098] The polymer chain of the specific resin is preferably a polymer chain containing repeating units represented by any of the formulas (P-1) to (P-4). [ka]

[0099] In the above formula, R G1 ~R G4 Each of these independently represents an alkylene group. G1 ~R G4 The alkylene group represented is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and even more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.

[0100] The polymer chain of a particular resin may contain two or more repeating units. For example, it may contain a repeating unit represented by any of formulas (P1-1) to (P1-3) and a repeating unit represented by formula (P1-4).

[0101] The terminal structure of the polymer chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, ethylenically unsaturated bond-containing groups, epoxy groups, and oxetanyl groups.

[0102] The specific resin is preferably a resin represented by formula (1). [ka] In formula (1), R 1 This represents an acid anhydride group, X 1 and X 2 Each of these is independent of the following: single bond, -O-, -CO-, -COO-, -OCO-, -NR x1 -, -CONR x1 -, -NR x1 CO- or -S- represents R x1 represents a hydrogen atom or substituent, L 1 This represents a single bond or an m+n valence linking group. P 1 This represents a polymer chain containing repeating units of at least one structure selected from polyether structures and polyester structures. m and n each represent an independent integer greater than or equal to 1.

[0103] R in equation (1) 1 The acid anhydride group represented is preferably a cyclic acid anhydride group because it can further improve the dispersibility of the pigment.

[0104] R in equation (1) 1 The acid anhydride group represented by is preferably a group represented by any of the above formulas (RAH-1) to (RAH-7), and more preferably a group represented by formula (RAH-4).

[0105] P in equation (1) 1 The polymer chain represented by may contain at least one selected from ethylenically unsaturated bond-containing groups, epoxy groups, and oxetanyl groups. These groups are preferably located at the ends of the polymer chain. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

[0106] P in equation (1) 1The polymer chain represented by is preferably a polymer chain containing repeating units represented by any of the above formulas (P-1) to (P-4).

[0107] P in equation (1) 1 The terminal structure of the polymer chain represented by is not particularly limited. It may be a hydrogen atom or a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, ethylenically unsaturated bond-containing groups, epoxy groups, and oxetanyl groups.

[0108] P 1 The polymer chain represented is preferably a polymer chain represented by formula (P100). *-P 10 -Lp 10 -(Rp 10 ) q ...(P100) In formula (P100), * represents a coupling, P 10 This represents a polymer chain containing repeating units of at least one structure selected from polyether structures and polyester structures. LP 10 represents a single bond or a q+1 valent group, Rp 10 This represents a hydrogen atom or substituent. q represents either 1 or 2.

[0109] P in equation (P100) 10 In this, the repeating unit of the polyether structure is preferably the repeating unit represented by the above formula (P-4). 10 In this context, the repeating unit of the polyester structure is preferably a repeating unit represented by any of the above formulas (P-1) to (P-3).

[0110] Lp of formula (P100) 10The q+1 valent group represented by can be a hydrocarbon group, a heterocyclic group, or -NRp L1 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp L1 CO- and CONRp L1 - and groups formed by combining two or more of these are examples. Rp L1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and is preferably a hydrogen atom. Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The cyclic aliphatic hydrocarbon group may be monocyclic or fused. The cyclic aliphatic hydrocarbon group may also have a crosslinking structure. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have substituents. An example of a substituent is substituent T, which will be described later. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. A five-membered or six-membered heterocyclic group is preferred. Examples of heteroatoms constituting the ring of the heterocyclic group include nitrogen, oxygen, and sulfur atoms. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic group or a fused ring. The heterocyclic group may have substituents. Examples of substituents include substituent T, which will be discussed later.

[0111] Rp of formula (P100) 10 Examples of substituents represented by include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, ethylenically unsaturated bond-containing groups, epoxy groups, and oxetanyl groups, with ethylenically unsaturated bond-containing groups, epoxy groups, and oxetanyl groups being preferred. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

[0112] In formula (P100), q represents either 1 or 2, and is preferably 1.

[0113] P 1 Specific examples of polymer chains represented by include P1-1 to P1-22 shown below. In the following formulas, * represents a linkage. [ka] [ka]

[0114] L in equation (1) 1 L represents a single bond or an m+n valence linking group. 1 The m+n valent linking groups represented by include hydrocarbon groups, heterocyclic groups, and -NR groups. L1 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NR L1 CO- and -CONR L1 - and groups formed by combining two or more of these are examples. L1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and is preferably a hydrogen atom. Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The cyclic aliphatic hydrocarbon group may be monocyclic or fused. The cyclic aliphatic hydrocarbon group may also have a crosslinking structure. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have substituents. An example of a substituent is substituent T, which will be described later. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. A five-membered or six-membered heterocyclic group is preferred. Examples of heteroatoms constituting the ring of the heterocyclic group include nitrogen, oxygen, and sulfur atoms. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic group or a fused ring. The heterocyclic group may have substituents. Examples of substituents include substituent T, which will be discussed later.

[0115] The m+n valence linking group is hydrocarbon group; Heterocyclic group; hydrocarbon groups, heterocyclic groups, -NR L1 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NR L1 CO- and -CONR L1 A group of structures that combines at least one group selected from; or, Heterocyclic groups, hydrocarbon groups, -NR L1 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NR L1 CO- and -CONR L1 It is preferable that the group has a structure that combines at least one group selected from the above.

[0116] L 1 Specific examples of the m+n valence linking group represented by include -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, and (Z1-1) to (Z1-23) shown below. [ka]

[0117] X in equation (1) 1 and X 2 Each of these is independent of the following: single bond, -O-, -CO-, -COO-, -OCO-, -NR x1 -, -CONR x1 -, -NR x1 R represents CO- or -S-.x1 R represents a hydrogen atom or substituent. x1 Examples of substituents represented by are substituents T, which will be described later, and are preferably alkyl groups. x1 It is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

[0118] X in equation (1) 1 -S-, -CO-, -COO-, -OCO-, -NR x1 -, -CONR x1 -or-NR x1 It is preferably CO-, more preferably -CO-, -COO- or -OCO-, and even more preferably -COO-. X in equation (1) 2 These are single bonds, -O- or -NR x1 - is preferable. L in equation (1) 1 X is a single bond, 1 If -COO-, X 2 It is preferable that the bond is a single bond.

[0119] In formula (1), m and n each represent an integer of 1 or greater independently. m is preferably an integer between 1 and 5, more preferably an integer between 1 and 3, even more preferably 1 or 2, and particularly preferably 1 because it can further improve the dispersibility of the pigment. n is preferably an integer between 1 and 5, more preferably an integer between 1 and 4, even more preferably an integer between 1 and 3, even more preferably 1 or 2, and particularly preferably 1 because it can further suppress the generation of developing residue.

[0120] The specific resin is preferably the resin represented by formula (2). [ka] In formula (2), X 2 These are single bonds, -O-, -CO-, -COO-, -OCO-, -NR x1 -, -CONR x1 -, -NRx1 CO- or -S- represents R x1 represents a hydrogen atom or substituent, L 1 This represents a single bond or an m+n valence linking group. P 1 This represents a polymer chain containing repeating units of at least one structure selected from polyether structures and polyester structures. m and n each represent an independent integer greater than or equal to 1.

[0121] X in equation (2) 2 X in equation (1) 2 This is synonymous with the same thing, and the preferred range is also similar. L in equation (2) 1 L is in equation (1) 1 This is synonymous with the same thing, and the preferred range is also similar. P in equation (2) 1 P in equation (1) 1 This is synonymous with the same thing, and the preferred range is also similar. The value of m in equation (2) is the same as the value of m in equation (1), and the preferred range is also the same. The value of n in equation (2) is the same as the value of n in equation (1), and the preferred range is also the same.

[0122] (substituent T) The substituent T may be an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group (preferably a heteroaryloxy group having 1 to 30 carbon atoms), or an acyl group (preferably Acyl group having 2 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfa Moyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably a heteroarylthio group having 1 to 30 carbon atoms), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), arylsulfonyl group (preferably an arylsulfonyl group having 6 to 30 carbon atoms), heteroarylsulfonyl group (preferably a group having 1 to 30 carbon atoms) 30 heteroarylsulfonyl groups), alkylsulfinyl groups (preferably alkylsulfinyl groups with 1 to 30 carbon atoms), arylsulfinyl groups (preferably arylsulfinyl groups with 6 to 30 carbon atoms), heteroarylsulfinyl groups (preferably heteroarylsulfinyl groups with 1 to 30 carbon atoms), ureido groups (preferably ureido groups with 1 to 30 carbon atoms), phosphate amide groups (preferably phosphate amide groups with 1 to 30 carbon atoms), hydroxyl groups, mercapto groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), cyano groups, sulfo groups,Examples include carboxyl groups, nitro groups, hydroxamic acid groups, sulfino groups, hydrazino groups, imino groups, and heterocyclic groups. These groups may have further substituents if they are further substituted. Further substituents include the groups described above under substituent T.

[0123] The weight-average molecular weight of the specific resin is preferably 500 or more and less than 10,000. The lower limit is preferably 800 or more, and more preferably 1,000 or more. The upper limit is preferably 8,000 or less, and more preferably 6,000 or less.

[0124] When a specific resin has ethylenically unsaturated bonding groups, the ethylenically unsaturated bonding group value of the specific resin is preferably 0.1 to 2.0 mmol / g, more preferably 0.2 to 1.5 mmol / g, and even more preferably 0.3 to 1.0 mmol / g. Furthermore, if the specific resin has epoxy groups, the epoxy value of the specific resin is preferably 0.1 to 2.0 mmol / g, more preferably 0.2 to 1.5 mmol / g, and even more preferably 0.3 to 1.0 mmol / g. Furthermore, if the specific resin has an oxetanyl group, the oxetanyl group value of the specific resin is preferably 0.1 to 2.0 mmol / g, more preferably 0.2 to 1.5 mmol / g, and even more preferably 0.3 to 1.0 mmol / g.

[0125] Specific resins can be synthesized, for example, by the following methods. (1) A method of synthesizing macromonomers obtained by ring-opening polymerization of lactones using compounds having a hydroxyl group and a mercapto group (for example, mercaptoethanol, mercaptopropanol, mercaptohexanol, mercaptoglycerol, etc.), and reacting them with an acid anhydride or acid anhydride chloride. (2) A method of synthesis by reacting a macromonomer obtained by ring-opening polymerization of a lactone using a compound having a hydroxyl group (e.g., 2-ethylhexanol) with an acid anhydride or acid anhydride chloride.

[0126] In the resin composition, some specific resins may react with other materials in the resin composition.

