Resin composition, method for producing resin composition, method for producing film, method for producing optical filter, method for producing solid-state imaging device, and method for producing image display device

Abstract

Provided is a resin composition exhibiting suppressed variations in pigment average particle diameter even after long-term storage at a low temperature. The resin composition contains a pigment, a resin, and a solvent, and the solvent contains an ether-based solvent represented by formula (1). In formula (1), R1 is a hydrocarbon group and R2 through R6 are each independently a hydrogen atom or a hydrocarbon group.

Description

[Technical Field]

[0001] The present invention relates to a resin composition containing a pigment, and also to a method for producing the resin composition, a film, an optical filter, a solid-state imaging device, and an image display device. [Background technology]

[0002] 2. Description of the Related Art Optical filters such as color filters are produced using resin compositions containing pigments.

[0003] For example, Patent Document 1 describes the production of a color filter using a resin composition containing a colorant (A) such as an organic pigment or an inorganic pigment, a binder polymer (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E) containing propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-199040 Summary of the Invention [Problem to be solved by the invention]

[0005] When forming a film using a resin composition, the film may be formed using a resin composition that has been stored at low temperature for a long period of time.

[0006] However, if the dispersibility of the pigment in the resin composition is low, even if the average particle diameter of the pigment is small in the resin composition immediately after production, the pigment in the resin composition is likely to aggregate during storage of the resin composition, resulting in an increase in the average particle diameter of the pigment. If the average particle diameter of the pigment present in the resin composition increases, the viscosity of the resin composition increases, and the coatability of the resin composition is likely to decrease. Therefore, as the storage period of the resin composition increases, the thickness of the resulting film tends to become more uneven. Furthermore, the increase in the average particle diameter of the pigment during storage of the resin composition may result in differences in the performance, such as the spectral characteristics, of the film between a film formed using a resin composition immediately after production and a film formed using a resin composition after long-term storage.

[0007] The present inventors have studied the resin composition described in Patent Document 1 and found that there is room for further improvement in terms of pigment dispersibility.

[0008] Therefore, an object of the present invention is to provide a resin composition in which fluctuations in the average particle size of the pigment are suppressed even after long-term storage at low temperatures. The present invention also provides methods for producing a resin composition, a film, an optical filter, a solid-state imaging device, and an image display device. [Means for solving the problem]

[0009] According to the inventors' investigations, it was found that the above object can be achieved by the following constitution, and the present invention was completed based on this finding. <1> Contains a pigment, a resin, and a solvent, a resin composition, wherein the solvent contains an ether-based solvent represented by formula (1); [ka] In formula (1), R 1 represents a hydrocarbon group, and R 2 ~R 6 each independently represents a hydrogen atom or a hydrocarbon group. <2> The ether solvent represented by the formula (1) is at least one selected from anisole, phenetole, 4-methylanisole, 3-methylanisole, and 2-methylanisole. <1> The resin composition according to claim 1. <3> The solvent contains 1 to 100 mass % of an ether solvent represented by the formula (1). <1> or <2> The resin composition according to claim 1. <4> The solvent contains 1 to 50 mass % of an ether solvent represented by the formula (1). <1> or <2> The resin composition according to claim 1. <5> The resin composition contains 0.5 mass % or more of an ether-based solvent represented by the formula (1). <1> ~ <4> The resin composition according to any one of the above. <6> The solvent includes an ether-based solvent represented by the formula (1) above and a solvent other than the ether-based solvent represented by the formula (1) above. <1> ~ <5> The resin composition according to any one of the above. <7> Solvents other than the ether solvent represented by the above formula (1) include propylene glycol monomethyl ether acetate. <6> The resin composition according to claim 1. <8> The ether solvent represented by the formula (1) contains 100 to 9900 parts by mass of propylene glycol monomethyl ether acetate. <7> The resin composition according to claim 1. <9> The solvent other than the ether-based solvent represented by the above formula (1) includes a ketone-based solvent. <6> ~ <8> The resin composition according to any one of the above. <10> The pigment includes at least one selected from a chromatic pigment and a near-infrared absorbing pigment. <1> ~ <9> The resin composition according to any one of the above. <11> <1> ~ <10> a method for producing the resin composition according to any one of the above items, the method comprising a step of dispersing a pigment in the presence of a resin and a solvent containing an ether-based solvent represented by formula (1); [ka] In formula (1), R 1 represents a hydrocarbon group, and R 2 ~R 6each independently represents a hydrogen atom or a hydrocarbon group. <12> <1> ~ <10> 10. A method for producing a film, comprising the step of applying the resin composition according to any one of the above items to a support. <13> <12> 2. A method for producing an optical filter, comprising the method for producing the film according to claim 1. <14> <12> 10. A method for manufacturing a solid-state imaging device, comprising the method for manufacturing the film according to claim 9. <15> <12> 2. A method for producing an image display device, comprising the method for producing the film according to claim 1. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a resin composition in which fluctuations in the average particle size of the pigment are suppressed even after long-term storage at low temperatures, and it is also possible to provide methods for producing the resin composition, a film, an optical filter, a solid-state imaging device, and an image display device. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (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 bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, "(meth)acrylate" refers to either or both of acrylate and methacrylate, "(meth)acrylic" refers to either or both of acrylic and methacrylic, and "(meth)acryloyl" refers to either or both of acryloyl and methacryloyl. In this specification, in the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, Pr represents a propyl group, and Ph represents a phenyl group. In this specification, the weight average molecular weight and number average molecular weight are values ​​measured by GPC (gel permeation chromatography) in terms of polystyrene. In this specification, near-infrared light refers to light with a wavelength of 700 to 2500 nm. In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In this specification, the term "pigment" refers to a coloring material that is difficult to dissolve in a solvent. For example, the solubility of the pigment in 100 g of water at 23°C and 100 g of propylene glycol monomethyl ether acetate at 23°C is preferably 0.1 g or less, and more preferably 0.01 g or less. In this specification, the term "dye" refers to a coloring material that is easily soluble in a solvent. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved.

[0012] <Resin composition> The resin composition of the present invention comprises a pigment, a resin, and a solvent, and is characterized in that the solvent comprises an ether-based solvent represented by formula (1). JPEG0007752127000003.jpg4157In formula (1), R 1 represents a hydrocarbon group, and R 2 ~R 6 each independently represents a hydrogen atom or a hydrocarbon group.

[0013] The ether-based solvent contained in the resin composition of the present invention is presumed to have a high affinity with pigments and to be able to weaken the tendency for pigments to aggregate with each other. Therefore, the resin composition of the present invention can suppress fluctuations in the average particle size of the pigments even after long-term storage at low temperatures (e.g., 5°C). It is presumed that the ether-based solvent represented by formula (1) interacts with the conjugated system of the organic pigment, thereby further increasing its affinity with the organic pigment. Therefore, when an organic pigment is used as the pigment, fluctuations in the average particle size can be more effectively suppressed.

[0014] Furthermore, by using the resin composition of the present invention, it is possible to form a film with excellent film thickness uniformity. The reason for this effect is presumably that the thixotropy of the resin composition can be reduced by suppressing the aggregation of the pigment.

[0015] 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, and color filters are preferred. The resin composition of the present invention is also preferably used for solid-state imaging devices. More specifically, it is preferably used as a resin composition for optical filters used in solid-state imaging devices, and more preferably used as a resin composition for forming colored pixels of color filters used in solid-state imaging devices.

[0016] The color filter may have colored pixels that transmit light of a specific wavelength. Examples of the colored pixels include red, green, blue, magenta, cyan, and yellow pixels. Green or cyan pixels are preferred, and green pixels are more preferred. The colored pixels of the color filter can be formed using a resin composition containing a chromatic pigment.

[0017] The maximum absorption wavelength of the near-infrared cut filter is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. The transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. The ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm (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. The near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing pigment.

[0018] The near-infrared transmission filter is a filter that transmits at least a portion of near-infrared light. The near-infrared transmission filter may be a filter (transparent film) that transmits both visible light and near-infrared light, or may be a filter that blocks at least a portion of visible light and transmits at least a portion of near-infrared light. Preferred examples of the near-infrared transmission filter include filters that satisfy the spectral characteristics of 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. The near-infrared transmission filter is preferably a filter that satisfies any one 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.

[0019] The resin composition of the present invention can also be used as a light-shielding film.

[0020] The solid content of the resin composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0021] Each component used in the resin composition of the present invention will be described below.

[0022] <<Pigments>> The resin composition of the present invention contains a pigment. Examples of the pigment include a white pigment, a black pigment, a chromatic pigment, and a near-infrared absorbing pigment. In this specification, the white pigment includes not only pure white pigments but also light gray pigments close to white (e.g., off-white, light gray, etc.).

[0023] When the resin composition is used for a color filter, a chromatic pigment is used as the pigment. The chromatic pigment may be of only one type, or may contain two or more types. When the resin composition is used for forming a near-infrared cut filter, a near-infrared absorbing pigment is used as the pigment. The near-infrared absorbing pigment may be of only one type, or may contain two or more types. When forming pixels for a near-infrared transmission filter from the resin composition, two or more chromatic pigments are used in combination, or a black pigment is used as the pigment.

[0024] The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In the present invention, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of ​​the primary particles of the pigment is determined, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment. In the present invention, the average primary particle diameter is the arithmetic mean value of the primary particle diameters of 400 primary particles of the pigment. Furthermore, primary particles of the pigment refer to independent particles that are not aggregated.

[0025] The pigment used in the present invention is preferably an organic pigment, as this more significantly enhances the effects of the present invention. It is more preferably at least one selected from phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, isoindoline pigments, azo pigments, azomethine pigments, quinophthalone pigments, dioxazine pigments, and pteridine pigments, and even more preferably a phthalocyanine pigment. Preferred phthalocyanine pigments include green pigments such as Color Index (CI) Pigment Green 7, 36, 58, 59, 62, and 63, and blue pigments such as CI Pigment Blue 15:3, 15:4, 15:6, and 16. Preferred diketopyrrolopyrrole pigments include red pigments such as CI Pigment Red 254, 264, 272, and 291. Preferred anthraquinone pigments include red pigments such as CI Pigment Red 177. Preferred isoindoline pigments include yellow pigments such as CI Pigment Yellow 139 and 185. Preferred azo pigments include CI Pigment Yellow 150, a yellow pigment, and CI Pigment Red 269, a red pigment. Furthermore, azobarbituric acid nickel complex pigments having the following structure can also be used as azo pigments. Preferred quinophthalone pigments include CI Pigment Yellow 138, 231, and 233, which are yellow pigments. Preferred dioxazine pigments include CI Pigment Violet 23, which is a purple pigment. Preferred pteridine pigments include CI Pigment Yellow 215, which is a yellow pigment. Preferred azomethine pigments include CI Pigment Yellow 129, which is a yellow pigment. [ka]

[0026] The pigments used in the present invention will be described in more detail below.

[0027] (chromatic pigments) The chromatic pigment is not particularly limited, and known chromatic pigments can be used. Examples of chromatic pigments include pigments having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples include yellow pigments, orange pigments, red pigments, green pigments, purple pigments, and blue pigments. The chromatic pigment is preferably an organic pigment. Specific examples of these include the following:

[0028] CIPigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63, 65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,12 6,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,215,228,231,232,233,234,235,236 etc. (yellow pigments), CIPigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (orange pigments), CIPigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53: 1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155, 166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294,295,296,297 etc. (above, red pigments), CIPigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66, etc. (above, green pigments), CIPigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61, etc. (purple pigments), CIPigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. (all blue pigments).

[0029] Alternatively, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms per molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule may be used. Specific examples include the phthalocyanine pigments described in International Publication No. 2015 / 118720. Other examples of green pigments that may be used include compounds described in Chinese Patent Application No. 106909027, phthalocyanine compounds having a phosphate ester as a ligand described in International Publication No. 2012 / 102395, phthalocyanine compounds described in Japanese Patent Application Laid-Open No. 2019-008014, phthalocyanine compounds described in Japanese Patent Application Laid-Open No. 2018-180023, compounds described in Japanese Patent Application Laid-Open No. 2019-038958, and core-shell pigments described in Japanese Patent Application Laid-Open No. 2020-076995.

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

[0031] In addition, as the yellow pigment, azobarbituric acid nickel complex pigments having the above-mentioned structure can also be used. In addition, as the yellow pigment, the compounds described in JP-A-2017-201003, the compounds described in JP-A-2017-197719, the compounds described in JP-A-2017-171912, paragraphs 0011 to 0062 and 0137 to 0276, the compounds described in JP-A-2017-171913, paragraphs 0010 to 0062 and 0138 to 0295, the compounds described in JP-A-2017-171914, paragraphs 0011 to 0062 and 0139 to 0190, the compounds described in JP-A-2017-171915, paragraphs 0010 to 0065, JP-A-2013-054339, paragraphs 0011 to 0034 of the quinophthalone compounds described in JP-A-2014-026228, paragraphs 0013 to 0058 of the quinophthalone compounds described in JP-A-2014-026228, isoindoline compounds described in JP-A-2018-062644, JP-A-2018-203798, JP-A-2018-062578, JP-A-6432076, JP-A-2018-1558 81 , quinophthalone compounds described in JP 2018-111757 A, quinophthalone compounds described in JP 2018-040835 A, quinophthalone compounds described in JP 2017-197640 A, quinophthalone compounds described in JP 2016-145282 A, quinophthalone compounds described in JP 2014-085565 A, quinophthalone compounds described in JP 2014-021139 A, quinophthalone compounds described in JP 2013-209614 A, JP 201 quinophthalone compounds described in JP-A-3-209435, quinophthalone compounds described in JP-A-2013-181015, quinophthalone compounds described in JP-A-2013-061622, quinophthalone compounds described in JP-A-2013-032486, quinophthalone compounds described in JP-A-2012-226110, quinophthalone compounds described in JP-A-2008-074987, quinophthalone compounds described in JP-A-2008-081565, quinophthalone compounds described in JP-A-2008-074986,Quinophthalone compounds described in JP 2008-074985 A, quinophthalone compounds described in JP 2008-050420 A, quinophthalone compounds described in JP 2008-031281 A, quinophthalone compounds described in JP 48-032765 A, quinophthalone compounds described in JP 2019-008014 A, quinophthalone compounds described in Japanese Patent No. 6607427 A, compounds represented by the following formula (QP1), compounds represented by the following formula (QP2), compounds described in Korean Patent Publication No. 10-2014-0034963, compounds described in JP 2017-095706 A, compounds described in Taiwan Patent Application Publication No. 201920495, and Japanese Patent No. 66074 Compounds described in JP-A-27, compounds described in JP-A-2020-033525, compounds described in JP-A-2020-033524, compounds described in JP-A-2020-033523, compounds described in JP-A-2020-033522, compounds described in JP-A-2020-033521, compounds described in WO 2020 / 045200, compounds described in WO 2020 / 045199, compounds described in WO 2020 / 045197, perylene compounds described in JP-A-2020-083982, perylene compounds described in WO 2020 / 105346, and quinophthalone compounds described in JP-T-2020-517791 can also be used. Polymerized versions of these compounds are also preferably used from the viewpoint of improving color value. [ka]

[0032] In formula (QP1), X 1 ~X 16 each independently represents a hydrogen atom or a halogen atom; Z 1 represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by formula (QP1) include the compounds described in paragraph 0016 of Japanese Patent No. 6443711. [ka]

[0033] In formula (QP2), Y 1 ~Y 3 each independently represents a halogen atom. n and m represent integers of 0 to 6, and p represents an integer of 0 to 5. (n+m) is 1 or greater. Specific examples of the compound represented by formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.

[0034] Examples of red pigments include diketopyrrolopyrrole compounds having at least one bromine atom substituted in the structure described in JP 2017-201384 A, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, diketopyrrolopyrrole compounds described in WO 2012 / 102399, diketopyrrolopyrrole compounds described in WO 2012 / 117965, naphthol azo compounds described in JP 2012-229344 A, red pigments described in Japanese Patent No. 6516119, and Examples of the red pigment include the red pigment described in Japanese Patent Publication No. 525101, the brominated diketopyrrolopyrrole compound described in paragraph 0229 of Japanese Patent Application Laid-Open No. 2020-090632, the anthraquinone compound described in Korean Patent Publication No. 10-2019-0140741, the anthraquinone compound described in Korean Patent Publication No. 10-2019-0140744, the perylene compound described in Japanese Patent Application Laid-Open No. 2020-079396, and the diketopyrrolopyrrole compound described in paragraphs 0025 to 0041 of Japanese Patent Application Laid-Open No. 2020-066702. Also usable as the red pigment are compounds having a structure in which an aromatic ring group, in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to the aromatic ring, is bonded to a diketopyrrolopyrrole skeleton.

[0035] Furthermore, from the viewpoint of improving spectral characteristics, it is also preferable to use a halogenated zinc phthalocyanine pigment having the Raman spectrum described in Japanese Patent No. 6744002. Furthermore, from the viewpoint of viscosity adjustment, it is also preferable to use a dioxazine pigment having a controlled contact angle described in International Publication No. 2019 / 107166.

[0036] For the diffraction angles that various pigments preferably have, please refer to the descriptions in Japanese Patent Nos. 6561862, 6413872, 6281345, and JP-A-2020-026503, the contents of which are incorporated herein by reference. It is also preferable that the crystallite size of the pyrrolopyrrole pigment in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight (±1±1±1) crystal lattice planes is 140 Å or less. It is also preferable that the physical properties of the pyrrolopyrrole pigment be set as described in paragraphs 0028 to 0073 of JP-A-2020-097744.

[0037] Two or more chromatic pigments may be used in combination. For example, when the resin composition of the present invention is used for forming green pixels of a color filter, it is preferable to use a green pigment and a yellow pigment in combination. When the resin composition of the present invention is used for forming red pixels of a color filter, it is preferable to use a red pigment and a yellow pigment in combination. When the resin composition of the present invention is used for forming blue pixels of a color filter, it is preferable to use a blue pigment and a purple pigment in combination.

[0038] The pigment used in the coloring composition of the present invention preferably contains a green pigment, and more preferably contains both a green pigment and a yellow pigment. Furthermore, the green pigment is preferably a phthalocyanine pigment (also referred to as a phthalocyanine green pigment). Phthalocyanine green pigments tend to have high pigment aggregation and low dispersibility. However, according to the resin composition of the present invention, even when a phthalocyanine green pigment is used, excellent dispersibility can be obtained, and the effects of the present invention are significantly achieved when a phthalocyanine green pigment is used. The phthalocyanine green pigment is preferably a phthalocyanine pigment having a central metal (also referred to as a metal phthalocyanine pigment). Examples of metal phthalocyanine pigments include copper phthalocyanine pigments, zinc phthalocyanine pigments, and aluminum phthalocyanine pigments, with copper phthalocyanine pigments and zinc phthalocyanine pigments being preferred.

[0039] Furthermore, when two or more chromatic pigments are used in combination, the combination of two or more chromatic pigments may form a black color. Examples of such combinations include the following embodiments (1) to (7). When the resin composition contains two or more chromatic pigments and exhibits a black color through the combination of two or more chromatic pigments, the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared transmission filter. (1) An embodiment containing a red pigment and a blue pigment. (2) An embodiment containing a red pigment, a blue pigment, and a yellow pigment. (3) An embodiment containing a red pigment, a blue pigment, a yellow pigment, and a purple pigment. (4) An embodiment containing a red pigment, a blue pigment, a yellow pigment, a purple pigment, and a green pigment. (5) An embodiment containing a red pigment, a blue pigment, a yellow pigment, and a green pigment. (6) An embodiment containing a red pigment, a blue pigment, and a green pigment. (7) An embodiment containing a yellow pigment and a purple pigment.

[0040] (white pigment) Examples of white pigments include titanium oxide, 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. The white pigment is preferably a particle having a titanium atom, more preferably titanium oxide. Furthermore, the white pigment is preferably a particle having a refractive index of 2.10 or more for light with a wavelength of 589 nm. The refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.

[0041] Furthermore, the white pigment may be titanium oxide as described in "Titanium Oxide: Physical Properties and Application Technology, by Kiyono Manabu, pages 13-45, published June 25, 1991, by Gihodo Publishing."

[0042] The white pigment may be composed of a single inorganic substance or a composite particle of other materials. For example, it is preferable to use particles having internal voids or other materials, particles with a large number of inorganic particles attached to a core particle, or core-shell composite particles consisting of a core particle made of a polymer particle and a shell layer made of inorganic nanoparticles. For examples of core-shell composite particles consisting of a core particle made of a polymer particle and a shell layer made of inorganic nanoparticles, see, for example, paragraphs 0012 to 0042 of JP 2015-047520 A, the contents of which are incorporated herein by reference.

[0043] The white pigment may also be hollow inorganic particles. Hollow inorganic particles are inorganic particles with a structure having a cavity inside, and refer to inorganic particles having a cavity surrounded by an outer shell. Examples of hollow inorganic particles include those described in JP 2011-075786 A, WO 2013 / 061621 A, JP 2015-164881 A, etc., the contents of which are incorporated herein by reference.

[0044] (black pigment) The black pigment is not particularly limited, and known pigments can be used. Examples include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black refers to black particles containing titanium atoms, and low-order titanium oxide or titanium oxynitride is preferred. The surface of titanium black can be modified as needed for purposes such as improving dispersibility and suppressing aggregation. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. It can also be treated with a water-repellent substance, as described in JP 2007-302836 A. Examples of black pigments include CI Pigment Black 1 and 7. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, with the Si atom to Ti atom ratio adjusted to a range of 0.20 to 0.50, can be used. For details of the dispersion, please refer to paragraphs 0020 to 0105 of JP 2012-169556 A, the contents of which are incorporated herein by reference. Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R-N, and 13M-T (trade names: manufactured by Mitsubishi Materials Corporation) and Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.).

[0045] (Near infrared absorbing pigment) The near-infrared absorbing pigment is preferably an organic pigment. The near-infrared absorbing pigment preferably has a maximum absorption wavelength in the wavelength range of more than 700 nm to 1400 nm. The maximum absorption wavelength of the near-infrared absorbing pigment is preferably 1200 nm or less, more preferably 1000 nm or less, and even more preferably 950 nm or less. The near-infrared absorbing pigment preferably has an absorbance A at a wavelength of 550 nm. 550 and absorbance A at the maximum absorption wavelength max A is the ratio of 550 / A maxis preferably 0.1 or less, more preferably 0.05 or less, even more preferably 0.03 or less, and particularly preferably 0.02 or less. The lower limit is not particularly limited, but can be, for example, 0.0001 or more, or even 0.0005 or more. If the absorbance ratio is within the above range, a near-infrared absorbing pigment with excellent visible transparency and near-infrared shielding properties can be obtained. In the present invention, the maximum absorption wavelength and absorbance values ​​at each wavelength of the near-infrared absorbing pigment are values ​​determined from the absorption spectrum of a film formed using a resin composition containing the near-infrared absorbing pigment.

[0046] The near-infrared absorbing pigment is not particularly limited, but examples thereof include pyrrolopyrrole compounds, rylene compounds, oxonol compounds, squarylium compounds, cyanine compounds, croconium compounds, phthalocyanine compounds, naphthalocyanine compounds, pyrylium compounds, azulenium compounds, indigo compounds, and pyrromethene compounds, and is preferably at least one selected from pyrrolopyrrole compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, and naphthalocyanine compounds, more preferably a pyrrolopyrrole compound or squarylium compound, and particularly preferably a pyrrolopyrrole compound. Specific examples of near-infrared absorbing pigments include the compounds described in the Examples below.

[0047] The content of the pigment in the total solid content of the resin composition is preferably 30 to 80% by mass. The lower limit is preferably 35% by mass or more, and more preferably 40% by mass or more. The upper limit is preferably 75% by mass or less, and more preferably 70% by mass or less. The content of the organic pigment in the pigment is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass. The content of the chromatic pigment in the pigment is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass.