[0127] (Other resins) The resin composition of the present invention may contain resins other than the specific resins described above. Examples of other resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene etherphosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins, and cardo resins. Other resins include the resin described in the examples of International Publication No. 2016 / 088645, the resin described in JP 2017-057265, the resin described in JP 2017-032685, the resin described in JP 2017-075248, the resin described in JP 2017-066240, the resin described in JP 2017-167513, the resin described in JP 2017-173787, the resin described in paragraphs 0041 to 0060 of JP 2017-206689, the resin described in paragraphs 0022 to 0071 of JP 2018-010856, and JP 2016-2 The following resins may also be used: the block polyisocyanate resin described in Japanese Patent Publication No. 22891, the resin described in Japanese Patent Application Publication No. 2020-122052, the resin described in Japanese Patent Application Publication No. 2020-111656, the resin described in Japanese Patent Application Publication No. 2020-139021, the resin described in Japanese Patent Application Publication No. 2017-138503 which includes a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain, the resin described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Application Publication No. 2020-186325, and the resin represented by formula 1 described in Korean Published Patent No. 10-2020-0078339. In addition, other resins may include by-products from the synthesis of specific resins or modified products of specific resins.

[0128] The weight-average molecular weight (Mw) of the other resins is preferably between 3,000 and 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0129] For other resins, it is preferable to use resins that are alkali-developable or resins that act as dispersants.

[0130] [Resin with alkali developability] The weight-average molecular weight (Mw) of the alkali-developable resin is preferably between 3,000 and 2,000,000. The upper limit is more preferably 1,000,000 or less, and even more preferably 500,000 or less. The lower limit is more preferably 4,000 or more, and even more preferably 5,000 or more.

[0131] Examples of alkali-developable resins include (meth)acrylic resins, polyimine resins, polyether resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and polyimide resins, with (meth)acrylic resins and polyimine resins being preferred, and (meth)acrylic resins being more preferred.

[0132] As a resin having alkali developability, it is preferable to use a resin having acidic groups. Examples of acidic groups include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, phosphonic acid groups, active imide groups, and sulfonamide groups, with carboxyl groups being preferred. Alternatively, as a resin having acidic groups, a resin in which acidic groups are introduced by reacting an acid anhydride with a hydroxyl group generated by epoxy ring opening may be used. An example of such a resin is the resin described in Japanese Patent Publication No. 6349629. The resin having acidic groups can be used, for example, as an alkali-soluble resin. The alkali-soluble resin may be a cardo resin having a cardo skeleton. An example of a cardo resin is V-259ME (manufactured by Nippon Steel & Sumitomo Metal Corporation).

[0133] The alkali-developable resin preferably contains repeating units having acid groups, and more preferably contains 1 to 70 mol% of the total repeating units of the resin. The upper limit of the content of repeating units having acid groups is preferably 50 mol% or less, and more preferably 40 mol% or less. The lower limit of the content of repeating units having acid groups is preferably 2 mol% or more, and more preferably 5 mol% or more.

[0134] The acid value of the alkali-developable resin is preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, even more preferably 120 mg KOH / g or less, and particularly preferably 100 mg KOH / g or less. Furthermore, the acid value of the alkali-developable resin is preferably 5 mg KOH / g or more, more preferably 10 mg KOH / g or more, and even more preferably 20 mg KOH / g or more.

[0135] The alkali-developable resin is also preferably further possessing an ethylenically unsaturated bond-containing group. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, allyl groups, and (meth)acryloyl groups, with allyl and (meth)acryloyl groups being preferred, and (meth)acryloyl groups being more preferred.

[0136] The alkali-developable resin may also preferably contain repeating units derived from monomer components including the compound represented by the following formula (ED1) and / or the compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers").

[0137] [ka]

[0138] In formula (ED1), R 1 and R 2 Each of these independently represents a hydrocarbon group having 1 to 25 carbon atoms, which may have a hydrogen atom or a substituent. [ka] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Regarding the details of formula (ED2), the description in JP-A-2010-168539 can be referred to, and this content is incorporated herein.

[0139] As a specific example of the ether dimer, for example, the description in paragraph number 0317 of JP-A-2013-029760 can be referred to, and this content is incorporated herein.

[0140] It is also preferable that the resin having alkali developability contains a repeating unit derived from a compound represented by the following formula (X).

Chemical formula

[0141] Examples of the resin having alkali developability include resins having the following structures. In the following structural formulas, Me represents a methyl group.

Chemical formula

[0142] 〔Dispersant〕 The resin composition of the present invention may also contain a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, an acidic dispersant (acidic resin) refers to a resin in which the amount of acidic groups is greater than the amount of basic groups. When the total amount of acidic groups and basic groups is taken as 100 mol%, it is preferable that the acidic group accounts for 70 mol% or more of the acidic resin, and more preferably a resin consisting substantially only of acidic groups. The acidic group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mg KOH / g, more preferably 50 to 105 mg KOH / g, and even more preferably 60 to 105 mg KOH / g. A basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acidic groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acidic groups and basic groups is set to 100 mol%. The basic groups of the basic dispersant are preferably amino groups.

[0143] The resin used as a dispersant preferably contains repeating units having acidic groups.

[0144] The resin used as a dispersant is preferably a graft polymer. Examples of graft polymers include those described in paragraphs 0025 to 0094 of Japanese Patent Application Publication No. 2012-255128, the details of which are incorporated herein by reference.

[0145] The resin used as a dispersant is preferably a polyimine-based dispersant (polyimine resin) containing a nitrogen atom in at least one of its main chain and side chains. Preferred polyimine-based dispersants are resins having a main chain with a substructure having a pKa of 14 or less and side chains with 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and side chains. The basic nitrogen atom is not particularly limited as long as it exhibits basic properties. Examples of polyimine-based dispersants include the resins described in paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, the details of which are incorporated herein by reference.

[0146] The resin used as a dispersant is preferably a resin with a structure in which multiple polymer chains are bonded to the core. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0147] Furthermore, the dispersant can also be the block copolymer (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, the resin described in Japanese Patent Application Publication No. 2018-087939, the polyethyleneimine having polyester side chains described in International Publication No. 2016 / 104803, the block copolymer described in International Publication No. 2019 / 125940, the block polymer having acrylamide structural units described in Japanese Patent Application Publication No. 2020-066687, the block polymer having acrylamide structural units described in Japanese Patent Application Publication No. 2020-066688, the dispersant described in International Publication No. 2016 / 104803, the resin described in Japanese Patent Application Publication No. 2019-095548, and others.

[0148] Dispersants are also available commercially, and specific examples include the DISPERBYK series from BYKChemie (e.g., DISPERBYK-111, 161, etc.) and the Solsperse series from Lubrizol (e.g., Solsperse 36000, etc.). In addition, pigment dispersants described in paragraphs 0041 to 0130 of Japanese Patent Application Publication No. 2014-130338 can also be used, and this information is incorporated herein.

[0149] Furthermore, the resin described above as a dispersant can also be used for purposes other than dispersing. For example, it can be used as a binder.

[0150] The resin content in the total solids of the resin composition is preferably 5 to 60% by mass. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0151] The content of the above-mentioned specific resin in the total solid content of the resin composition is preferably 0.1 to 60% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0152] The content of the specified resin mentioned above is preferably 10 to 80 parts by mass per 100 parts by mass of pigment. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. The upper limit is preferably 70 parts by mass or less, and more preferably 50 parts by mass or less.

[0153] The total content of the colorant and the specified resin mentioned above in the total solid content of the resin composition is preferably 30 to 100% by mass. The lower limit is more preferably 35% by mass or more, and even more preferably 40% by mass or more. The upper limit is more preferably 90% by mass or less, and even more preferably 80% by mass or less.

[0154] In the resin composition, the content of the other resins mentioned above is preferably 230 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 150 parts by mass or less, per 100 parts by mass of the specified resin mentioned above. The lower limit may be 0 parts by mass, or it may be 5 parts by mass or more, or it may be 10 parts by mass or more. Furthermore, it is also preferable that the resin composition substantially does not contain the other resins mentioned above. According to this embodiment, better dispersibility can be obtained. Substantially containing other resins means that the content of other resins in the total solid content of the resin composition is 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably not containing any resins at all.

[0155] <Solvent C> The resin composition of the present invention contains solvent C (hereinafter referred to as "solvent"). The solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the resin composition. The solvent is preferably an organic solvent. Examples of solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. It is preferable to include at least one selected from ester solvents, ether solvents, alcohol solvents, and ketone solvents because they have good affinity with specific resins and can further improve the dispersibility of pigments. For further details, refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. Furthermore, ester solvents and ketone solvents substituted with cyclic alkyl groups can also be used.

[0156] 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, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, and anisole. However, the amount of aromatic hydrocarbons used as organic solvents (benzene, toluene, xylene, ethylbenzene, etc.) may be reduced for environmental reasons (for example, it may be possible to reduce the amount to 50 ppm (parts per million) or less, 10 ppm or less, or 1 ppm or less relative to the total amount of organic solvent).

[0157] In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015). Examples of methods for removing impurities such as metals from the organic solvent include distillation (such as molecular distillation and thin-film distillation) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0158] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Also, only one type of isomer may be contained, or a plurality of types may be contained.

[0159] The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.

[0160] The content of the solvent in the resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.

[0161] <Pigment Derivative> The resin composition of the present invention may contain a pigment derivative. Examples of pigment derivatives include compounds having a structure in which a portion of the chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group. Examples of chromophores constituting the pigment derivative include a quinoline skeleton, a benzimidazolon skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, a perinone skeleton, a perylene skeleton, a thioindigo skeleton, an isoindoline skeleton, an isoindolinone skeleton, a quinophthalone skeleton, a surene skeleton, and a metal complex skeleton. The quinoline skeleton, benzimidazolon skeleton, diketopyrrolopyrrole skeleton, azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferred, and the azo skeleton and the benzimidazolon skeleton are more preferred. The acid group of the pigment derivative is preferably a sulfo group or a carboxyl group, and more preferably a sulfo group. The basic group possessed by the pigment derivative is preferably an amino group, and more preferably a tertiary amino group.

[0162] As a pigment derivative, a pigment derivative with excellent visible light transparency (hereinafter also referred to as a transparent pigment derivative) can be used. The maximum molar extinction coefficient (εmax) of the transparent pigment derivative in the wavelength region of 400-700 nm is 3000 L·mol -1 ·cm -1 Preferably, the following: 1000 L·mol -1 ·cm -1 It is more preferable that the following conditions apply: 100 L·mol -1 ·cm -1 It is even more preferable that the following conditions are met: The lower limit of εmax is, for example, 1 L·mol. -1 ·cm -1 That is all. 10 L·mol -1 ·cm -1 That's fine too.

[0163] The crystallite size of the pigment derivative is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm. The crystallite size can be determined from the full width at half maximum of the diffraction angle peak using an X-ray diffractometer, and is calculated using Scherrer's formula. The crystallite size of the pigment derivative can be adjusted by known methods such as adjusting the manufacturing conditions or grinding after manufacturing. Any grinding method that can adjust the crystallite size is acceptable, but dry grinding and wet grinding are examples. Dry grinding is preferred because it does not require solvent removal and there is a low concern about re-aggregation.