[0048] <<dye>> The resin composition of the present invention may contain a dye. The dye is not particularly limited, and known dyes can be used. Examples of dyes include chromatic dyes, black dyes, and near-infrared absorbing dyes. Known dyes can be used. Also usable are methine dyes described in JP-A-2019-073695, JP-A-2019-073696, JP-A-2019-073697, JP-A-2019-073698, and azo dyes described in JP-A-2020-093994. Dye multimers can also be used as dyes. Dye multimers have two or more dye structures in one molecule, and preferably three or more dye structures. The upper limit is not particularly limited, but can be 100 or less. The multiple dye structures in one molecule may be the same or different dye structures. The weight-average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. As the dye multimer, compounds described in JP-A Nos. 2011-213925, 2013-041097, 2015-028144, 2015-030742, 2016-102191, WO 2016 / 031442, etc. can also be used.

[0049] The content of the dye in the total solid content of the resin composition is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The content of the dye in the resin composition is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 60 parts by mass or less, per 100 parts by mass of the pigment.

[0050] It is also preferable that the resin composition of the present invention is substantially free of dyes. According to this embodiment, the proportion of pigments in the resin composition can be increased, and the effects of the present invention are more pronounced. In this specification, "substantially free of dyes" means that the content of dyes in the total solid content of the resin composition is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably free of dyes.

[0051] <<Resin>> The resin composition of the present invention contains a resin. The resin is blended, for example, to disperse pigments or the like in the resin composition or as a binder. Resins used primarily to disperse pigments are also called dispersants. However, these uses of resins are merely examples, and the resin can also be used for purposes other than these.

[0052] The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4,000 or more, more preferably 5,000 or more.

[0053] Examples of resins include (meth)acrylic resins, enethiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyimine resins, polyolefin resins, cyclic olefin resins, polyester resins, and styrene resins. These resins may be used alone or in combination. Also usable are the resins described in paragraphs 0041 to 0060 of JP 2017-206689 A, the resins described in paragraphs 0022 to 0071 of JP 2018-010856 A, and the blocked polyisocyanate resins described in JP 2016-222891 A.

[0054] The resin composition of the present invention preferably contains a resin having an acid group. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and the carboxyl group is preferred. The resin having an acid group can be used, for example, as an alkali-soluble resin.

[0055] The resin having an acid group preferably contains a repeating unit having an acid group on a side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group on a side chain based on all repeating units of the resin. The upper limit of the content of repeating units having an acid group on a side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having an acid group on a side chain is preferably 10 mol% or more, more preferably 20 mol% or more.

[0056] It is also preferable that the resin having an acid group contains a repeating unit derived from a monomer component containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimers").

[0057] [ka]

[0058] In formula (ED1), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [ka] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), reference can be made to the description in JP-A-2010-168539, the contents of which are incorporated herein by reference.

[0059] Specific examples of ether dimers can be found in, for example, paragraph 0317 of JP-A-2013-029760, the contents of which are incorporated herein by reference.

[0060] The resin used in the present invention also preferably contains a repeating unit derived from a compound represented by the following formula (X). [ka] In formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 10 carbon atoms, R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and n represents an integer of 1 to 15.

[0061] For resins having acid groups, see paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding to paragraphs 0685 to 0700 of US Patent Application Publication No. 2012 / 0235099 A), and paragraphs 0076 to 0099 of JP 2012-198408 A, the contents of which are incorporated herein by reference. In addition, resins having acid groups can also be used, such as those described in paragraphs 0107 to 0111 of JP 2010-002457 A and those described in paragraphs 0095 to 0098 of JP 2020-046655 A.

[0062] The acid value of the resin having acid groups is preferably 5 to 200 mgKOH / g. The upper limit is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less. The lower limit is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and even more preferably 20 mgKOH / g or more. The weight average molecular weight (Mw) of the resin having acid groups is preferably 3,000 to 35,000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The lower limit is preferably 4,000 or more, more preferably 6,000 or more, and even more preferably 7,000 or more.

[0063] The resin composition of the present invention may also use a resin having a basic group. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in a side chain, more preferably a copolymer having a repeating unit having a basic group in a side chain and a repeating unit not having a basic group, and even more preferably a block copolymer having a repeating unit having a basic group in a side chain and a repeating unit not having a basic group. The resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mgKOH / g. The lower limit is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more. The upper limit is preferably 200 mgKOH / g or less, more preferably 100 mgKOH / g or less. Examples of resins having a basic group include the block copolymer (B) described in paragraphs 0063 to 0112 of JP-A No. 2014-219665 and the block copolymer A1 described in paragraphs 0046 to 0076 of JP-A No. 2018-156021.

[0064] Commercially available resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919, and BYK-LPN21116 (all manufactured by BYK-Chemie), SOLS Examples of such acrylic resins include PERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, and 7100 (all manufactured by Lubrizol Japan), and Efka PX 4300, 4330, 4046, 4060, and 4080 (all manufactured by BASF).

[0065] The resin composition of the present invention preferably contains a graft resin having an acid group (hereinafter also referred to as an acidic graft resin). The acidic graft resin can be preferably used as a dispersant. Here, the graft resin means a resin containing a repeating unit having a graft chain. Furthermore, the graft chain means a polymer chain that branches off from the main chain of the repeating unit.

[0066] The graft chain is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure, and more preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure.

[0067] The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, a hydroxy group, and an amino group. Among these, from the viewpoint of improving the dispersibility of pigments and the like, a group having a steric repulsion effect is preferred, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched groups are preferred.

[0068] The weight-average molecular weight of the graft chain is preferably 500 to 10,000. The upper limit is preferably 5,000 or less, more preferably 3,000 or less. The lower limit is preferably 800 or more, more preferably 1,000 or more. In this specification, the weight-average molecular weight of the graft chain is a value calculated from the weight-average molecular weight of the raw material monomer used in the polymerization of the repeating unit having the graft chain. For example, the repeating unit having the graft chain can be formed by polymerizing a macromonomer. Here, the macromonomer refers to a polymer compound having a polymerizable group introduced at the polymer terminal. The weight-average molecular weight of the raw material monomer is a polystyrene-equivalent value measured by GPC (gel permeation chromatography).

[0069] Examples of the acid group contained in the acidic graft resin include a carboxyl group, a sulfo group, and a phosphate group, with a carboxyl group being preferred. The acid value of the acidic graft resin is preferably 20 to 150 mgKOH / g. The upper limit is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less. The lower limit is preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 35 mgKOH / g or more.

[0070] The weight average molecular weight of the acidic graft resin is preferably 3,000 to 35,000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The lower limit is preferably 4,000 or more, more preferably 6,000 or more, and even more preferably 7,000 or more.

[0071] Examples of acidic graft resins include resins containing a repeating unit having a graft chain and a repeating unit having an acid group, and resins containing a repeating unit represented by the following formula (Ac-2). The acidic graft resin may further contain other repeating units, such as a repeating unit having a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group.

[0072] When the acidic graft resin is a resin containing a repeating unit having a graft chain and a repeating unit having an acid group, the acidic graft resin preferably contains 1 mol% or more of the repeating unit having a graft chain, more preferably 2 mol% or more, and even more preferably 3 mol% or more of the repeating unit having a graft chain, based on the total repeating units of the acidic graft resin. The upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, or even 50 mol% or less. Furthermore, the acidic graft resin preferably contains 1 mol% or more of the repeating unit having an acid group, more preferably 2 mol% or more, and even more preferably 3 mol% or more of the repeating unit. The upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, or even 50 mol% or less.

[0073] Next, the repeating unit represented by formula (Ac-2) will be described. [ka] In formula (Ac-2), Ar 10 represents a group containing an aromatic carboxyl group, and L 11 represents -COO- or -CONH-, and L 12 represents a trivalent linking group, P 10 represents a polymer chain.

[0074] In formula (Ac-2), Ar 10 Examples of the group containing an aromatic carboxyl group represented by the formula (I) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, etc. Examples of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures: [ka]

[0075] In the above formula, Q 1 represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2). [ka]

[0076] Ar 10 The group containing an aromatic carboxyl group represented by may have a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated bond-containing group or a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group. 10 Specific examples of the group containing an aromatic carboxyl group represented by formula (Ar-11), a group represented by formula (Ar-12), a group represented by formula (Ar-13), etc. [ka]

[0077] In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2. In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2. In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1. However, at least one of n3 and n4 is an integer of 1 or greater. In formula (Ar-13), Q 1 represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the above formula (Q-1) or a group represented by the above formula (Q-2). In formulas (Ar-11) to (Ar-13), *1 represents L 11 represents the bonding position with

[0078] In formula (Ac-2), L 11 is preferably —COO—.

[0079] In formula (Ac-2), L 12 Examples of the trivalent linking group represented by include hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups combining two or more of these. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. L 12 The trivalent linking group represented by is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2). [ka]

[0080] In formula (L12-1), L 12b represents a trivalent linking group, and X 1 represents S, and *1 represents L in formula (Ac-2). 11 *2 represents the bonding position of P in formula (Ac-2).10 It represents the bond position with L 12b Examples of the trivalent linking group represented by the formula (I) include a hydrocarbon group; and a group combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and a hydrocarbon group or a group combining a hydrocarbon group with -O- is preferred.

[0081] In formula (L12-2), L 12c represents a trivalent linking group, and X 1 represents S, and *1 represents L in formula (Ac-2). 11 *2 represents the bonding position of P in formula (Ac-2). 10 It represents the bond position with L 12c Examples of the trivalent linking group represented by the formula (I) include a hydrocarbon group; and a group combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and a hydrocarbon group is preferred.

[0082] P in formula (Ac-2) 10 The polymer chain represented by P includes a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure, and is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure. 10 The weight average molecular weight of the polymer chain represented by is preferably 500 to 10,000. The upper limit is preferably 5,000 or less, more preferably 3,000 or less. The lower limit is preferably 800 or more, more preferably 1,000 or more.

[0083] P 10 The polymer chain represented by may contain a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group. 10The proportion of repeating units containing a polymerizable group in all repeating units constituting the copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. The upper limit can be set to 100% by mass, and is preferably 90% by mass or less, and more preferably 60% by mass or less.

[0084] P 10 The polymer chain represented by P preferably contains a repeating unit containing an acid group. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group. 10 The proportion of repeating units containing an acid group in all repeating units constituting the polymer is preferably from 1 to 30 mass %, more preferably from 2 to 20 mass %, and even more preferably from 3 to 10 mass %.

[0085] Furthermore, a polyimine resin containing a nitrogen atom in at least one of the main chain and the side chain can also be used as the acidic graft resin. As the polyimine resin, a resin having a main chain with a partial structure having a functional group with a pKa of 14 or less and a side chain with 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and the side chain is preferred. There are no particular limitations on the basic nitrogen atom, as long as it is a nitrogen atom that exhibits basicity.

[0086] Specific examples of the acidic graft resin include resins B-1 to B-5 described in the Examples below. Furthermore, the acidic graft resin may also be the resins described in paragraphs 0025 to 0094 of JP-A-2012-255128 and the polyimine resins described in paragraphs 0102 to 0166 of JP-A-2012-255128.

[0087] The resin composition of the present invention preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the term "acidic dispersant (acidic resin)" refers to a resin in which the amount of acid groups is greater than the amount of basic groups. When the total amount of acid groups and basic groups is taken as 100 mol%, the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more, and more preferably a resin consisting essentially of acid groups. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g. The term "basic dispersant (basic resin)" refers to a resin in which the amount of basic groups is greater than the amount of acid 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 acid groups and basic groups is taken as 100 mol %. The basic groups possessed by the basic dispersant are preferably amino groups.

[0088] The resin used as a dispersant is preferably a resin having a structure in which multiple polymer chains are bonded to a core portion. 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 JP 2013-043962 A.

[0089] Furthermore, resins such as the above-mentioned block copolymers and acidic graft resins can also be used as dispersants.

[0090] Further, as dispersants, resins described in JP 2018-087939 A, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077 A, polyethyleneimine having a polyester side chain described in WO 2016 / 104803 A, block copolymers described in WO 2019 / 125940 A, block polymers having an acrylamide structural unit described in JP 2020-066687 A, block polymers having an acrylamide structural unit described in JP 2020-066688 A, and the like can also be used.

[0091] Dispersants are also commercially available, and specific examples include the BYK series and DISPERBYK series manufactured by BYK-Chemie, the SOLSPERSE series manufactured by Lubrizol Japan, and the Efka series manufactured by BASF. Pigment dispersants described in paragraphs 0041 to 0130 of JP 2014-130338 A can also be used, the contents of which are incorporated herein by reference. The resins described above as dispersants can also be used for purposes other than as dispersants. For example, they can be used as binders.

[0092] The resin content of the resin composition is preferably 5 to 40% by mass based on the total solid content. The lower limit is preferably 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The content of the resin having an acid group in the total solid content of the resin composition is preferably 5 to 40% by mass. The lower limit is preferably 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The content of the resin as a dispersant is preferably 10 to 60 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.

[0093] <<Solvent>> The resin composition of the present invention contains a solvent. The solvent is preferably liquid at 20°C. The solvent contained in the resin composition of the present invention includes an ether-based solvent (hereinafter also referred to as solvent SA) represented by formula (1). Only one type of solvent SA may be used, or two or more types may be used in combination. [ka] In formula (1), R 1 represents a hydrocarbon group, and R 2 ~R 6 each independently represents a hydrogen atom or a hydrocarbon group.

[0094] R in Equation (1) 1 ~R 6 Examples of the hydrocarbon group represented by include an alkyl group, an alkenyl group, and an alkynyl group, and an alkyl group is preferred, and a methyl group is more preferred.

[0095] The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. The alkyl group is preferably a linear or branched alkyl group, and is preferably a linear alkyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 5, and more preferably 2 or 3. The alkenyl group is preferably a linear or branched alkenyl group, and more preferably a linear alkenyl group. The number of carbon atoms in the alkynyl group is preferably 2 to 5, and more preferably 2 or 3. The alkynyl group is preferably a linear or branched alkynyl group, and more preferably a linear alkynyl group.

[0096] R in Equation (1) 2 ~R 6 Among these, it is preferable that one or more of them are hydrogen atoms, more preferable that two or more of them are hydrogen atoms, and even more preferable that three or more of them are hydrogen atoms. 2 ~R 6is preferably any one of the following embodiments (R-1) to (R-3), more preferably embodiment (R-1) or (R-2), and even more preferably embodiment (R-1). (R-1):R 2 ~R 6 are all hydrogen atoms. (R-2):R 2 ~R 6 one of the groups is an alkyl group and the rest are hydrogen atoms (R-3):R 2 ~R 6 Any two of the groups are alkyl groups and the remaining group is a hydrogen atom.

[0097] The molecular weight of the solvent SA is preferably 108-200, more preferably 108-180, and even more preferably 108-160.

[0098] The boiling point of the solvent SA is preferably from 100 to 220°C, more preferably from 120 to 180°C, and even more preferably from 140 to 180°C.

[0099] The solubility parameter (SP value) of solvent SA at 25°C is 15 to 24 (MPa). 0.5 Preferably, the pressure is 17 to 22 (MPa). 0.5 More preferably, it is 19 to 20 (MPa). 0.5 The viscosity of the solvent SA at 25° C. is preferably 0.5 to 2.0 mPa·s, more preferably 0.6 to 1.7 mPa·s, and even more preferably 0.7 to 1.4 mPa·s.

[0100] Specific examples of solvent SA include anisole, phenetole, 4-methylanisole, 3-methylanisole, 2-methylanisole, 4-ethylanisole, 3-ethylanisole, 2-ethylanisole, isopropoxybenzene, propoxybenzene, 2,4-dimethylanisole, 2,5-dimethylanisole, 2,6-dimethylanisole, 3,5-dimethylanisole, butylphenyl ether, 4-ethylphenetole, and 4-tert-butylanisole. At least one selected from anisole, phenetole, 4-methylanisole, 3-methylanisole, and 2-methylanisole is preferred, and anisole is more preferred, because this allows for a resin composition with excellent film thickness uniformity during film formation.

[0101] The solvent contained in the resin composition preferably contains 1 to 100% by mass of solvent SA, more preferably 1 to 99% by mass, and even more preferably 1 to 50% by mass. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.

[0102] The solvent contained in the resin composition may be only solvent SA, but it is preferable to contain a solvent other than the ether-based solvent represented by formula (1) (hereinafter also referred to as solvent SB) in order to improve the solvent solubility of the polymerizable compound, resin, photopolymerization initiator, etc. used in the resin composition, or to control the drying speed during film formation of the resin composition. Examples of solvent SB include ether-based solvents, ester-based solvents, and ketone-based solvents. Only one type of solvent SB may be used, or two or more types may be used in combination.

[0103] Examples of ether-based solvents used as solvent SB include propylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether, with propylene glycol monomethyl ether being preferred.

[0104] Examples of ester solvents used as the solvent SB include propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl ... Examples include methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, cyclohexyl acetate, and 1-methyl-2-methoxyethyl propionate, and propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate are preferred.

[0105] Examples of ketone solvents used as solvent SB include 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cyclopentanone, diacetone alcohol, methyl ethyl ketone, methyl isoamyl ketone, and methyl isobutyl ketone, with cyclohexanone, cyclopentanone, 2-octanone, and diacetone alcohol being preferred.

[0106] Solvent SB preferably contains at least one selected from an ester-based solvent and a ketone-based solvent, more preferably contains an ester-based solvent, and even more preferably contains propylene glycol monomethyl ether acetate.

[0107] When the solvent contained in the resin composition includes solvent SA and solvent SB, the content of solvent SB is preferably 100 to 9900 parts by mass per 100 parts by mass of solvent SA. The lower limit is preferably 150 parts by mass or more, more preferably 200 parts by mass or more. The upper limit is preferably 3500 parts by mass or less, more preferably 2000 parts by mass or less.

[0108] In addition, ester-based solvents (hereinafter referred to as solvent SB) were used as solvent SB. 1 When using the solvent SB 1 The content is preferably 100 to 9900 parts by mass relative to 100 parts by mass of solvent SA. The lower limit is preferably 150 parts by mass or more, more preferably 200 parts by mass or more. The upper limit is preferably 3500 parts by mass or less, more preferably 2000 parts by mass or less.

[0109] Furthermore, when propylene glycol monomethyl ether acetate is used as solvent SB, the content of propylene glycol monomethyl ether acetate is preferably 100 to 9900 parts by mass per 100 parts by mass of solvent SA. The lower limit is preferably 150 parts by mass or more, more preferably 200 parts by mass or more. The upper limit is preferably 3500 parts by mass or less, more preferably 2000 parts by mass or less. The total content of the solvent SA and propylene glycol monomethyl ether acetate in the solvent contained in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, and the upper limit can be set to 100% by mass or less, 90% by mass or less, or 80% by mass or less.

[0110] In addition, ketone-based solvents (hereinafter referred to as solvent SB) were used as solvent SB. 2 When using the solvent SB 2 The content is preferably 10 to 900 parts by mass per 100 parts by mass of solvent SA. The lower limit is preferably 25 parts by mass or more, more preferably 40 parts by mass or more. The upper limit is preferably 400 parts by mass or less, more preferably 250 parts by mass or less.

[0111] In addition, ester-based solvents (solvent SB) 1 ) and ketone solvents (solvent SB 2 ) is used in combination, the solvent contained in the resin composition is 1 to 50 mass % of solvent SA and 1 to 50 mass % of solvent SB 1 The content is 20 to 95 mass %, and the solvent SB 2 The content of the solvent SA is preferably 1 to 40% by mass. In this case, the content of the solvent SA is preferably 3 to 45% by mass, more preferably 5 to 40% by mass. 1 The content of the solvent SB is preferably 25 to 90 mass %, more preferably 30 to 85 mass %. 2The content is preferably 3 to 35 mass %, more preferably 5 to 30 mass %. In addition, solvent SA and solvent SB contained in the resin composition 1 and solvent SB 2 The total content of is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit can be set to 100% by mass or less, 90% by mass or less, or 80% by mass or less.

[0112] The content of the solvent in the resin composition is preferably 50 to 95% by mass. The upper limit is preferably 92.5% by mass or less, and more preferably 90% by mass or less. The lower limit is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more. The content of the solvent SA in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0113] Furthermore, from the viewpoint of environmental regulations, the resin composition of the present invention preferably contains substantially no environmentally restricted substances. In the present invention, "substantially no environmentally restricted substances" means that the content of environmentally restricted substances in the resin composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmentally restricted substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) Act, and the VOC (Volatile Organic Compounds) regulations, and their usage amounts and handling methods are strictly regulated. These compounds may be used as solvents when producing components used in the resin composition and may be mixed into the resin composition as residual solvents. From the viewpoints of human safety and environmental considerations, it is preferable to reduce the content of these substances as much as possible. Methods for reducing environmentally regulated substances include heating or reducing the pressure in the system to a temperature above the boiling point of the environmentally regulated substance, thereby distilling off the environmentally regulated substance from the system. When distilling off a small amount of an environmentally regulated substance, it is also useful to perform azeotropy with a solvent having a boiling point similar to that of the solvent in question in order to increase efficiency. Furthermore, when a radically polymerizable compound is contained, a polymerization inhibitor or the like may be added before distillation under reduced pressure to prevent intermolecular crosslinking due to the progression of a radical polymerization reaction during distillation under reduced pressure. These distillation methods can be used at any stage, such as the stage of raw materials, the stage of a product obtained by reacting the raw materials (e.g., a resin solution or a polyfunctional monomer solution after polymerization), or the stage of a resin composition prepared by mixing these compounds.

[0114] <<Polyalkyleneimine>> The resin composition of the present invention may also contain a polyalkyleneimine. The polyalkyleneimine is used, for example, as a dispersing aid. A dispersing aid is a material for improving the dispersibility of a pigment in a resin composition. The polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine, and has a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group. The alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.

[0115] The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. Regarding the molecular weight value of the polyalkyleneimine, if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, if the molecular weight of the specific amine compound cannot be calculated from the structural formula or calculation is difficult, the number average molecular weight value measured by boiling point elevation method is used. If the number average molecular weight cannot be measured by boiling point elevation method or measurement is difficult, the number average molecular weight value measured by viscosity method is used. If the number average molecular weight cannot be measured by viscosity method or measurement by viscosity method is difficult, the number average molecular weight value measured in terms of polystyrene by GPC (gel permeation chromatography) method is used.

[0116] The amine value of the polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.

[0117] Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. The polyalkyleneimine is particularly preferably polyethyleneimine. Furthermore, the polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).

[0118] The content of alkyleneimine in the total solid content of the resin composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. The content of alkyleneimine is preferably 0.5 to 20 parts by mass per 100 parts by mass of pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. Only one type of alkyleneimine may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0119] <<Pigment derivatives>> The resin composition of the present invention may contain a pigment derivative. The pigment derivative is used, for example, as a dispersing aid. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.

[0120] Examples of dye skeletons that constitute the pigment derivative include a quinoline dye skeleton, a benzimidazolone dye skeleton, a benzisoindole dye skeleton, a benzothiazole dye skeleton, an iminium dye skeleton, a squarylium dye skeleton, a croconium dye skeleton, an oxonol dye skeleton, a pyrrolopyrrole dye skeleton, a diketopyrrolopyrrole dye skeleton, an azo dye skeleton, an azomethine dye skeleton, a phthalocyanine dye skeleton, a naphthalocyanine dye skeleton, an anthraquinone dye skeleton, a quinacridone dye skeleton, a dioxazine dye skeleton, a perinone dye skeleton, a perylene dye skeleton, a thioindigo dye skeleton, an isoindoline dye skeleton, an isoindolinone dye skeleton, a quinophthalone dye skeleton, an iminium dye skeleton, a dithiol dye skeleton, a triarylmethane dye skeleton, and a pyrromethene dye skeleton.

[0121] Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imidic acid group, and salts thereof. Examples of the atom or atomic group constituting the salt include an alkali metal ion (Li + , Na + , K. + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ Examples of the carboxylic acid amide group include -NHCOR X1 As the sulfonamide group, a group represented by -NHSO2R is preferred. X2 As the imide acid group, a group represented by -SO2NHSO2R is preferred. X3 , -CONHSO2R X4 , -CONHCOR X5 or -SO2NHCOR X6 A group represented by the formula: -SO2NHSO2R is preferred. X3 is more preferable. X1 ~R X6 R each independently represents an alkyl group or an aryl group. X1 ~R X6The alkyl group and aryl group represented by may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.