[0164] Specific examples of pigment derivatives include the compounds described in Japanese Patent Publication No. 56-118462, Japanese Patent Publication No. 63-264674, Japanese Patent Publication No. 01-217077, Japanese Patent Publication No. 03-009961, Japanese Patent Publication No. 03-026767, Japanese Patent Publication No. 03-153780, Japanese Patent Publication No. 03-045662, Japanese Patent Publication No. 04-285669, and Compounds described in Japanese Patent Publication No. 06-145546, compounds described in Japanese Patent Publication No. 06-212088, compounds described in Japanese Patent Publication No. 06-240158, compounds described in Japanese Patent Publication No. 10-030063, compounds described in Japanese Patent Publication No. 10-195326, compounds described in paragraphs 0086-0098 of International Publication No. 2011 / 024896, compounds described in paragraphs 0063-0094 of International Publication No. 2012 / 102399, International Publication No. 2017 The compound described in paragraph 0082 of Patent No. 038252, the compound described in paragraph 0171 of JP 2015-151530, the compound described in paragraphs 0162-0183 of JP 2011-252065, the compound described in JP 2003-081972, the compound described in Patent No. 5299151, the compound described in JP 2015-172732, the compound described in JP 2014-199308, JP 2014-0855 Examples include the compounds described in Japanese Patent Publication No. 62, the compounds described in Japanese Patent Publication No. 2014-035351, the compounds described in Japanese Patent Publication No. 2008-081565, the compounds described in Japanese Patent Publication No. 2019-109512, the compounds described in Japanese Patent Publication No. 2019-133154, the diketopyrrolopyrrole compounds having thiol linking groups described in International Publication No. 2020 / 002106, the benzimidazolone compounds described in Japanese Patent Publication No. 2018-168244, or salts thereof.

[0165] The pigment derivative content is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, per 100 parts by mass of pigment. Only one type of pigment derivative may be used, or two or more types may be used in combination.

[0166] <Polymerizable monomers> The resin composition of the present invention preferably contains a polymerizable monomer. For example, known compounds that can be crosslinked by radicals, acids, or heat can be used as the polymerizable monomer. Examples of polymerizable monomers include compounds having ethylenically unsaturated bond-containing groups and compounds having cyclic ether groups, with compounds having ethylenically unsaturated bond-containing groups being preferred. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. Examples of cyclic ether groups include epoxy groups and oxetane groups. Compounds having ethylenically unsaturated bond-containing groups can preferably be used as radical polymerizable monomers. Compounds having cyclic ether groups can preferably be used as cationic polymerizable monomers. Polymerizable monomers are preferably polyfunctional polymerizable monomers. That is, polymerizable monomers are preferably monomers having two or more polymerizable groups such as ethylenically unsaturated bond-containing groups and cyclic ether groups.

[0167] The molecular weight of the polymerizable monomer is preferably between 100 and 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.

[0168] (Compounds containing ethylenically unsaturated bond groups) The compound having an ethylenically unsaturated bond-containing group used as a polymerizable monomer is preferably a polyfunctional compound. Specifically, it is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing three or more ethylenically unsaturated bond-containing groups, even more preferably a compound containing three to fifteen ethylenically unsaturated bond-containing groups, and even more preferably a compound containing three to six ethylenically unsaturated bond-containing groups. Furthermore, the compound having an ethylenically unsaturated bond-containing group is preferably a 3 to 15-functional (meth)acrylate compound, and more preferably a 3 to 6-functional (meth)acrylate compound. Specific examples of compounds having an ethylenically unsaturated bond-containing group include the compounds described in paragraphs 0095 to 0108 of Japanese Patent Publication No. 2009-288705, paragraph 0227 of Japanese Patent Publication No. 2013-029760, paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970, paragraphs 0034 to 0038 of Japanese Patent Publication No. 2013-253224, paragraph 0477 of Japanese Patent Publication No. 2012-208494, Japanese Patent Publication No. 2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, and Japanese Patent Publication No. 2017-194662, the contents of which are incorporated herein by reference.

[0169] Preferred compounds containing ethylenically unsaturated bond groups include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and compounds in which the (meth)acryloyl groups of these compounds are linked via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499, commercially available from Sartomer). Furthermore, compounds containing ethylenically unsaturated bond-containing groups can also be used, such as diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronics TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), and light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0170] Furthermore, it is also preferable to use trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxy-modified tri(meth)acrylate, trimethylolpropaneethylene oxy-modified tri(meth)acrylate, isocyanurate ethylene oxy-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate as compounds having an ethylenically unsaturated bond-containing group. Commercially available trifunctional (meth)acrylate compounds include Aronics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0171] Compounds containing ethylenically unsaturated bond groups can also be compounds containing acidic groups. Using compounds with acidic groups can suppress the generation of developing residue. Examples of acidic groups include carboxyl groups, sulfol groups, and phosphate groups, with carboxyl groups being preferred. Commercially available polymerizable monomers containing acidic groups include Aronics M-305, M-510, M-520, and Aronics TO-2349 (manufactured by Toagosei Co., Ltd.). The preferred acid value of polymerizable monomers containing acidic groups is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or higher, it has good solubility in the developing solution, and if it is 40 mgKOH / g or lower, it is advantageous in terms of manufacturing and handling.

[0172] A preferred embodiment is that the compound having an ethylenically unsaturated bond-containing group is a compound having a caprolactone structure. Compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

[0173] Compounds containing ethylenically unsaturated bond groups may also include compounds containing alkylene oxy groups. Compounds containing alkylene oxy groups are preferably those containing ethylene oxy groups and / or propylene oxy groups, more preferably those containing ethylene oxy groups, and even more preferably 3-6 functional (meth)acrylate compounds having 4-20 ethylene oxy groups. Examples of commercially available alkylene oxy compounds include SR-494, a tetrafunctional (meth)acrylate with 4 ethylene oxy groups, manufactured by Sartomer, and KAYARAD TPA-330, a trifunctional (meth)acrylate with 3 isobutylene oxy groups.

[0174] Compounds containing ethylenically unsaturated bond groups can also be compounds with a fluorene skeleton. Commercially available compounds with a fluorene skeleton include Ogusol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomers with a fluorene skeleton).

[0175] As for compounds containing ethylenically unsaturated bond groups, it is also preferable to use compounds that substantially do not contain environmentally regulated substances such as toluene. Examples of commercially available such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

[0176] Suitable compounds containing ethylenically unsaturated bond groups include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. It is also preferable to use polymerizable compounds having an amino structure or sulfide structure in the molecule as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238. In addition, commercially available polymerizable compounds such as UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, and LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

[0177] (Compounds containing a cyclic ether group) Compounds having cyclic ether groups that can also be used as polymerizable monomers include compounds having epoxy groups (hereinafter also referred to as epoxy compounds) and compounds having oxetane groups (hereinafter also referred to as oxetane compounds). Epoxy compounds are preferably polyfunctional epoxy compounds. That is, epoxy compounds are preferably compounds having two or more epoxy groups. The upper limit of the number of epoxy groups is preferably 20 or less, and more preferably 10 or less. Similarly, oxetane compounds are preferably polyfunctional oxetane compounds. That is, oxetane compounds are preferably compounds having two or more oxetane groups. The upper limit of the number of oxetane groups is preferably 20 or less, and more preferably 10 or less.

[0178] Commercial epoxy compounds include JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and other commercially available products described in paragraph 0189 of Japanese Patent Publication No. 2011-221494. Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX -512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX- 850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-2 14L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (all manufactured by Nagase Chemtec), YH-3 Examples include 00, YH-301, YH-302, YH-315, YH-324, YH-325 (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolid GT400, Cellvinace B0134, B0177 (manufactured by Daicel Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company Inc.).

[0179] Commercially available oxetane compounds include OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, and OX-SQ TX-100 (all manufactured by Toagosei Co., Ltd.).

[0180] The polymerizable monomer content in the total solids of the resin composition is preferably 0.1 to 40% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 20% by mass or less.

[0181] When using a compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer, the content of the compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably 1 to 50 parts by mass per 100 parts by mass of the specified resin described above. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

[0182] When using a compound having a cyclic ether group as a polymerizable monomer, the content of the compound having a cyclic ether group as a polymerizable monomer is preferably 1 to 50 parts by mass per 100 parts by mass of the specified resin described above. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

[0183] When using a compound having an ethylenically unsaturated bond-containing group and a compound having a cyclic ether group as polymerizable monomers, the resin composition preferably contains 10 to 500 parts by mass of the compound having a cyclic ether group per 100 parts by mass of the compound having an ethylenically unsaturated bond-containing group. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. The upper limit is preferably 400 parts by mass or less, and more preferably 300 parts by mass or less. If the ratio of the two is within the above range, a film with excellent heat resistance (crack suppression and film shrinkage suppression) can be formed.

[0184] <Photopolymerization initiator> The resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds that are photosensitive to light in the ultraviolet to visible light region are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0185] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, hexaarylbiimidazole compound, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound, and 3-arylsubstituted coumarin compound, more preferably a compound selected from oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, and even more preferably an oxime compound.Furthermore, as photopolymerization initiators, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiator described in MATERIAL STAGE 37-60p, vol.19, No.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 JP 2019-043864, the photopolymerization initiator described in JP 2019-044030, the peroxide-based initiator described in JP 2019-167313, and the aminoacetophenone-based initiator having an oxazolidine group described in JP 2020-055992 are all included. Examples include oxime-based photopolymerization initiators described in Japanese Patent Publication No. 2013-190459, polymers described in Japanese Patent Publication No. 2020-172619, compounds represented by formula 1 described in International Publication No. 2020 / 152120, aminoacetophenone-based initiators having aromatic ring-condensing groups which may contain heteroatoms described in Japanese Patent Publication No. 2007-163542, and aminoacetophenone-based initiators having aromatic ring-condensing groups which may contain heteroatoms described in Japanese Patent Publication No. 2008-031280, the contents of which are incorporated herein by reference.

[0186] Examples of hexaarylbiimidazole compounds include 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5-tetrakis(3,4,5-trimethoxyphenyl)-1,2'-biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole. Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), and Api307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one) (manufactured by MFCI). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (both manufactured by BASF).

[0187] Examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-080068, the compounds described in Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). Furthermore, it is also preferable to use compounds that do not produce color or compounds that are highly transparent and resistant to discoloration as oxime compounds. Commercially available products include ADEKA Arclus NCI-730, NCI-831, NCI-930 (all manufactured by ADEKA Corporation).

[0188] As a photopolymerization initiator, an oxime compound having a fluorene ring can also be used. A specific example of an oxime compound having a fluorene ring is the compound described in Japanese Patent Application Publication No. 2014-137466.

[0189] Furthermore, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring can also be used as photopolymerization initiators. Specific examples of such oxime compounds include those described in International Publication No. 2013 / 083505.

[0190] Oxime compounds containing a fluorine atom can also be used as photopolymerization initiators. Specific examples of oxime compounds containing a fluorine atom include the compound described in Japanese Patent Publication No. 2010-262028, compounds 24, 36-40 described in Japanese Patent Publication No. 2014-500852, and compound (C-3) described in Japanese Patent Publication No. 2013-164471.

[0191] As a photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in International Publication No. 2019 / 088055.

[0192] As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably in dimer form. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and ADEKA Arclus NCI-831 (manufactured by ADEKA Corporation).

[0193] Oxime compounds having a benzofuran skeleton can also be used as photopolymerization initiators. Specific examples include OE-01 to OE-75, described in International Publication No. 2015 / 036910.