[0122] Examples of basic groups include amino groups, pyridinyl groups and their salts, ammonium salts, and phthalimidomethyl groups. Examples of atoms or atomic groups that constitute salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0123] Pigment derivatives with excellent visible transparency (hereinafter referred to as transparent pigment derivatives) can also be used. The maximum molar absorption coefficient (εmax) of transparent pigment derivatives in the wavelength range of 400 to 700 nm is 3000 L·mol -1 ·cm -1 It is preferable that the concentration is less than 1000 L·mol -1 ·cm -1 It is more preferable that it is less than 100 L·mol -1 ·cm -1 The lower limit of εmax is, for example, 1 L mol -1 ·cm -1 is greater than or equal to 10 L mol -1 ·cm -1 More than that is fine.

[0124] Specific examples of pigment derivatives include compounds described in the examples described below, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, JP-A-03-153780, and JP-A-03-045662. , JP 04-285669 A, JP 06-145546 A, JP 06-212088 A, JP 06-240158 A, JP 10-030063 A, JP 10-195326 A, paragraphs 0086 to 0098 of International Publication No. 2011 / 024896, International Publication No. 2012 / 1 No. 02399, paragraph numbers 0063 to 0094, paragraph number 0082 of International Publication No. 2017 / 038252, paragraph number 0171 of JP 2015-151530 A, paragraph numbers 0162 to 0183 of JP 2011-252065 A, JP 2003-081972 A, Japanese Patent No. 5299151, JP 2015-172732 A, JP 2014-199308 A, JP 2014-085562 A, JP 2014-035351 A, compounds described in JP 2008-081565 A, diketopyrrolopyrrole compounds having a thiol linking group described in WO 2020 / 002106 can be mentioned.

[0125] The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of the pigment. Only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0126] <<Polymerizable compounds>> The resin composition of the present invention preferably contains a polymerizable compound. Known compounds that can be crosslinked by radicals, acids, or heat can be used as the polymerizable compound. In the present invention, the polymerizable compound is preferably, for example, a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.

[0127] The polymerizable compound may be in any chemical form such as a monomer, prepolymer, or oligomer, but is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 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.

[0128] The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and even more preferably a compound containing 3 to 6 ethylenically unsaturated bond-containing groups. The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples of the polymerizable compound include compounds described in paragraphs 0095 to 0108 of JP 2009-288705 A, paragraph 0227 of JP 2013-029760 A, paragraphs 0254 to 0257 of JP 2008-292970 A, paragraphs 0034 to 0038 of JP 2013-253224 A, paragraph 0477 of JP 2012-208494 A, JP 2017-048367 A, Japanese Patent No. 6057891 A, and Japanese Patent No. 6031807 A, the contents of which are incorporated herein by reference.

[0129] Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds in which the (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (e.g., SR454 and SR499, commercially available from Sartomer). The polymerizable compounds include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product: M-460, manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (KAYARAD, manufactured by Nippon Kayaku Co., Ltd.). HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like can also be used.

[0130] In addition, the polymerizable compound may also be a trifunctional (meth)acrylate compound such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy-modified tri(meth)acrylate, trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, isocyanuric acid ethyleneoxy-modified tri(meth)acrylate, or pentaerythritol tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and 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, and TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), and KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0131] Furthermore, a compound having an acid group can also be used as the polymerizable compound. By using a polymerizable compound having an acid group, the polymerizable compound in the unexposed area can be easily removed during development, thereby suppressing the generation of development residues. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group, with a carboxyl group being preferred. Examples of polymerizable compounds having an acid group include succinic acid-modified dipentaerythritol penta(meth)acrylate. Examples of commercially available polymerizable compounds having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The acid value of the polymerizable compound having an acid group is preferably 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 more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous in terms of production and handling.

[0132] Furthermore, a compound having a caprolactone structure can also be used as the polymerizable compound. Commercially available polymerizable compounds having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.).

[0133] Furthermore, the polymerizable compound may also be a polymerizable compound having an alkyleneoxy group. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and even more preferably a tri- to hexafunctional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494 (manufactured by Sartomer Corporation), which is a tetrafunctional (meth)acrylate having four ethyleneoxy groups, and KAYARAD TPA-330 (manufactured by Nippon Kayaku Co., Ltd.), which is a trifunctional (meth)acrylate having three isobutyleneoxy groups.

[0134] Furthermore, the polymerizable compound may also be a polymerizable compound having a fluorene skeleton. The polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound. Examples of the polymerizable compound having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr): [ka]

[0135] The wavy lines in the formula represent bonds, and R f1 and R f2 each independently represents a substituent, and m and n each independently represent an integer of 0 to 5. When m is 2 or more, m R f1 may be the same or different, and m R f1 Two of the R f1 When n is 2 or more, n R f2may be the same or different, and n R f2 Two of the R f2 They may be bonded to each other to form a ring. f1 and R f2 The substituent represented by is a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR f11 , -COR f12 , -COOR f13 , -OCOR f14 , -NR f15 R f16 , -NHCOR f17 , -CONR f18 R f19 , -NHCONR f20 R f21 , -NHCOOR f22 , -SR f23 , -SO2R f24 , -SO2OR f25 , -NHSO2R f26 or -SO2NR f27 R f28 Examples include: R f11 ~R f28 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

[0136] Specific examples of polymerizable compounds having a fluorene skeleton include compounds having the following structure: Commercially available polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton). [ka]

[0137] It is also preferable to use a polymerizable compound that is substantially free of environmentally restricted substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

[0138] The content of the polymerizable compound in the total solid content of the resin composition is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The polymerizable compound may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total content thereof preferably falls within the above range.

[0139] <<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, a compound having photosensitivity to light in the ultraviolet to visible range is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0140] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl-substituted coumarin compound, more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173 and Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60pp, vol. 19, No. 3, 2019, peroxide-based photopolymerization initiators described in, for example, WO 2018 / 221177, WO 2018 / 110179, photopolymerization initiators described in, for example, JP 2019-043864 A, photopolymerization initiators described in, for example, JP 2019-044030 A, peroxide-based initiators described in, for example, JP 2019-167313 A, aminoacetophenone-based initiators having an oxazolidine group described in, for example, JP 2020-055992 A, oxime-based photopolymerization initiators described in, for example, JP 2013-190459 A, and the like. The contents of these initiators are incorporated herein by reference.

[0141] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (manufactured by BASF), etc. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by BASF), etc. Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819 and Irgacure TPO (both manufactured by BASF).

[0142] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (all manufactured by BASF), TR-PBG-304 and TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and Adeka Optomer N-1919 (manufactured by ADEKA Corporation; photopolymerization initiator 2 described in JP 2012-014052 A). It is also preferable to use, as the oxime compound, a compound that is not colorable or a compound that is highly transparent and does not easily discolor.Commercially available products include ADEKA Arcles NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

[0143] As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP 2014-137466 A and Japanese Patent No. 06636081 A.

[0144] As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in WO 2013 / 083505.

[0145] As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and compound (C-3) described in JP-A-2013-164471.

[0146] As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 A, and ADEKA ARCLES NCI-831 (manufactured by ADEKA Corporation).

[0147] As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in WO 2015 / 036910.

[0148] The photopolymerization initiator may be an oxime compound having a carbazole skeleton to which a hydroxyl-containing substituent is bonded. Examples of such a photopolymerization initiator include the compounds described in WO 2019 / 088055.

[0149] As a photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring is used. OX1 It is also possible to use an oxime compound having the aromatic ring group Ar OX1 Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred, and an acyl group is more preferred because it is easier to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group is more preferred, and an alkoxy group, an alkylsulfanyl group, or an amino group is even more preferred.

[0150] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). [ka] In the formula, R X1represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group; R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group; R X3 ~R X14 each independently represents a hydrogen atom or a substituent; X10 ~R X14 At least one of the groups is an electron-withdrawing group.

[0151] Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, and an acyl group is more preferred because a film having excellent light resistance can be easily formed, and a benzoyl group is even more preferred.

[0152] In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 is preferably a hydrogen atom.

[0153] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.

[0154] Specific examples of oxime compounds that can be preferably used in the present invention are shown below, but the present invention is not limited to these.

[0155] [ka] [ka]

[0156] The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Furthermore, from the viewpoint of sensitivity, the molar absorption 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 absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0157] As the photopolymerization initiator, a bifunctional or trifunctional or higher functional 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, resulting in good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, thereby improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, WO-A-2015 / 004565, WO-A-2016-532675, paragraphs 0407 to 0412, and WO-A-2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-A-2013-522445; Examples of such initiators include Cmpd1 to 7 described in JP 2016 / 034963 A, the oxime ester photoinitiators described in paragraph 0007 of JP 2017-523465 A, the photoinitiators described in paragraphs 0020 to 0033 of JP 2017-167399 A, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP 2017-151342 A, and the oxime ester photoinitiators described in Japanese Patent No. 6469669 A.

[0158] The content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less. The photopolymerization initiator may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total content thereof is preferably within the above range.

[0159] <<Compounds with cyclic ether groups>> The resin composition of the present invention may contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups contained in the epoxy compound is preferably 2 or more. As the epoxy compound, compounds described in paragraphs 0034 to 0036 of JP 2013-011869 A, paragraphs 0147 to 0156 of JP 2014-043556 A, paragraphs 0085 to 0092 of JP 2014-089408 A, and compounds described in JP 2017-179172 A can also be used. The contents of these compounds are incorporated herein by reference.

[0160] The epoxy compound may be either a low molecular weight compound (for example, a molecular weight of less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 3,000 or less.

[0161] As the epoxy compound, an epoxy resin can be preferably used. Examples of the epoxy resin include epoxy resins obtained by glycidyl etherification of phenolic compounds, epoxy resins obtained by glycidyl etherification of various novolac resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensates of silicon compounds having epoxy groups with other silicon compounds, and copolymers of polymerizable unsaturated compounds having epoxy groups with other polymerizable unsaturated compounds. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and even more preferably 310 to 1000 g / eq.

[0162] Commercially available compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).

[0163] The content of the compound having a cyclic ether group in the total solid content of the resin composition is preferably 0.1 to 20% by mass. The lower limit is, for example, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is, for example, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Only one type of compound having a cyclic ether group 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 thereof is within the above range.

[0164] <<Curing accelerator>> The resin composition of the present invention may contain a curing accelerator, such as a thiol compound, a methylol compound, an amine compound, a phosphonium salt compound, an amidine salt compound, an amide compound, a base generator, an isocyanate compound, an alkoxysilane compound, or an onium salt compound. Specific examples of the curing accelerator include compounds described in paragraphs 0094 to 0097 of International Publication No. 2018 / 056189, JP-A-2015-034963, JP-A-2013-041165, JP-A-2013-041165, JP-A-2014-055114, JP-A-2012-150180, JP-A-2011-253054, JP-A-2011-253054, JP-A-5765059, JP-A-2017-036379, and carboxyl group-containing epoxy curing agents described in paragraphs 0085 to 0092. The content of the curing accelerator in the total solid content of the resin composition is preferably 0.3 to 8.9 mass %, more preferably 0.8 to 6.4 mass %.

[0165] <<Surfactants>> The resin composition of the present invention may contain a surfactant. Various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used as the surfactant. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. Examples of the surfactant include those described in paragraphs 0238 to 0245 of WO 2015 / 166779, the contents of which are incorporated herein by reference.

[0166] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the resin composition.

[0167] Examples of fluorine-based surfactants include those described in paragraphs 0060 to 0064 of JP 2014-041318 A (corresponding paragraphs 0060 to 0064 of WO 2014 / 017669 A), those described in paragraphs 0117 to 0132 of JP 2011-132503 A, and those described in JP 2020-008634 A, the contents of which are incorporated herein by reference. Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, and R-01. , R-40, R-40-LM, R-41, R-41-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, FTX-218, (All manufactured by NEOS Corporation)

[0168] In addition, acrylic compounds that have a molecular structure with a functional group containing a fluorine atom and that volatilize when heated by cleavage of the fluorine atom-containing functional group can also be used as fluorosurfactants. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac DS-21.

[0169] Furthermore, it is also preferable to use a polymer 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 as the fluorine-containing surfactant. Examples of such a fluorine-containing surfactant include the fluorine-containing surfactants described in JP 2016-216602 A, the contents of which are incorporated herein by reference.

[0170] The fluorosurfactant may also be a block polymer. The fluorosurfactant may also preferably be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A No. 2010-032698 and the following compounds are also exemplified as the fluorosurfactant used in the present invention. [ka] The weight-average molecular weight of the above compound is preferably 3000 to 50000, for example, 14000. In the above compound, % indicating the proportion of repeating units is mol %.

[0171] The fluorine-containing surfactant may also be a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, and Megafac RS-101, RS-102, RS-718K, and RS-72-K manufactured by DIC Corporation. The fluorine-containing surfactant may also be the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A.

[0172] In addition, it is also preferable from the viewpoint of environmental regulations to use the surfactants described in WO 2020 / 084854 as a substitute for surfactants having a perfluoroalkyl group having 6 or more carbon atoms.

[0173] It is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant. [ka] In formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, α represents 1 or 2, and X α+ is an α-valent metal ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion, or NH4 + Represents.

[0174] Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, 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. Examples of suitable surfactants include esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0175] Examples of silicone surfactants include DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400, SH 8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. OIL (all manufactured by DuPont Toray Specialty Materials Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie).

[0176] The content of the surfactant in the total solid content of the resin composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. Only one surfactant may be used, or two or more surfactants may be used. When two or more surfactants are used, the total amount thereof is preferably within the above range.

[0177] <<Silane coupling agent>> The resin composition of the present invention may contain a silane coupling agent. In this specification, the term "silane coupling agent" refers to a silane compound having a hydrolyzable group and other functional groups. The term "hydrolyzable group" refers to a substituent directly bonded to a silicon atom that can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than the hydrolyzable group include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups, with amino groups, (meth)acryloyl groups, and epoxy groups being preferred. Specific examples of silane coupling agents include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), and 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503). Specific examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP-A No. 2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP-A No. 2009-242604, the contents of which are incorporated herein by reference.

[0178] 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 more preferably 3% by mass or less, and even more preferably 2% by mass or less. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0179] <<Ultraviolet absorber>> The resin composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers that can be used include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Examples of such compounds include those described in paragraphs 0038-0052 of JP 2009-217221 A, paragraphs 0052-0072 of JP 2012-208374 A, paragraphs 0317-0334 of JP 2013-068814 A, and paragraphs 0061-0080 of JP 2016-162946 A, the contents of which are incorporated herein by reference. Commercially available ultraviolet absorbers include UV-503 manufactured by Daito Chemical Co., Ltd., and the Tinuvin and Uvinul series manufactured by BASF. Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil & Fats (The Chemical Daily, February 1, 2016). The ultraviolet absorber may also be a compound described in paragraphs 0049-0059 of Japanese Patent No. 6268967, a compound described in paragraphs 0059-0076 of International Publication No. 2016 / 181987, or a thioaryl group-substituted benzotriazole ultraviolet absorber described in International Publication No. 2020 / 137819. The content of the ultraviolet absorber in the total solid content of the resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0180] <<Antioxidants>> The resin composition of the present invention may contain an antioxidant. Examples of antioxidants include phenolic compounds, phosphite ester compounds, and thioether compounds. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. A preferred phenolic compound is a hindered phenolic compound. A compound having a substituent at the ortho position adjacent to the phenolic hydroxy group is preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. A compound having a phenolic group and a phosphite ester group in the same molecule is also preferred. Phosphorus-based antioxidants can also be suitably used as the antioxidant. The compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used as the antioxidant. The content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one antioxidant or two or more antioxidants may be used. When two or more antioxidants are used, the total amount is preferably within the above range.

[0181] <<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, cerous 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 mass%. One type of polymerization inhibitor may be used alone, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

[0182] <<Other ingredients>> In the present invention, the resin composition may optionally contain a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, and other auxiliary agents (e.g., conductive particles, bulking agents, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately incorporating these components, film properties and other characteristics can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812 ), and paragraphs 0101-0104 and 0107-0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. Furthermore, the resin composition of the present invention may optionally contain a latent antioxidant. Examples of latent antioxidants include compounds in which the moiety functioning as an antioxidant is protected with a protecting group, and the compound functions as an antioxidant when heated at 100 to 250°C or at 80 to 200°C in the presence of an acid / base catalyst, resulting in the elimination of the protecting group. Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Laid-Open No. 2017-008219. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Corporation). The resin composition of the present invention may also contain an aromatic group-containing phosphonium salt described in Japanese Patent Application Laid-Open No. 2020-079833.

[0183] The resin composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, the compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of JP-A-2017-129774, the compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of JP-A-2017-129674, the compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of JP-A-2017-122803, the compounds described in paragraphs 0025 to 0039 of WO 2017 / 164127, and the compounds described in paragraphs 0026 to 0039 of JP-A-2017-186546. JP-A-2015-025116, paragraphs 0019 to 0041, JP-A-2012-145604, paragraphs 0101 to 0125, JP-A-2012-103475, paragraphs 0018 to 0021, JP-A-2011-257591, paragraphs 0015 to 0018, JP-A-2011-191483, paragraphs 0017 to 0021, JP-A-2011-145668, paragraphs 0108 to 0116, JP-A-2011-253174, paragraphs 0103 to 0153, and the like.

[0184] The resin composition of the present invention preferably contains 100 ppm or less, more preferably 50 ppm or less, even more preferably 10 ppm or less, and particularly preferably substantially no free metal that is not bonded or coordinated to a pigment, etc. This embodiment is expected to have various effects, such as stabilizing pigment dispersibility (preventing aggregation), improving spectral characteristics due to improved dispersibility, stabilizing curable components, preventing fluctuations in conductivity due to elution of metal atoms and metal ions, and improving display characteristics. In addition, the effects described in JP 2012-153796 A, JP 2000-345085 A, JP 2005-200560 A, JP 08-043620 A, JP 2004-145078 A, JP 2014-119487 A, JP 2010-083997 A, JP 2017-090930 A, JP 2018-025612 A, JP 2018-025797 A, JP 2017-155228 A, JP 2018-036521 A, etc. can also be obtained. Examples of the free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Ni, Cd, Pb, and Bi. Furthermore, the resin composition of the present invention preferably contains 100 ppm or less of free halogens that are not bonded or coordinated to pigments or the like, more preferably 50 ppm or less, even more preferably 10 ppm or less, and particularly preferably substantially no halogens. Examples of halogens include F, Cl, Br, I, and anions thereof. Methods for reducing the amount of free metals and halogens in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.

[0185] It is also preferable that the resin composition of the present invention is substantially free of terephthalic acid esters. Here, "substantially free" means that the content of terephthalic acid esters in the total amount of the resin composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0186] From the viewpoint of environmental regulations, the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be restricted. When the content of the above-mentioned compounds in the resin composition of the present invention is reduced, the content of perfluoroalkyl sulfonic acid (particularly perfluoroalkyl sulfonic acid having a perfluoroalkyl group with 6 to 8 carbon atoms) and its salts, and perfluoroalkyl carboxylic acid (particularly perfluoroalkyl carboxylic acid having a perfluoroalkyl group with 6 to 8 carbon atoms) 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, based on the total solid content of the resin composition. The resin composition of the present invention may be substantially free of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. For example, by using a compound that can replace perfluoroalkyl sulfonic acid and its salts, and a compound that can replace perfluoroalkyl carboxylic acid and its salts, a resin composition that is substantially free of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, may be selected. Examples of compounds that can replace regulated compounds include compounds that are exempt from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above content 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, within the maximum allowable range.

[0187] <<Containment Container>> The container for storing the resin composition is not particularly limited, and known containers can be used. Furthermore, in order to prevent impurities from being mixed into the raw materials or the resin composition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six-layer resin or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A. Furthermore, it is also preferable to make the inner wall of the container out of glass or stainless steel in order to prevent metal elution from the inner wall, improve the storage stability of the resin composition, and prevent deterioration of the components.

[0188] <Method of manufacturing resin composition> The resin composition of the present invention can be produced by mixing the above-mentioned materials. When producing the resin composition, all components may be simultaneously dissolved and / or dispersed in a solvent to produce the resin composition, or, if necessary, the materials may be prepared as two or more solutions or dispersions, which are mixed at the time of use (application) to produce the resin composition.

[0189] The method for producing a resin composition of the present invention preferably includes a step (dispersion step) of dispersing a pigment in the presence of a resin and a solvent containing an ether-based solvent (solvent SA) represented by the above-mentioned formula (1). According to this embodiment, the dispersibility of the pigment in the resin composition can be further improved, and the average particle size of the pigment in the resin composition can be further reduced. While the detailed reasons for this effect are unclear, it is presumed to be due to the following: It is presumed that solvent SA has a high affinity with the pigment and can weaken the tendency for the pigments to aggregate. Therefore, by dispersing the pigment in the presence of a resin and a solvent containing solvent SA, it is possible to effectively suppress reagglomeration of the pigment during dispersion, thereby further reducing the average particle size of the pigment in the resin composition. It is also presumed that solvent SA interacts with the conjugated system of the organic pigment, thereby further increasing its affinity with the organic pigment. Therefore, when an organic pigment is used as the pigment, it is possible to more effectively suppress reagglomeration of the pigment during dispersion, thereby further reducing the average particle size of the pigment in the resin composition.

[0190] The solvent used in the dispersion step preferably contains a solvent other than solvent SA (solvent SB) from the viewpoints of the solubility of the resin used during dispersion, the solubility of the polymerizable compound, resin, photopolymerization initiator, etc. in the solvent, and control of the drying rate during film formation of the resin composition. Examples of solvent SB include the solvents mentioned above, and preferably contains at least one selected from ester-based solvents and ketone-based solvents, more preferably contains an ester-based solvent, and even more preferably contains propylene glycol monomethyl ether acetate.

[0191] The solvent used in the dispersion step preferably contains solvent SA in an amount of 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, with the upper limit being 100% by mass or less, 50% by mass or less, or 30% by mass or less. Furthermore, when the solvent used in the dispersion step further contains solvent SB, the content of solvent SB is preferably 1 to 99% by mass, more preferably 30 to 90% by mass, and even more preferably 50 to 70% by mass. Furthermore, the content of solvent SB is preferably 10 to 3,000 parts by mass per 100 parts by mass of solvent SA. The lower limit is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more. The upper limit is preferably 2,000 parts by mass or less, and more preferably 1,000 parts by mass or less. The solvent used in the dispersion step preferably contains 1 to 99% by mass of propylene glycol monomethyl ether acetate, more preferably 30 to 90% by mass, and even more preferably 50 to 70% by mass. The content of propylene glycol monomethyl ether acetate is preferably 10 to 3,000 parts by mass per 100 parts by mass of solvent SA. The lower limit is preferably 30 parts by mass or more, more preferably 50 parts by mass or more. The upper limit is preferably 2,000 parts by mass or less, more preferably 1,000 parts by mass or less.

[0192] Mechanical forces used to disperse pigments include compression, squeezing, impact, shear, and cavitation. Specific methods 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. When grinding pigments in a sand mill (bead mill), it is preferable to use small-diameter beads and increase the bead packing ratio to improve grinding efficiency. After grinding, it is also preferable to remove coarse particles by filtration, centrifugation, or other methods. Pigment dispersion processes and dispersers can be suitably used, such as those described in "Dispersion Technology Encyclopedia," published by Johokki Co., Ltd., July 15, 2005, and "Comprehensive Data Collection of Dispersion Technology and Industrial Applications Focused on Suspensions (Solid / Liquid Dispersion Systems)," published by the Management Development Center Publishing Department, October 10, 1978, and in paragraph 0022 of JP 2015-157893 A. In addition, in the process of dispersing the pigment, particle size reduction treatment may be performed in a salt milling step. Materials, equipment, treatment conditions, etc. used in the salt milling step can be found in, for example, JP-A Nos. 2015-194521 and 2012-046629.