[0194] As a photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in International Publication No. 2019 / 088055.

[0195] Specific examples of oxime compounds are shown below, but the present invention is not limited to these.

[0196] [ka] [ka] [ka]

[0197] The oxime compound is preferably one having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably one having a maximum absorption wavelength in the range of 360 to 480 nm. Furthermore, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1,000 to 300,000, even more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar extinction coefficient of the compound can be measured using known methods. For example, it is preferable to measure it using a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) with ethyl acetate at a concentration of 0.01 g / L.

[0198] As the photopolymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, crystallinity is reduced and solubility in solvents is improved, making precipitation less likely over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include the dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445. Examples include Cmpd1-7 described in International Publication No. 2016 / 034963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime compounds described in Japanese Patent No. 6469669.

[0199] The content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. One type of photopolymerization initiator may be used, or two or more types may be used.

[0200] <Silane coupling agent> The resin composition of the present invention may contain a silane coupling agent. In this specification, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. A hydrolyzable group is a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. That is, silane coupling agents are preferably compounds having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups, with amino groups, (meth)acryloyl groups, and epoxy groups being preferred. Specific examples of silane coupling agents include the compounds described in paragraphs 0018 to 0036 of Japanese Patent Publication No. 2009-288703 and the compounds described in paragraphs 0056 to 0066 of Japanese Patent Publication No. 2009-242604, the contents of which are incorporated herein by reference.

[0201] The content of the silane coupling agent in the total solid content of the resin composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be one type or two or more types.

[0202] <Curing accelerator> The resin composition of the present invention may further contain a curing accelerator for the purpose of promoting the reaction of the resin or polymerizable compound or lowering the curing temperature. The curing accelerator can also be a methylol compound (for example, the compound exemplified as a crosslinking agent in paragraph 0246 of Japanese Patent Publication No. 2015-034963), amines, phosphonium salts, amidine salts, amide compounds (for example, the curing agents described in paragraph 0186 of Japanese Patent Publication No. 2013-041165), base generators (for example, the ionic compounds described in Japanese Patent Publication No. 2014-055114), cyanate compounds (for example, the compound described in paragraph 0071 of Japanese Patent Publication No. 2012-150180), alkoxysilane compounds (for example, the alkoxysilane compound having an epoxy group described in Japanese Patent Publication No. 2011-253054), onium salt compounds (for example, the compound exemplified as an acid generator in paragraph 0216 of Japanese Patent Publication No. 2015-034963, the compound described in Japanese Patent Publication No. 2009-180949), etc.

[0203] If the resin composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass, of the total solid content of the resin composition.

[0204] <Polymerization inhibitor> The resin composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerium salts, etc.). Among these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass.

[0205] <<Surfactants>> The resin composition of the present invention may contain a surfactant. Various surfactants can be used, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The surfactant is preferably a fluorinated surfactant or a silicone surfactant. Examples of surfactants are those described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which are incorporated herein by reference.

[0206] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in resin compositions.

[0207] Examples of fluorinated surfactants include those described in paragraphs 0060 to 0064 of Japanese Patent Publication No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding International Publication No. 2014 / 017669), and those described in paragraphs 0117 to 0132 of Japanese Patent Publication No. 2011-132503, the contents of which are incorporated herein by reference. Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, R-30, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, and R-01. R-40, R-40-LM, R-41, R-41-LM, RS-43, R-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox Examples include the PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), the F-Tergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, and the FTX-218 (all manufactured by NEOS Corporation).

[0208] Fluorine-based surfactants may also preferably be polymers of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Such fluorine-based surfactants can be described in Japanese Patent Application Publication No. 2016-216602, the contents of which are incorporated herein by reference.

[0209] Fluorine-based surfactants can also be made from block polymers. For example, the compounds described in Japanese Patent Publication No. 2011-089090 can be used. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). The following compounds are also examples of fluorine-based surfactants used in the present invention. [ka] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds, the percentage indicating the proportion of repeating units is expressed as mole percent.

[0210] Furthermore, fluorinated surfactants can also be fluorinated polymers having ethylenically unsaturated bond-containing groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Publication No. 2010-164965, and Megafac RS-101, RS-102, RS-718K, RS-72-K, etc., manufactured by DIC Corporation. Additionally, fluorinated surfactants can also be compounds described in paragraphs 0015-0158 of Japanese Patent Publication No. 2015-117327.

[0211] Furthermore, using the surfactant described in International Publication No. 2020 / 084854 as a substitute for surfactants having a perfluoroalkyl group with 6 or more carbon atoms is also preferable from an environmental regulatory standpoint.

[0212] Furthermore, it is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant. [ka] In equation (fi-1), m represents 1 or 2, n represents an integer from 1 to 4, a represents 1 or 2, and X a+This refers to α-valent metal ions, primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, quaternary ammonium ions, or NH4. + It represents.

[0213] Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Examples include Lubrizol® L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0214] Cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, and imidazolium salts. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, and stearamidemethylpyridium chloride.

[0215] Examples of anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, and sodium t-octylphenoxyethoxypolyethoxyethyl sulfate.

[0216] Examples of silicone-based surfactants include DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400, SH 8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. Examples include OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, and BYK-UV3510 (manufactured by BIC Chemie).

[0217] Furthermore, silicone-based surfactants can also be compounds with the following structure. [ka]

[0218] The surfactant content in the total solids of the resin composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be one type or two or more types. If two or more types are used, the total amount is preferably within the above range.

[0219] <<UV absorber>> The resin composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. For further details, please refer to paragraphs 0052-0072 of Japanese Patent Publication No. 2012-208374, paragraphs 0317-0334 of Japanese Patent Publication No. 2013-068814, and paragraphs 0061-0080 of Japanese Patent Publication No. 2016-162946, the contents of which are incorporated herein by reference. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), the Tinuvin series and Uvinul series from BASF, and the Sumisorb series from Sumika Chemtex Co., Ltd. Furthermore, examples of benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil & Fat Co., Ltd. (Chemical Daily, February 1, 2016). In addition, as UV absorbers, compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967, compounds described in paragraphs 0059 to 0076 of International Publication No. 2016 / 181987, and thioaryl group-substituted benzotriazole-type UV absorbers described in International Publication No. 2020 / 137819 can also be used. The content of UV absorbers in the total solid content of the resin composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. Only one type of UV absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0220] <Antioxidant> The resin composition of the present invention may contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. Compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group are preferred. As the substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenol group and a phosphite ester group in the same molecule are also preferred as antioxidants. Phosphorus-based antioxidants can also be suitably used as antioxidants. Furthermore, compounds described in Korean Published Patent No. 10-2019-0059371 can also be used as antioxidants. The content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0221] <Other ingredients> The resin composition of the present invention may optionally contain sensitizers, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, defoamers, flame retardants, leveling agents, peel accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109, etc., of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. The resin composition may also optionally contain latent antioxidants. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100-250°C or at 80-200°C in the presence of an acid / base catalyst, thereby removing the protecting group. Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219. Examples of commercially available products include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation).

[0222] The resin composition of the present invention may also contain a lightfastness modifier. As lightfastness modifiers, the compounds described in paragraphs 0036 to 0037 of JP 2017-198787, the compounds described in paragraphs 0029 to 0034 of JP 2017-146350, the compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of JP 2017-129774, the compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of JP 2017-129674, the compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of JP 2017-122803, the compounds described in paragraphs 0025 to 0039 of International Publication No. 2017 / 164127, and the compounds described in paragraphs 0025 to 0039 of JP 2017-186546 Examples include the compounds described in paragraphs 0034 to 0047, the compounds described in paragraphs 0019 to 0041 of Japanese Patent Publication No. 2015-025116, the compounds described in paragraphs 0101 to 0125 of Japanese Patent Publication No. 2012-145604, the compounds described in paragraphs 0018 to 0021 of Japanese Patent Publication No. 2012-103475, the compounds described in paragraphs 0015 to 0018 of Japanese Patent Publication No. 2011-257591, the compounds described in paragraphs 0017 to 0021 of Japanese Patent Publication No. 2011-191483, the compounds described in paragraphs 0108 to 0116 of Japanese Patent Publication No. 2011-145668, and the compounds described in paragraphs 0103 to 0153 of Japanese Patent Publication No. 2011-253174.

[0223] From an environmental perspective, the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be restricted. In the resin composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acid (particularly perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkyl carboxylic acid (particularly perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01 ppb to 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solid content of the resin composition. The resin composition of the present invention may substantially not contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. For example, a resin composition substantially free of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, may be selected by using compounds that can substitute for perfluoroalkyl sulfonic acid and its salts, and compounds that can substitute for perfluoroalkyl carboxylic acid and its salts. Examples of compounds that can substitute for regulated compounds include compounds that have been excluded from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. The resin composition of the present invention may contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, to the maximum permissible extent.

[0224] The resin composition of the present invention is preferably substantially free of terephthalate esters. Here, "substantially free" means that the terephthalate ester content is 1000 ppb by mass or less of the total amount of the resin composition, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0225] <container> There are no particular limitations on the container used to house the resin composition, and any known container can be used. Furthermore, to suppress the incorporation of impurities into the raw materials and resin composition, it is preferable to use a multilayer bottle with an inner wall constructed of six types of resin in six layers, or a bottle with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Publication No. 2015-123351. Additionally, the inner wall of the container may be made of glass, stainless steel, or other materials to prevent metal leaching from the inner wall, enhance the storage stability of the resin composition, and suppress component deterioration.

[0226] <Method for preparing resin compositions> The resin composition of the present invention can be prepared by mixing the aforementioned components. When preparing the resin composition, all components may be dissolved and / or dispersed simultaneously in an organic solvent, or, if necessary, each component may be prepared as two or more solutions or dispersions and mixed at the time of use (coating) to prepare the resin composition.

[0227] Furthermore, it is preferable that the preparation of the resin composition includes a process for dispersing the pigment. Examples of mechanical forces used for dispersing the pigment in this process include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. In addition, when grinding the pigment in a sand mill (bead mill), it is preferable to process under conditions that improve grinding efficiency, such as using beads with a small diameter or increasing the bead filling rate. Furthermore, it is preferable to remove coarse particles after the grinding process by filtration, centrifugation, etc. Furthermore, the processes and dispersers for dispersing the pigments can suitably be those described in "Complete Collection of Dispersion Technologies, published by Joho Kiko Co., Ltd., July 15, 2005," "Comprehensive Data Collection on Dispersion Technologies and Practical Industrial Applications, Centered on Suspensions (Solid / Liquid Dispersion Systems), published by Keiei Kaihatsu Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Publication No. 2015-157893. In addition, in the process of dispersing the pigments, particle refinement treatment may be performed in a salt milling step. For materials, equipment, and processing conditions used in the salt milling step, refer to, for example, the descriptions in Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629.