[0193] The resin composition materials (particularly the dispersion, polymerizable compound, photopolymerization initiator, etc.) are preferably stored refrigerated at a temperature of 5 to 10° C. In addition, when producing the resin composition, it is preferable to store the refrigerated materials in an environment of a temperature of 17 to 27° C. and a relative humidity of 40 to 80% for 12 hours or more, and then return the temperature of the materials to 17 to 27° C. before mixing with other materials.

[0194] Furthermore, when a resin, a polymerizable compound, a photopolymerization initiator, and the like are further added to the dispersion liquid produced through the above-described dispersion step, the order of adding each material is not particularly limited, but for the purpose of increasing the dissolution rate and handleability, it is also preferable to mix the polymerizable compound, resin, and solvent, and then further mix the photopolymerization initiator, polymerization inhibitor, and other additives to produce a monomer liquid, and then add the monomer liquid to the dispersion liquid.

[0195] Furthermore, it is preferable to produce the resin composition in an environment with a temperature of 17 to 27°C and a relative humidity of 40 to 80% in order to prevent excess moisture from being mixed into the resin composition.

[0196] The method for producing a resin composition preferably includes a step of filtering the resin composition with a filter for the purpose of removing foreign matter, reducing defects, etc. The filter may be any filter conventionally used for filtration, etc., without any particular limitation. Examples include 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 (including high-density and ultra-high-molecular-weight polyolefin resins) such as polyethylene and polypropylene (PP). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0197] 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 pore size of the filter is within the above range, fine foreign matter can be removed more reliably. The nominal value of the filter manufacturer can be referred to for the pore size value of the filter. Various filters provided by Nippon Pall Corporation (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Microfilter Co., Ltd., etc. can be used.

[0198] It is also preferable to use a fibrous filter medium as the filter. Examples of fibrous filter medium 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.) manufactured by ROKI TECHNO CORPORATION.

[0199] When using filters, different filters (for example, a first filter and a second filter) may be combined. In this case, filtration with each filter may be performed only once or two or more times. Filters with different pore sizes within the above-mentioned range may also be combined. Furthermore, filtration with the first filter may be performed on the dispersion alone, and after mixing with other components, filtration with the second filter may be performed.

[0200] From the viewpoint of providing stability, it is also preferable to fill the produced resin composition (especially when it contains a green pigment) in a light-shielded container. Also, from the viewpoint of providing stability, it is preferable that the gas occupying the space inside the container has an oxygen concentration of 23% or more.

[0201] <Membrane manufacturing method> Next, a method for producing the film of the present invention will be described. The method for producing the film of the present invention includes a step of applying the resin composition of the present invention to a support.

[0202] The thickness of the membrane produced by the membrane production method of the present invention can be adjusted appropriately depending on the purpose. For example, the membrane 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 membrane thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0203] The film produced by the film production method of the present invention can be used as a color filter, a near-infrared transmitting filter, a near-infrared cutting filter, a black matrix, a light-shielding film, etc.

[0204] The film manufacturing method of the present invention preferably further includes a step of forming a pattern (pixels). Methods for forming the pattern (pixels) include photolithography and dry etching, with photolithography being preferred.

[0205] The pattern formation by the photolithography method preferably 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 to light in a pattern, and developing and removing the unexposed areas of the resin composition layer to form a pattern (pixels). If necessary, a step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

[0206] In the step of forming a resin composition layer, a resin composition layer is formed on a support using the resin composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. Examples include a glass substrate and a silicon substrate, with a silicon substrate being preferred. The silicon substrate may also be formed with a charge-coupled device (CCD), a complementary metal-oxide semiconductor (CMOS), a transparent conductive film, or the like. A black matrix is ​​sometimes formed on the silicon substrate to isolate each pixel. The silicon substrate may also be provided with an underlayer to improve adhesion with an upper layer, prevent material diffusion, or flatten the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. It is also preferably 30 to 80° when measured with water. A surface contact angle of the underlayer within the above range ensures good wetting of the resin composition. The surface contact angle of the underlayer can be adjusted by, for example, adding a surfactant.

[0207] The resin composition can be applied by any known method, including, for example, a dropping method (drop casting), a slit coating method, a spray method, a roll coating method, a spin coating method, a casting method, a slit-and-spin method, a pre-wetting method (e.g., the method described in JP-A-2009-145395), various printing methods such as inkjet (e.g., on-demand method, piezo method, thermal method) and nozzle jet printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing, a transfer method using a mold, and a nanoimprint method. The inkjet application method is not particularly limited, and examples thereof include the method described in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents -", ​​published in February 2005 by Sumibe Techno Research (particularly pages 115 to 133), and the methods described in JP-A Nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-169325. Furthermore, for the method of applying the resin composition, reference can be made to the descriptions in International Publication Nos. 2017 / 030174 and 2017 / 018419, the contents of which are incorporated herein by reference.

[0208] The resin composition layer formed on the support may be dried (prebaked). When a film is produced by a low-temperature process, prebaking may not be performed. When prebaking is performed, the prebaking 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, or can also be 80°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.

[0209] Next, the resin composition layer is exposed to light in a pattern (exposure step). For example, the resin composition layer can be exposed to light in a pattern by using a stepper exposure machine, a scanner exposure machine, or the like, through a mask having a predetermined mask pattern. This allows the exposed portions to be cured.

[0210] Examples of radiation (light) that can be used for 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.

[0211] Furthermore, the exposure may be performed by continuous irradiation with light or by pulsed irradiation (pulse exposure), which is an exposure method in which light irradiation and pauses are repeated in short cycles (for example, milliseconds or less).

[0212] The irradiation amount (exposure amount) is, for example, 0.03 to 2.5 J / cm 2 is preferable, and 0.05 to 1.0 J / cm 2 The oxygen concentration during exposure can be appropriately selected. In addition to being performed in the atmosphere, exposure may be performed in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration of more than 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). The exposure illuminance can be appropriately set, and is usually 1000 W / m 2 ~100,000W / m 2 (e.g., 5000W / m 2 , 15000W / m 2 , or 35,000 W / m 2 The oxygen concentration and exposure illuminance may be appropriately combined. For example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m 2, oxygen concentration 35% by volume, illuminance 20000W / m 2 etc.

[0213] Next, the unexposed portions of the resin composition layer are developed and removed to form a pattern (pixels). The unexposed portions of the resin composition layer can be developed and removed using a developer. As a result, the unexposed portions of the resin composition layer in the exposure step are dissolved into the developer, leaving only the photocured portions. 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 residue removal, the process of shaking off the developer every 60 seconds and then supplying fresh developer may be repeated several times.

[0214] Examples of the developer include organic solvents and alkaline developers, with alkaline developers being preferred. The alkaline developer is preferably an alkaline aqueous solution (alkaline developer) prepared by diluting an alkaline agent with pure water. Examples of the alkaline agent 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 high 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, more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. For ease of transportation and storage, the developer may be prepared as a concentrated solution and then diluted to the required concentration before use. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) the developed resin composition layer with pure water after development. Rinsing is preferably performed by supplying a rinse solution to the developed resin composition layer while rotating the support on which the developed resin composition layer has been formed. It is also preferable to perform this by moving the nozzle ejecting the rinse solution from the center of the support to the periphery of the support. In this case, the nozzle movement speed may be gradually reduced as the nozzle moves from the center to the periphery of the support. Rinsing in this manner can suppress in-plane variations in rinsing. A similar effect can be achieved by gradually reducing the rotation speed of the support while moving the nozzle from the center to the periphery of the support.

[0215] After development and drying, it is preferable to perform additional exposure treatment or heating treatment (post-baking). The additional exposure treatment or post-baking is a post-development curing treatment to ensure complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to heat the developed film to the above conditions. When additional exposure treatment is performed, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure treatment may also be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

[0216] Pattern formation by dry etching preferably includes the steps of forming a resin composition layer on a support using the resin composition of the present invention and curing the entire resin composition layer to form a cured layer; forming a photoresist layer on the cured layer; exposing the photoresist layer to light in a pattern and developing it to form a resist pattern; and dry etching the cured layer using an etching gas as a mask. In forming the photoresist layer, it is preferable to further perform a pre-baking treatment. In particular, the photoresist layer formation process preferably includes a post-exposure heat treatment and a post-development heat treatment (post-baking treatment). For details on pattern formation by dry etching, please refer to the description in paragraphs 0010 to 0067 of JP 2013-064993 A, the contents of which are incorporated herein by reference.

[0217] <Method of manufacturing optical filters> The method for producing an optical filter of the present invention includes the method for producing the film of the present invention described above. That is, the method for producing an optical filter of the present invention includes a step of applying the resin composition of the present invention described above to a support. Types of optical filters include color filters, near-infrared cut filters, and near-infrared transmission filters, and color filters are preferred. The color filter preferably has the film of the present invention as its pixel, more preferably has the film of the present invention as a color pixel, and even more preferably has the film of the present invention as a green pixel.

[0218] The thickness of the film of the present invention in the optical filter can be adjusted appropriately depending on the purpose. The thickness is preferably 2 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less. The lower limit of the thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0219] The width of the pixels included in the optical filter is preferably 0.1 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.

[0220] <Method of manufacturing a solid-state imaging device> The method for producing a solid-state imaging device of the present invention includes the method for producing the film of the present invention described above. That is, the method for producing a solid-state imaging device of the present invention includes a step of applying the resin composition of the present invention described above to a support. The configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device, and examples thereof include the following configurations.

[0221] The substrate includes a plurality of photodiodes constituting the light receiving area of ​​a solid-state imaging device (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film is formed on the photodiodes and transfer electrodes, with only the light-receiving portions of the photodiodes exposed. A device protection film made of silicon nitride or the like is formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes. A color filter is also provided on the device protection film. Furthermore, the device protection film may include a light-collecting means (e.g., a microlens, etc.; the same applies hereinafter) below the color filter (closer to the substrate), or on the color filter. The color filter may have a structure in which each pixel is embedded in a space partitioned by partitions, for example, in a grid pattern. In this case, the partitions preferably have a low refractive index relative to each pixel. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018 / 043654 A. Furthermore, as shown in JP 2019-211559 A, an ultraviolet absorbing layer may be provided within the structure of the solid-state imaging element to improve light resistance. An imaging device including the solid-state imaging element of the present invention can be used in digital cameras, electronic devices with imaging functions (such as mobile phones), as well as in-vehicle cameras and surveillance cameras.

[0222] <Manufacturing Method of Image Display Device> The manufacturing method of the image display device of the present invention includes the manufacturing method of the film of the present invention described above. That is, the manufacturing method of the image display device of the present invention includes a step of applying the resin composition of the present invention described above to a support. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. Definitions of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Nobuaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994). There are no particular limitations on the liquid crystal display device to which the present invention can be applied, and the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology." [Example]

[0223] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0224] <Conditions for measuring weight-average molecular weight and number-average molecular weight by gel permeation chromatography> Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 columns connected together Developing solvent: tetrahydrofuran Column temperature: 40℃ Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1% by mass) Device name: Tosoh HLC-8220GPC Detector: RI (refractive index) detector Calibration curve base resin: polystyrene resin

[0225] <Production of dispersion liquid> (Dispersion formulation 1) A mixture of 13.3 parts by mass of pigment, 0.7 parts by mass of dispersing aid, 4.9 parts by mass of resin, and 81.1 parts by mass of solvent was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm diameter) to prepare a dispersion. Then, a pressure of 2000 kg / cm was applied using a NANO-3000-10 high-pressure disperser equipped with a vacuum mechanism (manufactured by Nippon BEE Co., Ltd.). 3 The dispersion process was carried out under conditions of a flow rate of 500 g / min. This dispersion process was repeated a total of 10 times to obtain a dispersion liquid. The pigment, dispersing agent, resin, and solvent used were the materials shown in the table below.

[0226] (Dispersion formulation 2) A mixture of 13.3 parts by mass of pigment, 0.7 parts by mass of dispersing aid, 3.5 parts by mass of resin, and 82.5 parts by mass of solvent was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm diameter) to prepare a dispersion. Then, a high-pressure disperser equipped with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), was used to mix the mixture at a pressure of 2000 kg / cm. 3 The dispersion process was carried out under conditions of a flow rate of 500 g / min. This dispersion process was repeated a total of 10 times to obtain a dispersion liquid. The pigment, dispersing agent, resin solution, and solvent used were the materials shown in the table below.