[0228] In preparing a resin composition, it is preferable to filter the resin composition with a filter for purposes such as removing foreign matter and reducing defects. Any filter that has been conventionally used for filtration purposes can be used without particular limitations. For example, filters made of materials such as fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight polyolefin resins) can be used. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0229] The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the filter pore size is within the above range, fine foreign matter can be removed more reliably. The nominal value of the filter pore size can be referred to from the filter manufacturer. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), and KITZ Microfilter Corporation can be used.

[0230] Furthermore, it is also preferable to use fibrous filter media as a filter. Examples of fibrous filter media include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) from Rokitechno Co., Ltd.

[0231] When using filters, different filters (for example, a first filter and a second filter) may be combined. In this case, filtration with each filter may be performed only once or two or more times. Filters with different pore sizes within the range described above may also be combined. Furthermore, filtration with the first filter may be performed only on the dispersion, and then filtration with the second filter may be performed after mixing in other components. In addition, filters can be selected appropriately according to the hydrophilicity and hydrophobicity of the resin composition.

[0232] (film) The film of the present invention is obtained from the resin composition of the present invention described above. The film of the present invention can be used in optical filters such as color filters, near-infrared transmission filters, and near-infrared cut filters. The film of the present invention can also be used as a light-shielding film. In addition to sensors, it can also be used as a filter for optical communication and the like.

[0233] The film thickness of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0234] When the film of the present invention is used as a color filter, it is preferable that the film has a hue of green, red, blue, cyan, magenta, or yellow. Furthermore, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

[0235] When the film of the present invention is used as a near-infrared cut filter, the maximum absorption wavelength of the film of the present invention is preferably in the range of 700 to 1800 nm, more preferably in the range of 700 to 1300 nm, and even more preferably in the range of 700 to 1100 nm. Furthermore, the transmittance of the film over the entire range of wavelengths 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 of the film at at least one point in the range of wavelengths from 700 to 1800 nm is preferably 20% or less. In addition, the ratio of absorbance Amax at the maximum absorption wavelength to absorbance A550 at a wavelength of 550 nm, which is absorbance Amax / absorbance A550, is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400.

[0236] When the film of the present invention is used as a near-infrared transmission filter, it is preferable that the film of the present invention has any of the following spectral characteristics (i1) to (i5). (i1): A filter having 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. A film having such spectral characteristics can block light in the wavelength range of 400 to 640 nm and transmit light with a wavelength greater than 750 nm. (i2): A filter having 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. A film having such spectral characteristics can block light in the wavelength range of 400 to 750 nm and transmit light with wavelengths exceeding 850 nm. (i3): A filter having 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. A film having such spectral characteristics can block light in the wavelength range of 400 to 830 nm and transmit light with a wavelength greater than 950 nm. (i4): A filter having 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. A film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength greater than 1050 nm. (i5): A filter having 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. A film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength greater than 1150 nm.

[0237] When the film of the present invention is used as a light-shielding film, the optical density (OD) per 1.5 μm of film thickness in the wavelength region of 400 to 1100 nm is preferably 2.5 or higher, and more preferably 3.0 or higher. There is no particular upper limit, but it is generally preferable to be 10 or lower. Furthermore, the reflectance of the above film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%. The lower limit is preferably 0% or more.

[0238] The light-shielding film can be used in optical filters and modules for portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; office automation (OA) equipment such as printers and scanners; industrial equipment such as surveillance cameras, barcode readers, automated teller machines (ATMs), high-speed cameras, and devices with personal authentication functions using facial recognition or biometric authentication; in-vehicle camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters; and space equipment such as biosensors, biosensors, military reconnaissance cameras, 3D map cameras, weather and ocean observation cameras, land resource exploration cameras, and space astronomy and deep space target exploration cameras. The light-shielding film can also be used in applications such as micro-LEDs (Light Emitting Diodes) and micro-OLEDs (Organic Light Emitting Diodes). Examples of micro-LEDs and micro-OLEDs are described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890, respectively. Furthermore, the light-shielding film is also suitable as an optical filter and optical film used in quantum dot sensors and quantum dot solid-state image sensors. Examples of quantum dot sensors and quantum dot solid-state image sensors are described in U.S. Patent Application Publication No. 2012 / 37789 and International Publication No. 2008 / 131313. The light-shielding film can also be used in headlight units for vehicles such as automobiles. When used in a headlight unit, the light-shielding film is preferably formed in a pattern so as to block at least a portion of the light emitted from the light source.

[0239] <Memory manufacturing method> The film of the present invention can be manufactured by a step of applying the resin composition of the present invention described above onto a support. In the method for manufacturing the film of the present invention, it is preferable to further include a step of forming a pattern (pixels). Examples of methods for forming the pattern (pixels) include photolithography and dry etching, with photolithography being preferred.

[0240] (Photolithography) First, we will describe the case in which a film is manufactured by forming a pattern using photolithography. Preferably, the pattern formation by photolithography includes the steps of: forming a resin composition layer on a support using the resin composition of the present invention; exposing the resin composition layer in a patterned manner; and developing and removing the unexposed parts of the resin composition layer to form a pattern (pixels). If necessary, a step of baking the resin composition layer (pre-bake step) and a step of baking the developed pattern (pixels) (post-bake step) may also be included.

[0241] In the step of forming the resin composition layer, the resin composition of the present invention is used to form the resin composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. Examples include glass substrates and silicon substrates, with silicon substrates being preferred. The silicon substrate may also have charge-coupled devices (CCDs), complementary metal-oxide-semiconductor (CMOS) elements, transparent conductive films, etc., formed on it. The silicon substrate may also have a light-shielding film, such as a black matrix, to isolate each pixel. The silicon substrate may also have a base layer to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane, and preferably 30 to 80° when measured with water. The surface contact angle of the base layer can be adjusted, for example, by adding a surfactant.

[0242] Known methods can be used for coating the resin composition. Examples include the drop method (drop casting); slit coating method; spray method; roll coating method; spin coating method; casting method; slit and spin method; pre-wetting method (for example, the method described in Japanese Patent Application Publication No. 2009-145395); various printing methods such as inkjet (for example, on-demand, piezo, and thermal methods), nozzle jet and other ejection-type printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; transfer methods using molds, etc.; and nanoimprint methods. The application method for inkjet printing is not particularly limited and includes methods shown in "Expanding and Usable Inkjet Printing - Infinite Possibilities Seen in Patents," published February 2005 by Sumibe Techno Research (especially pages 115-133), as well as methods described in Japanese Patent Publication Nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-169325. Furthermore, the method for coating the resin composition can also be the method described in International Publication Nos. 2017 / 030174 and 2017 / 018419, and these contents are incorporated herein by reference.

[0243] The resin composition layer formed on the support may be dried (pre-baked). Pre-baking is not necessary when manufacturing the film by a low-temperature process. If pre-baking is performed, the pre-baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, and also 80°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, oven, etc.

[0244] Next, the resin composition layer is exposed in a patterned manner (exposure step). For example, the resin composition layer can be exposed in a patterned manner by using a stepper exposure machine or a scanner exposure machine, etc., through a mask having a predetermined mask pattern. This allows the exposed areas to be cured.

[0245] Examples of radiation (light) that can be used during exposure include g-rays and i-rays. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. Long-wave light sources with wavelengths of 300 nm or more can also be used.

[0246] Furthermore, exposure may be performed by continuously irradiating with light, or by irradiating with light in pulses (pulsed exposure). Pulsed exposure is an exposure method in which light irradiation and pauses are repeated in short cycles (e.g., millisecond level or less). In the case of pulsed exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less. There is no particular limit to the lower limit of the pulse width, but it can be 1 femtosecond (fs) or more, and can also be 10 femtoseconds or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and even more preferably 4 kHz or more. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less. The maximum instantaneous illuminance is 50,000,000 W / m 2 Preferably, it is 10,000,000 W / m 2 It is more preferable that the value be greater than or equal to 20,000,000 W / m 2 It is even more preferable that the above be true. Also, the upper limit of the maximum instantaneous illuminance is 100,000,000 W / m 2 Preferably, it is 80,000,000 W / m 2 It is more preferable that the following conditions are met: 50,000,000 W / m2 The following is even more preferable. Pulse width refers to the duration of light irradiation within a pulse period. Frequency refers to the number of pulse periods per second. Maximum instantaneous illuminance refers to the average illuminance within the duration of light irradiation within a pulse period. Pulse period refers to the period in pulse exposure where light irradiation and pause constitute one cycle.

[0247] The irradiation dose (exposure dose) is, for example, 0.03 to 2.5 J / cm². 2 Preferably, 0.05 to 1.0 J / cm² 2 This is more preferable. The oxygen concentration during exposure can be appropriately selected. In addition to exposure in air, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19 vol% or less (e.g., 15 vol%, 5 vol%, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration exceeding 21 vol% (e.g., 22 vol%, 30 vol%, or 50 vol%). Furthermore, the exposure intensity can be appropriately set, usually 1000 W / m². 2 ~100,000 W / m 2 (For example, 5000W / m 2 , 15000W / m 2 , or 35000W / m 2 The oxygen concentration and exposure intensity can be combined as appropriate; for example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m². 2 At an oxygen concentration of 35% by volume, the illuminance is 20,000 W / m². 2 This can be done as follows.

[0248] Next, the unexposed areas of the resin composition layer are developed and removed to form a pattern (pixels). The unexposed areas of the resin composition layer can be developed and removed using a developer. This causes the unexposed parts of the resin composition layer in the exposure process to dissolve into the developer, leaving only the photocured parts. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve the ability to remove residue, the developer may be emptied every 60 seconds, and the process of supplying fresh developer may be repeated several times.

[0249] Examples of developing solutions include organic solvents and alkaline developers, with alkaline developers being preferred. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferred. Examples of alkaline agents include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene, as well as inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. Alkaline agents with larger molecular weights are preferred from an environmental and safety perspective. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The developer may also contain a surfactant. Examples of surfactants include those mentioned above, and nonionic surfactants are preferred. For convenience of transport and storage, the developer may be manufactured as a concentrated solution and then diluted to the required concentration at the time of use. The dilution ratio is not particularly limited, but can be set in the range of 1.5 to 100 times, for example. It is also preferable to wash (rinse) with pure water after development. It is preferable to perform rinsing by supplying the rinsing solution to the resin composition layer after development while rotating the support on which the resin composition layer has been formed after development. It is also preferable to move the nozzle that discharges the rinsing solution from the center of the support to the periphery of the support. In this case, when moving the nozzle from the center to the periphery of the support, the speed of movement of the nozzle may be gradually reduced. By performing rinsing in this manner, in-plane variation of the rinse can be suppressed. Furthermore, a similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center to the periphery of the support.

[0250] After development and drying, it is preferable to perform additional exposure or heat treatment (post-bake). Additional exposure and post-bake are curing treatments after development to ensure complete hardening. The heating temperature in post-bake is preferably 100 to 240°C, and more preferably 200 to 240°C. Post-bake can be performed continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to achieve the above conditions. When performing additional exposure, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure may also be performed by the method described in Korean Published Patent No. 10-2017-0122130.

[0251] (Dry etching method) The dry etching method for pattern formation preferably includes the steps of: forming a resin composition layer on a support using the resin composition of the present invention; curing the entire resin composition layer to form a cured product layer; forming a photoresist layer on the cured product layer; exposing the photoresist layer in a patterned manner, then developing it to form a resist pattern; and using the resist pattern as a mask to dry etch the cured product layer using an etching gas. In the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a photoresist layer formation process, it is desirable to perform a heat treatment after exposure and a heat treatment after development (post-bake treatment). For the dry etching method for pattern formation, refer to paragraphs 0010 to 0067 of Japanese Patent Application Publication No. 2013-064993, and this content is incorporated herein by reference.

[0252] <Optical filters> The optical filter of the present invention has the film of the present invention described above. Examples of optical filters include color filters, near-infrared transmission filters, and near-infrared cut filters, with color filters being preferred. For color filters, it is preferable that the film of the present invention is used as the colored pixels of the color filter. The optical filter may also have a light-shielding film. For example, a color filter, near-infrared transmission filter, near-infrared cut filter, etc., may be formed in the openings of a light-shielding film formed on a support. The optical filter of the present invention can be used in solid-state image sensors such as CCDs (charge-coupled devices) and CMOS (complementary metal-oxide-semiconductor devices), as well as in image display devices.

[0253] In optical filters, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness of pixels included in the optical filter is preferably 5 μm or less, more preferably 1 μm or less, and even more preferably 0.6 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0254] The width of the pixels included in the optical filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and even more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.8 μm or less. The Young's modulus of the pixels is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

[0255] Each pixel in the optical filter preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. There is no lower limit, but it is preferably 0.1 nm or more. The surface roughness of the pixel can be measured using, for example, a Veeco AFM (atomic force microscope) Dimension3100. The water contact angle on the pixel can be set to a suitable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT·A (manufactured by Kyowa Interface Science Co., Ltd.). Furthermore, it is preferable that the volume resistivity of the pixel is high. Specifically, the volume resistivity of the pixel should be 10 9 It is preferable that it be Ω·cm or more, 10 11 It is more preferable that it be Ω·cm or greater. There is no upper limit specified, but for example, 10 14 It is preferable that the resistance is Ω·cm or less. The volume resistivity of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest Corporation).

[0256] Furthermore, if the optical filter includes a light-shielding film, the thickness of the light-shielding film is preferably 5 μm or less, and more preferably 2.5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more.

[0257] In optical filters, a protective layer may be provided on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflectivity, hydrophilicity, and shielding of light of specific wavelengths (ultraviolet rays, near-infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Methods for forming the protective layer include applying a protective layer-forming resin composition dissolved in an organic solvent, chemical vapor deposition, and attaching molded resin with an adhesive. The components constituting the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene etherphosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al2O3, Mo, SiO2, Si2N4, etc. Two or more of these components may be included. For example, in the case of a protective layer intended for oxygen barrier protection, the protective layer preferably contains polyol resin, SiO2, and Si2N4. In the case of a protective layer intended for low reflectivity, the protective layer preferably contains (meth)acrylic resin and fluororesin.

[0258] When forming a protective layer by applying a protective layer-forming resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the application method for the protective layer-forming resin composition. The organic solvent contained in the protective layer-forming resin composition can be a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermochemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used.

[0259] The protective layer may contain additives such as organic and inorganic fine particles, light absorbers of specific wavelengths (e.g., ultraviolet, near-infrared, etc.), refractive index adjusters, antioxidants, adhesives, and surfactants, as needed. Examples of organic and inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium dioxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known light absorbers can be used as light absorbers of specific wavelengths. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, relative to the total mass of the protective layer. Alternatively, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Publication No. 2017-151176 can also be used.

[0260] The optical filter may have a structure in which each pixel is embedded in a space partitioned, for example, in a grid pattern by a partition wall. Furthermore, the resin composition of the present invention can be suitably used in the pixel configuration described in International Publication No. 2019 / 102887.

[0261] <Solid-state image sensor> The solid-state image sensor of the present invention has the film of the present invention described above. The configuration of the solid-state image sensor of the present invention is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor, but for example, the following configuration can be given.

[0262] The device has a substrate on which multiple photodiodes and transfer electrodes made of polysilicon or the like constitute the light-receiving area of ​​a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide-semiconductor) image sensor, etc.), a light-shielding film with an opening only for the light-receiving portion of the photodiode is placed on the photodiode and transfer electrodes, a device protection film made of silicon nitride or the like is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a color filter is placed on the device protection film. Furthermore, the device may have a configuration in which a light-gathering means (e.g., a microlens; the same applies hereinafter) is placed on the device protection film and below the color filter (on the side closer to the substrate), or a configuration in which the light-gathering means is placed on the color filter. In addition, the color filter may have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example in a grid pattern. In this case, it is preferable that the partitions have a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include those described in Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, International Publication No. 2018 / 043654, and the specification of U.S. Patent Application Publication No. 2018 / 0040656. Furthermore, as described in Japanese Patent Publication No. 2019-211559, a UV-absorbing layer may be provided within the structure of the solid-state image sensor to improve light resistance. Imaging devices equipped with the solid-state image sensor of the present invention can be used not only in digital cameras and electronic devices with imaging functions (such as mobile phones), but also in in-vehicle cameras and surveillance cameras. Moreover, the solid-state image sensor incorporating the color filter of the present invention may also incorporate other color filters, near-infrared cut filters, organic photoelectric conversion films, etc., in addition to the color filter of the present invention.

[0263] <Image display device> The image display device of the present invention has the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescent display devices. For definitions of image display devices and details of each image display device, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Yoshiaki Ibuki, Sangyo Tosho Co., Ltd., published in 1989). Liquid crystal display devices are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994). There are no particular restrictions on the liquid crystal display devices to which the present invention can be applied; for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next-Generation Liquid Crystal Display Technology". [Examples]

[0264] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0265] <Measurement of weight-average molecular weight (Mw) of the sample> The weight-average molecular weight of the samples was measured by gel permeation chromatography (GPC) under the following conditions. Column type: A combination of TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000. Column eluent: tetrahydrofuran Column temperature: 40℃ Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1% by mass) Device name: Tosoh Corporation HLC-8220GPC Detector: RI (refractive index) detector Calibration curve base resin: Polystyrene resin

[0266] <Measurement of the acid value of the sample> The acid value of a sample represents the mass of potassium hydroxide required to neutralize the acidic components per gram of solid content in the sample. The acid value of the sample was measured as follows: The sample was dissolved in a tetrahydrofuran / water = 9 / 1 (mass ratio) mixed solvent, and the resulting solution was titrated with a 0.1 mol / L potassium hydroxide aqueous solution at 25°C using a potentiometric titrator (product name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). The inflection point of the titration pH curve was used as the titration endpoint, and the acid value was calculated using the following formula. A = 56.11 × Vs × 0.5 × f / w A: Acid value (mgKOH / g) Vs: Volume of 0.1 mol / L potassium hydroxide solution used for titration (mL) f: Titer of 0.1 mol / L potassium hydroxide aqueous solution w: Mass of the sample (g) (calculated as solid content)

[0267] <Examples of resin synthesis> (Synthesis Example 1) 114.1 g of ε-caprolactone and 14.9 g of 6-mercaptohexanol were added to a nitrogen-purged three-necked flask and heated at 90°C. Next, 0.1 g of monobutyltin oxide (MBTO: manufactured by Mitsubishi Chemical Corporation) was added and the mixture was heated and stirred at 90°C under a nitrogen atmosphere for 4 hours, then the temperature was raised to 110°C and heated and stirred for another 4 hours. Finally, 128.6 g of propylene glycol monomethyl ether acetate was added to obtain a solution of a terminal mercapto group polymer with the structure shown below. The weight-average molecular weight of the obtained terminal mercapto group polymer was 980. [ka]

[0268] Next, the solution of the obtained terminal mercapto group polymer was heated to 60°C, 10.9 g of maleic anhydride was added, and 0.32 g of a thermal radical generator (V-65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. The mixture was then heated and stirred at 60°C under a nitrogen atmosphere for 8 hours to obtain a solution of resin B-1 with the structure shown below. The weight-average molecular weight of the obtained resin B-1 was 1150. [ka] Furthermore, resins B-2 to B-4 were synthesized using the same method as resin B-1.

[0269] (Synthesis Example 2) 114.1 g of ε-caprolactone and 14.5 g of 2-ethylhexanol were added to a nitrogen-purged three-necked flask and heated at 90°C. Next, 0.1 g of monobutyltin oxide (MBTO: manufactured by Mitsubishi Chemical Corporation) was added and the mixture was heated and stirred at 90°C under a nitrogen atmosphere for 4 hours, then the temperature was raised to 110°C and heated and stirred for another 4 hours. Finally, 128.6 g of propylene glycol monomethyl ether acetate was added to obtain a solution of a terminal hydroxyl group polymer with the structure shown below. The weight-average molecular weight of the obtained terminal hydroxyl group polymer was 1300. [ka]

[0270] Next, the solution of the obtained terminal hydroxyl group polymer was cooled to 5°C, 32.1 g of trimellitic chloride anhydride was added, and 15.3 g of N-methylimidazole was added dropwise over 6 hours. The mixture was then stirred at room temperature for 24 hours, and insoluble matter was filtered off to obtain a solution of resin B-5 with the structure shown below. The weight-average molecular weight of the obtained resin B-5 was 1440. [ka]

[0271] Furthermore, resins B-6 to B-41 were synthesized using the same method as resin B-5.

[0272] The structures and weight-average molecular weights of resins B-1 to B-41 are shown below. [ka] [Table 1]

[0273] AH-1~AH-7: The basic structure shown below (where * indicates a connecting part) [ka]

[0274] Z1-1, Z1-2, Z1-12, Z1-13, Z1-14: Base structure of the following (where * is a connector) [ka]

[0275] P1-1~P1-16, P1-18~P1-22: The basis of the following structure (where * is a connecting part) [ka] [ka]

[0276] <Manufacturing of dispersions> The mixture of raw materials listed in the table below was mixed and dispersed for 3 hours using a bead mill (using 0.3 mm diameter zirconia beads). Further dispersion was performed using a high-pressure disperser with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), at a pressure of 2000 MPa and a flow rate of 500 g / min. This dispersion process was repeated 10 times to obtain each dispersion.

[0277] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7]

[0278] The units of the numerical values ​​indicating the blending amounts of each ingredient listed in the table above are parts by mass. Details of the ingredients abbreviated in the table above are as follows: [Colorants] PR122: CI Pigment Red 122 (Red pigment, quinacridone pigment) PR179: CI Pigment Red 179 (Red pigment, Perylene pigment) PR254: CI Pigment Red 254 (Red pigment, diketopyrrolopyrrole pigment) PR264: CI Pigment Red 264 (Red pigment, diketopyrrolopyrrole pigment) PR291: CI Pigment Red 291 (Red pigment, diketopyrrolopyrrole pigment) PO71: CI Pigment Orange 71 (Orange pigment, diketopyrrolopyrrole pigment) PB15:6 : CI Pigment Blue 15:6 (Blue pigment, phthalocyanine pigment) PB16: CI Pigment Blue 16 (Blue pigment, phthalocyanine pigment) PG7: CI Pigment Green 7 (Green pigment, phthalocyanine pigment) PG36: CI Pigment Green 36 (Green pigment, phthalocyanine pigment) PG58: CI Pigment Green 58 (Green pigment, phthalocyanine pigment) PY185: CI Pigment Yellow 185 (yellow pigment, isoindoline pigment) PY215: CI Pigment Yellow 215 (yellow pigment, pteridine pigment) PV23: CI Pigment Violet 23 (Purple pigment, Dioxazine pigment) IR dyes: Compounds with the following structure (near-infrared absorbing pigments; in the structural formula, Me represents a methyl group and Ph represents a phenyl group) [ka]

[0279] Black pigment 1: Titanium black (a-1) manufactured by the following method. 100g of titanium dioxide MT-150A (manufactured by Teika Co., Ltd.) with an average particle size of 15nm, BET surface area of ​​300m² 2 25 g of silica particles AEROGIL300 / 30 (manufactured by Evonik) and 100 g of the dispersant Disperbyk190 (manufactured by Bic Chemie) were weighed out, and 71 g of deionized water was added. A homogeneous aqueous mixture was obtained by processing with a KURABO MAZERSTAR KK-400W at an orbital speed of 1360 rpm and a rotational speed of 1047 rpm for 20 minutes. This aqueous solution was filled into a quartz container and heated to 920°C in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama). After that, the atmosphere was replaced with nitrogen, and ammonia gas was flowed at the same temperature at a rate of 100 mL / min for 5 hours to perform a nitriding reduction treatment. After completion, the recovered powder was pulverized in a mortar and pestle, and the powder contained Si atoms with a specific surface area of ​​73 m². 2 A dispersion of titanium black (a-1) containing titanium black particles and Si atoms was obtained in a quantity of / g.

[0280] Black colorant 2: Coated carbon black manufactured by the following method Carbon black was produced using a conventional oil furnace process. However, ethylene bottom oil with low levels of Na, Ca, and S was used as the raw material oil, and combustion was carried out using gaseous fuel. Furthermore, pure water treated with ion exchange resin was used as reaction stop water. Using a homomixer, 540g of the obtained carbon black was stirred with 14500g of pure water at 5000-6000 rpm for 30 minutes to obtain a slurry. This slurry was transferred to a container with a screw-type stirrer, and 600g of toluene containing 60g of epoxy resin (Epicoat 828, manufactured by Mitsubishi Chemical Corporation) was added in small amounts while mixing at approximately 1000 rpm. After about 15 minutes, all of the carbon black dispersed in the water migrated to the toluene side, forming particles of approximately 1 mm. Next, after draining the water using a 60-mesh wire mesh, the separated particles were placed in a vacuum dryer and dried at 70°C for 7 hours to remove toluene and water, thereby obtaining coated carbon black. The amount of resin coating on the obtained coated carbon black was 10% by mass relative to the total amount of carbon black and resin.

[0281] Black pigment 3: Irgaphor Black S 0100 CF (manufactured by BASF, a compound with the following structure, lactam pigment) [ka]

[0282] Black colorant 4: Zirconium oxynitride (powdered, specific surface area 65 m²) 2 / g)

[0283] [Pigment derivatives] Derivative 1: Compound with the following structure [ka] Derivative 2: Compound with the following structure [ka] Derivative 3: Compound with the following structure [ka] Derivative 4: S12000 (manufactured by Lubrizol)

[0284] [Resin (dispersant)] B-1~B-38: The resins mentioned above

[0285] (Comparative resin) cB-1: Resin with the following structure (weight-average molecular weight 2500; the notation "Poly" indicates that polymer chains, in which repeating units of the structure indicated by "Poly" are linked by the number of subscripts, are bonded to sulfur atoms (S).) cB-2: Resin with the following structure (weight-average molecular weight 2800; the "Poly" notation indicates that polymer chains, where repeating units of the structure indicated by "Poly" are linked together according to the number of subscripts, are bonded to sulfur atoms (S).) [ka]

[0286] 〔solvent〕 S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-3: Cyclohexanone S-4: Cyclopentanone

[0287] <Manufacturing of resin compositions> The resin compositions of the examples and comparative examples were prepared by mixing the raw materials listed in the table below.

[0288] [Table 8]

[0289] [Table 9]

[0290] [Table 10]

[0291] The details of the ingredients listed in the table above, indicated by abbreviations, are as follows:

[0292] [Dispersion liquid] Dispersions R1~R15, B1~B14, G1~G14, I1~I7, Bk1~Bk17, TBk1~TBk17, CR1, CR2, CB1, CB2, CG1, CG2, CI1, CI2, CBk1, CBk2, CTBk1, CTBk2: The dispersions described above.

[0293] 〔resin〕 Ba-1: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight: 11000) [ka] Ba-2: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight: 15000) [ka] Ba-3: Resin with the following structure (the values ​​appended to the main chain are molar ratios. The sum of x, y, and z is 50. Mw = 15000) [ka] Ba-4: Cardo resin V-259ME (manufactured by Nippon Steel & Sumitomo Metal Corporation) Bb-1: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight: 13000) [ka] Bb-2: The resin cB-1 mentioned above B-11, B-12: Resins with the structure described above.

[0294] [Polymerizable monomers] D-1: Acrylate compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) D-2: Epoxy compound (TETRAD-X, manufactured by Mitsubishi Gas Chemical Company, Inc., N,N,N',N'-tetraglycidyl-m-xylylenediamine) D-3: Oxetane compound (OXT-221, manufactured by Toagosei Co., Ltd., 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane) D-4: Oxetane compound (OX-SQ TX-100, manufactured by Toagosei Co., Ltd.)

[0295] [Photopolymerization initiator] E-1: Omnirad 379EG (manufactured by IGM Resins BV, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one) E-2: Irgacure OXE01 (BASF, oxime compound) E-3: Compounds with the following structure [ka]

[0296] 〔solvent〕 S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-3: Cyclohexanone

[0297] <Rating> [Assessment of variance] (Storage stability) The viscosity (mPa·s) of the resin compositions of each example and comparative example was measured using the "RE-85L" manufactured by Toki Sangyo Co., Ltd. After the above measurement, the resin compositions were left to stand at 45°C, shielded from light, for 3 days, and the viscosity (mPa·s) was measured again. The storage stability was evaluated from the viscosity difference (ΔVis) before and after the above standing period according to the evaluation criteria below. A smaller viscosity difference (ΔVis) indicates better storage stability of the resin composition and better pigment dispersibility. All of the above viscosity measurements were performed in a laboratory where the temperature and humidity were controlled to 22±5°C and 60±20%, with the temperature of the resin composition adjusted to 25°C.

[0298] -Evaluation Criteria- A: ΔVis was 0.5 mPa·s or less. B: ΔVis was greater than 0.5 mPa·s and less than or equal to 1.0 mPa·s. C:ΔVis was greater than 1.0 mPa·s and less than or equal to 2.0 mPa·s. D:ΔVis was greater than 2.0 mPa·s and less than or equal to 2.5 mPa·s. E:ΔVis exceeded 2.5 mPa·s.

[0299] (Particle size) Using a dynamic light scattering particle size distribution analyzer (LB-500, Horiba, Ltd.) conforming to JIS 8826:2005, the resin composition obtained above was divided into 20 ml sample bottles and diluted with propylene glycol monomethyl ether acetate to a solid content concentration of 0.2% by mass. Using a 2 ml measuring quartz cell at a temperature of 25°C, data from the diluted solution was acquired 50 times, and the arithmetic mean particle size of the pigment (number-mean particle diameter) was determined. A smaller number-mean particle diameter indicates better pigment dispersibility. -Evaluation Criteria- A: The number-average particle size of the pigment was 0.05 μm or less. B: The number-average particle size of the pigment was greater than 0.05 μm and less than or equal to 0.10 μm. C: The number-average particle size of the pigment was greater than 0.10 μm and less than or equal to 0.20 μm. D: The number-average particle size of the pigment was greater than 0.20 μm and less than or equal to 0.50 μm. E: The number-average particle size of the pigment exceeded 0.50 μm.

[0300] [Evaluation of pattern formation ability] (Manufacturing Example 1) Method for forming patterns using resin compositions of Examples 1-77 and Comparative Examples 1-10 The resin compositions of Examples 1-77 and Comparative Examples 1-10 were applied to a glass substrate by spin coating and dried (pre-baked) at 100°C for 120 seconds using a hot plate to produce a coating film with a thickness of 0.6 μm. This coating film was then exposed to light at a wavelength of 365 nm at a rate of 500 mJ / cm² using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Corporation) through a mask pattern consisting of 1.1 μm square non-mask areas arranged in a 4 mm × 3 mm region. 2 The glass substrate was exposed using the specified exposure dose. Next, the glass substrate with the exposed coating was placed on the horizontal rotating table of a spin-shower developer (DW-30 model, manufactured by Chemitronics Co., Ltd.), and paddle-developed using developer (CD-2000, manufactured by Fujifilm Electronic Materials Co., Ltd.) at 23°C for 60 seconds. Then, while rotating the glass substrate at 50 rpm, pure water was supplied in a shower-like manner from a spray nozzle above the center of rotation to perform a rinsing treatment, and then spray-dried. The coating after rinsing was post-baked at 220°C for 300 seconds to form a patterned substrate.

[0301] (Manufacturing Example 2) Method for forming patterns using the resin compositions of Examples 78-94 and Comparative Examples 11 and 12 The resin compositions of Examples 78-94 and Comparative Examples 11 and 12 were applied to a glass substrate by spin coating and dried (pre-baked) at 100°C for 120 seconds using a hot plate to produce a 1.5 μm thick coating. This coating was then subjected to a high-pressure mercury lamp (lamp power 50 mW / cm²) using a UX-1000SM-EH04 (manufactured by Ushio Inc.) through a mask with an L / S pattern (line width:space width = 1:1) and an aperture line width of 50 μm. 2 ) at 500 mJ / cm 2 Exposure was performed using the proximity method with the specified exposure dose. Next, the exposed coating was paddle-developed using AD-1200 (Mikasa Corporation) with developer (CD-1040, Fujifilm Electronic Materials Corporation) at 23°C for 15 seconds, and then rinsed with pure water using a shower nozzle for 30 seconds. The rinsed coating was post-baked at 220°C for 300 seconds to form a patterned substrate.

[0302] [Residue] For patterned substrates prepared using the above method with each resin composition, the unpatterned areas (non-exposed areas) on the substrate were observed using a transmission microscope and evaluated from the following perspectives. A: No residue is present in the space area. B: Residue was found in less than 33.3% of the space area. C: Residue was found in an area of ​​33.3% to less than 66.7% of the space. D: Residue was found in over 66.7% of the space area.

[0303] [Adhesion (Peeling)] Patterned substrates were fabricated using each resin composition in the same manner as described above, except that the aperture line width of the mask used during exposure was changed to 10 μm and the exposure amount was varied for each sample. The resulting patterned substrate was observed using an optical microscope to view a 10 μm wide line pattern, and the presence or absence of pattern peeling was evaluated from the following perspectives. A smaller exposure amount is preferable when it is required to form a pattern (image area) that adheres closely to the substrate and does not peel off. A: A non-peeling pattern can be formed with an exposure dose of 1000 mJ or less. B: A pattern without peeling can be formed with an exposure dose of over 1000mJ and up to 1400mJ. C: A non-peeling pattern can be formed with an exposure dose of over 1400mJ and up to 1700mJ. At exposure levels exceeding D:1700mJ, a pattern without peeling can be formed.

[0304] [Undercut width] Patterned substrates were fabricated using each resin composition in the same manner as described above, except that the aperture line width of the mask used during exposure was changed to 300 μm. For the obtained patterned substrates, cross-sectional scanning electron microscope images of 300 μm wide patterns were observed using a scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation), and the undercut width was measured. The substrates were then evaluated from the following perspectives. The undercut width is defined as "[(Line width at the widest point in the pattern cross-section) - (Line width at the point where the line pattern touches the substrate in the pattern cross-section)] ÷ 2". The "line width at the widest point in the pattern cross-section" mentioned above refers to 300 μm. A: Undercut width is less than 1.0 μm B: Undercut width is 1.0 μm or more and less than 1.5 μm C: Undercut width is 1.5 μm or more and less than 2.0 μm D: Undercut width of 2.0 μm or more

[0305] [Table 11]

[0306] [Table 12]

[0307] [Table 13]

[0308] When using the resin composition of the example, both demonstrated superior storage stability and particle size evaluation compared to the resin composition of the comparative example, and exhibited excellent pigment dispersibility. Furthermore, when using the resin composition of the example, both demonstrated superior residue, adhesion, and undercut evaluation compared to the resin composition of the comparative example.

[0309] Dispersions R2-1 to R2-24 were prepared in the same manner as dispersion R2, except that derivative 2, which was also used as a pigment derivative in dispersion R2, was replaced with derivatives 10 to 33. A resin composition was prepared in the same manner as in Example 3, except that dispersion R2 was replaced with dispersions R2-1 to R2-24. When the obtained resin composition was evaluated in the same manner as above, the evaluation results were the same as in Example 3.

[0310] Derivatives 10-33: Compounds with the following structure. The crystallite size of each derivative was adjusted by grinding. [ka] [ka] [ka] [ka]

[0311] The crystallite sizes and crystallinity of derivatives 10-33 are as follows. Crystallinity was determined using the following formula, with the maximum diffraction intensity Ic originating from the amorphous region and the maximum diffraction intensity Ia originating from the crystal, when the diffraction peak originating from the amorphous region was clear. [Crystallinity]=Ic / (Ia+Ic)

[0312] [Table 14]

Claims

1. Colorant A containing pigment, Resin B and containing solvent C, The resin B is a resin composition comprising resin B1 which includes an acid anhydride group and a polymer chain which includes repeating units of at least one structure selected from a polyether structure and a polyester structure, The resin B1 is a resin represented by formula (2). resin composition; 【Chemistry 1】 In equation (2), X² represents -COO-, -CONH-, or -S-, L1 represents a single bond, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, a group represented by formula (Z1-1), a group represented by formula (Z1-2), a group represented by formula (Z1-12), a group represented by formula (Z1-13), or a group represented by formula (Z1-14). P1 represents a polymer chain containing repeating units represented by any of formulas (P-1) to (P-4), and the terminal structure of the polymer chain is a hydrogen atom, alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, ethylenically unsaturated bond-containing group, epoxy group, or oxetanyl group. m and n each represent an integer greater than or equal to 1 independently; 【Chemistry 2】 In the formula, * represents a coupling; 【Transformation 3】 In the formula, R G1 to R G4 each independently represent an alkylene group.

2. Colorant A containing pigment, Resin B and containing solvent C, The resin B is a resin composition comprising resin B1 which includes an acid anhydride group and a polymer chain which includes repeating units of at least one structure selected from a polyether structure and a polyester structure, The resin B1 is a resin represented by formula (1), The solvent C comprises at least one solvent selected from ether-based solvents, ester-based solvents, and ketone-based solvents. resin composition; 【Chemistry 4】 In formula (1), R1 represents a group represented by any of the formulas (RAH-1) to (RAH-7), X1 and X2 each independently represent -COO-, -CONH-, or -S-, L1 represents a single bond, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, a group represented by formula (Z1-1), a group represented by formula (Z1-2), a group represented by formula (Z1-12), a group represented by formula (Z1-13), or a group represented by formula (Z1-14). P1 represents a polymer chain containing repeating units represented by any of formulas (P-1) to (P-4), and the terminal structure of the polymer chain is a hydrogen atom, alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, ethylenically unsaturated bond-containing group, epoxy group, or oxetanyl group. m and n each represent an integer greater than or equal to 1 independently; 【Transformation 5】 In formulas (RAH-1) to (RAH-7), * represents a coupling, RAH1, RAH7, RAH8, RAH10, and RAH11 represent hydrogen atoms. RAH2, RAH3, RAH4, RAH5, RAH6, and RAH9 represent substituents, and these substituents are halogen atoms, carboxyl groups, alkyl groups, or hydroxyl groups. r2, r3, r4, r5, r6, and r7 represent 0; 【Transformation 6】 In the formula, * represents a coupling; 【Transformation 7】 In the formula, R G1 to R G4 each independently represent an alkylene group.

3. Colorant A containing pigment, Resin B and containing solvent C, The resin B is a resin composition comprising resin B1 which includes an acid anhydride group and a polymer chain which includes repeating units of at least one structure selected from a polyether structure and a polyester structure, The resin B1 is a resin represented by formula (1), The aforementioned colorant A contains a black pigment, The content of black pigment in the total solid content of the resin composition is 65% by mass or more. resin composition; 【Transformation 8】 In formula (1), R1 represents a group represented by any of the formulas (RAH-1) to (RAH-7), X1 and X2 each independently represent -COO-, -CONH-, or -S-, L1 represents a single bond, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, a group represented by formula (Z1-1), a group represented by formula (Z1-2), a group represented by formula (Z1-12), a group represented by formula (Z1-13), or a group represented by formula (Z1-14). P1 represents a polymer chain containing repeating units represented by any of formulas (P-1) to (P-4), and the terminal structure of the polymer chain is a hydrogen atom, alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, ethylenically unsaturated bond-containing group, epoxy group, or oxetanyl group. m and n each represent an integer greater than or equal to 1 independently; 【Chemistry 9】 In formulas (RAH-1) to (RAH-7), * represents a coupling, RAH1, RAH7, RAH8, RAH10, and RAH11 represent hydrogen atoms. RAH2, RAH3, RAH4, RAH5, RAH6, and RAH9 represent substituents, and these substituents are halogen atoms, carboxyl groups, alkyl groups, or hydroxyl groups. r2, r3, r4, r5, r6, and r7 represent 0; 【Chemistry 10】 In the formula, * represents a coupling; 【Chemistry 11】 In the formula, R G1 to R G4 each independently represent an alkylene group.

4. Colorant A containing pigment, Resin B and containing solvent C, The resin B is a resin composition comprising resin B1 which includes an acid anhydride group and a polymer chain which includes repeating units of at least one structure selected from a polyether structure and a polyester structure, The resin B1 is a resin represented by formula (1), The resin composition further comprises a polymerizable monomer. resin composition; 【Chemistry 12】 In formula (1), R1 represents a group represented by any of the formulas (RAH-1) to (RAH-7), X1 and X2 each independently represent -COO-, -CONH-, or -S-, L1 represents a single bond, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, a group represented by formula (Z1-1), a group represented by formula (Z1-2), a group represented by formula (Z1-12), a group represented by formula (Z1-13), or a group represented by formula (Z1-14). P1 represents a polymer chain containing repeating units represented by any of formulas (P-1) to (P-4), and the terminal structure of the polymer chain is a hydrogen atom, alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, ethylenically unsaturated bond-containing group, epoxy group, or oxetanyl group. m and n each represent an integer greater than or equal to 1 independently; 【Chemistry 13】 In formulas (RAH-1) to (RAH-7), * represents a coupling, RAH1, RAH7, RAH8, RAH10, and RAH11 represent hydrogen atoms. RAH2, RAH3, RAH4, RAH5, RAH6, and RAH9 represent substituents, and these substituents are halogen atoms, carboxyl groups, alkyl groups, or hydroxyl groups. r2, r3, r4, r5, r6, and r7 represent 0; 【Chemistry 14】 In the formula, * represents a coupling; 【Chemistry 15】 In the formula, R G1 to R G4 each independently represent an alkylene group.

5. Colorant A containing pigment, Resin B and containing solvent C, The resin B is a resin composition comprising resin B1 which includes an acid anhydride group and a polymer chain which includes repeating units of at least one structure selected from a polyether structure and a polyester structure, The resin B1 is a resin represented by formula (1), The aforementioned resin composition further comprises a photopolymerization initiator. resin composition; 【Chemistry 16】 In formula (1), R1 represents a group represented by any of the formulas (RAH-1) to (RAH-7), X1 and X2 each independently represent -COO-, -CONH-, or -S-, L1 represents a single bond, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, a group represented by formula (Z1-1), a group represented by formula (Z1-2), a group represented by formula (Z1-12), a group represented by formula (Z1-13), or a group represented by formula (Z1-14). P1 represents a polymer chain containing repeating units represented by any of formulas (P-1) to (P-4), and the terminal structure of the polymer chain is a hydrogen atom, alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, ethylenically unsaturated bond-containing group, epoxy group, or oxetanyl group. m and n each represent an integer greater than or equal to 1 independently; 【Chemistry 17】 In formulas (RAH-1) to (RAH-7), * represents a coupling, RAH1, RAH7, RAH8, RAH10, and RAH11 represent hydrogen atoms. RAH2, RAH3, RAH4, RAH5, RAH6, and RAH9 represent substituents, and these substituents are halogen atoms, carboxyl groups, alkyl groups, or hydroxyl groups. r2, r3, r4, r5, r6, and r7 represent integers equal to 0; [Chemistry 18] In the formula, * represents a coupling; 【Chemistry 19】 In the formula, R G1 to R G4 each independently represent an alkylene group.

6. The aforementioned P １ The polymer chain represented by comprises at least one selected from an ethylenically unsaturated bond-containing group, an epoxy group, and an oxetanyl group, according to any one of claims 1 to 5.

7. The resin composition according to any one of claims 1 to 5, wherein the weight-average molecular weight of the resin B1 is 500 or more and less than 10,000.

8. The resin composition according to claim 1, wherein the solvent C comprises at least one solvent selected from ether-based solvents, ester-based solvents, and ketone-based solvents.

9. The aforementioned colorant A contains a black pigment, The resin composition according to claim 1, wherein the content of black pigment in the total solid content of the resin composition is 65% by mass or more.

10. Furthermore, the resin composition according to claim 1, comprising a polymerizable monomer.

11. Furthermore, the resin composition according to claim 1, comprising a photopolymerization initiator.

12. A film obtained using the resin composition according to any one of claims 1 to 5.

13. An optical filter having the film described in claim 12.

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

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

Images