[0227] [Table 1] [Table 2] [Table 3]

[0228] [Table 4] [Table 5] [Table 6]

[0229] [Table 7] [Table 8] [Table 9]

[0230] [Table 10] [Table 11] [Table 12]

[0231] The details of the materials indicated by the abbreviations in the table showing the formulation of the dispersion are as follows:

[0232] (pigment) P-1: CI Pigment Green 7 (green pigment) P-2: CI Pigment Green 36 (green pigment) P-3: CI Pigment Green 58 (green pigment) P-4: CI Pigment Green 59 (green pigment) P-5: CI Pigment Green 63 (green pigment) P-6: CI Pigment Yellow 129 (yellow pigment) P-7: CI Pigment Yellow 138 (yellow pigment) P-8: CI Pigment Yellow 139 (yellow pigment) P-9: CI Pigment Yellow 150 (yellow pigment) P-10: CI Pigment Yellow 185 (yellow pigment) P-11: CI Pigment Yellow 215 (yellow pigment) P-12: CI Pigment Yellow 231 (yellow pigment) P-13: CI Pigment Yellow 233 (yellow pigment) P-14: CI Pigment Red 177 (red pigment) P-15: CI Pigment Red 254 (red pigment) P-16: CI Pigment Red 264 (red pigment) P-17: CI Pigment Red 272 (red pigment) P-18: CI Pigment Red 291 (red pigment) P-19: CI Pigment Blue 15:4 (blue pigment) P-20: CI Pigment Blue 15:6 (blue pigment) P-21: CI Pigment Blue 16 (blue pigment) P-22: CI Pigment Violet 23 (purple pigment) P-23: TiO2 (pigment containing titanium atoms, white pigment) P-24: TiON (pigment containing titanium atoms, black pigment) P-25: Compound with the following structure (near-infrared absorbing pigment) [ka] P-26: Compound with the following structure (near-infrared absorbing pigment) [ka]

[0233] (Dispersion aid) Syn-1: Compound with the following structure (pigment derivative) [ka]

[0234] Syn-2: Compound with the following structure (pigment derivative) [ka]

[0235] Syn-3: Compound with the following structure (pigment derivative) [ka]

[0236] Syn-4: Compound with the following structure (pigment derivative) [ka]

[0237] Syn-5: Polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd.)

[0238] Syn-6: Compound with the following structure (pigment derivative) [ka]

[0239] Syn-7: Compound with the following structure (pigment derivative) [ka]

[0240] Syn-8: Compound with the following structure (pigment derivative) [ka]

[0241] Syn-9: Compound with the following structure (pigment derivative) [ka]

[0242] Syn-10: Compound with the following structure (pigment derivative) [ka]

[0243] Syn-11: Compound with the following structure (pigment derivative) [ka]

[0244] (resin) B-1: Resin B-1 synthesized by the following method A reaction vessel was charged with 50 parts by weight of methyl methacrylate, 30 parts by weight of n-butyl methacrylate, 20 parts by weight of (3-ethyloxetan-3-yl)methyl methacrylate, and 45.4 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 70°C, and 6 parts by weight of 3-mercapto-1,2-propanediol was added. 0.12 parts by weight of AIBN (azobisisobutyronitrile) was then added, and the reaction was continued for 12 hours. Solids content measurement confirmed that 95% reaction had occurred. Next, 9.7 parts by weight of pyromellitic anhydride, 70.3 parts by weight of PGMEA, and 0.20 parts by weight of DBU (1,8-diazabicyclo[5.4.0]-7-undecene) as a catalyst were added, and the reaction was continued for 7 hours at 120°C. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value and terminating the reaction, the mixture was dried to remove the solvent, yielding Resin B-1 with the following structure, having an acid value of 43 mgKOH / g and a weight-average molecular weight of 9000. [ka]

[0245] B-2: Resin B-2 synthesized by the following method 108 parts by weight of 1-thioglycerol, 174 parts by weight of pyromellitic anhydride, 650 parts by weight of methoxypropyl acetate, and 0.2 parts by weight of monobutyltin oxide as a catalyst were charged into a reaction vessel. After the atmospheric gas was replaced with nitrogen gas, the mixture was reacted at 120 °C for 5 hours (first step). Measurement of the acid value confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts by weight (solids equivalent) of the compound obtained in the first step, 200 parts by weight of 2-hydroxypropyl methacrylate, 200 parts by weight of ethyl acrylate, 150 parts by weight of t-butyl acrylate, 200 parts by weight of 2-methoxyethyl acrylate, 200 parts by weight of methyl acrylate, 50 parts by weight of methacrylic acid, and 663 parts by weight of PGMEA were charged into a reaction vessel. The reaction vessel was heated to 80 °C, and 1.2 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The mixture was reacted for 12 hours (second step). Finally, 500 parts by mass of a 50% by mass PGMEA solution of the compound obtained in the second step, 27.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts by mass of hydroquinone were charged into a reaction vessel, and a reaction rate of 2270 cm based on the isocyanate group was obtained. -1 The reaction was continued until the disappearance of the peak was confirmed (third step). After the disappearance of the peak was confirmed, the reaction solution was cooled and then dried to remove the solvent, yielding Resin B-2 having the following structure, with an acid value of 68 mg KOH / g, an ethylenically unsaturated bond group value of 0.62 mmol / g, and a weight-average molecular weight of 13,000. [ka]

[0246] B-3: Resin with the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 16,000, acid value: 67 mg KOH / g) [ka]

[0247] B-4: Resin with the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 24,000, acid value: 52.5 mg KOH / g) [ka]

[0248] B-5: Resin with the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 21,000, acid value: 58.4 mg KOH / g) [ka]

[0249] B-6: BYK-LPN21116 (BYK-Chemie, quaternary ammonium salt type acrylic block copolymer) dried and adjusted to a non-volatile content (solid content concentration) of 100% by mass

[0250] B-7: Resin with the following structure (the numbers attached to the main chain are molar ratios. Weight average molecular weight: 11,000, acid value: 69.2 mg KOH / g) [ka]

[0251] B-8: Resin with the following structure (the number attached to the main chain is the molar ratio. Weight average molecular weight: 21,000) [ka]

[0252] B-9: Resin B-9 synthesized by the following method A flask equipped with a condenser and a stirrer was charged with 100 parts by weight of PGMEA and purged with nitrogen. The flask was heated to 80°C, and a mixed solution of 100 parts by weight of PGMEA, 15 parts by weight of methacrylic acid, 15 parts by weight of styrene, 5 parts by weight of benzyl methacrylate, 15 parts by weight of 2-hydroxyethyl methacrylate, 23 parts by weight of 2-ethylhexyl methacrylate, 12 parts by weight of N-phenylmaleimide, 15 parts by weight of mono(2-acryloyloxyethyl) succinate, and 6 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise over 1 hour at the same temperature. Polymerization was carried out for 2 hours while maintaining this temperature. The temperature of the reaction solution was then raised to 100°C. Polymerization was continued for another hour, and the mixture was dried to remove the solvent, yielding Resin B-9 (weight average molecular weight 12,000, acid value 137 mgKOH / g).

[0253] B-10: Resin B-10 synthesized by the following method A flask equipped with a condenser and a stirrer was charged with 100 parts by weight of PGMEA and purged with nitrogen. The mixture was heated to 80°C, and a mixed solution of 100 parts by weight of PGMEA, 7 parts by weight of methacrylic acid, 15 parts by weight of styrene, 10 parts by weight of benzyl methacrylate, 20 parts by weight of 2-hydroxyethyl methacrylate, 28 parts by weight of 2-ethylhexyl methacrylate, 15 parts by weight of N-phenylmaleimide, 5 parts by weight of mono(2-acryloyloxyethyl) succinate, and 4 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise over 1 hour. The temperature was maintained and polymerization was allowed to proceed for 2 hours. The reaction solution was then heated to 100°C and polymerized for an additional 1 hour. The mixture was then dried to remove the solvent, yielding Resin B-10 (weight average molecular weight 18,500, acid value 59 mgKOH / g).

[0254] B-11: Resin with the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 20,000, acid value: 77 mg KOH / g) [ka]

[0255] (solvent) [Ether solvent represented by formula (1)] [Table 13]

[0256] [Solvents other than the ether solvents represented by formula (1)] SB-1: Propylene glycol monomethyl ether acetate (PGMEA) SB-2: Propylene glycol monomethyl ether (PGME) SB-3: Ethyl 3-ethoxypropionate SB-4: 2-octanone SB-5: Cyclopentanone SB-6: Diacetone alcohol

[0257] <Production of Resin Composition> Each resin composition was produced by mixing the materials in the proportions according to the following recipes 1 to 4. Note that some of the dispersions, polymerizable compounds, and photopolymerization initiators listed in the tables below were stored refrigerated at 5 to 10°C. The refrigerated dispersions, polymerizable compounds, and photopolymerization initiators were removed from the refrigerator at least 12 hours before producing the resin compositions and temporarily stored in a room controlled at a temperature of 17 to 27°C and a relative humidity of 40 to 80%, and the materials were allowed to return to room temperature before use. Each resin composition was produced using the following procedure. Specifically, a polymerizable compound, resin, and solvent were added to a mixing vessel equipped with a stirring blade and installed in a room controlled at a temperature of 17 to 27°C and a relative humidity of 40 to 80%, and stirring was initiated. Next, a photopolymerization initiator, a polymerization inhibitor, and additives were added, and stirring was continued for a total of 30 minutes or more. A monomer liquid was produced using this procedure. Next, a dispersion was added to a mixing vessel equipped with a stirring blade and installed in the temperature- and humidity-controlled room, followed by the addition of the monomer liquid, followed by the addition of a surfactant and stirring for 10 minutes or more. A resin composition was produced using this procedure. Finally, the resulting resin composition was filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.), filled into a storage container, and then stored with the void space of the storage container filled with gas having an oxygen concentration of 30% by volume.

[0258] In the table below, the content of the pigment in the total solid content of the resin composition is shown in the "Pigment concentration" column.

[0259] (Formulation 1) Dispersion liquid shown in the table below: 54.1 parts by mass 3.6 parts by mass of a polymerizable compound listed in the table below 3.3 parts by mass of resin listed in the table below 0.9 parts by mass of photopolymerization initiator listed in the table below 0.02 parts by weight of surfactant listed in the table below Polymerization inhibitor listed in the table below: 0.0002 parts by mass Solvent listed in the table below: 38.1 parts by mass

[0260] (Prescription 2) Dispersion liquid shown in the table below: 67.7 parts by mass 2.7 parts by mass of polymerizable compound shown in the table below 1.6 parts by mass of resin listed in the table below 0.9 parts by mass of photopolymerization initiator listed in the table below 0.02 parts by weight of surfactant listed in the table below Polymerization inhibitor listed in the table below: 0.0002 parts by mass Solvent listed in the table below: 27.1 parts by mass

[0261] (Formulation 3) Dispersion liquid shown in the table below: 81.2 parts by mass 0.9 parts by mass of a polymerizable compound listed in the table below 1.2 parts by mass of the resin listed in the table below 0.5 parts by mass of photopolymerization initiator listed in the table below 0.02 parts by weight of surfactant listed in the table below Polymerization inhibitor listed in the table below: 0.0002 parts by mass Solvent listed in the table below: 16.1 parts by mass

[0262] (Formulation 4) Dispersion liquid shown in the table below: 88.0 parts by mass 0.9 parts by mass of a polymerizable compound listed in the table below 1.1 parts by mass of resin listed in the table below 0.5 parts by mass of photopolymerization initiator listed in the table below 0.02 parts by weight of surfactant listed in the table below Polymerization inhibitor listed in the table below: 0.0002 parts by mass 9.4 parts by weight of solvent listed in the table below

[0263] [Table 14]

[0264] [Table 15]

[0265] [Table 16] [Table 17] [Table 18] [Table 19]

[0266] [Table 20] [Table 21] [Table 22] [Table 23]

[0267] [Table 24] [Table 25] [Table 26] [Table 27]

[0268] [Table 28]

[0269] Among the materials indicated by abbreviations in the table showing the formulation of the resin composition, details other than the dispersion are as follows: The dispersion used was the dispersion described above.

[0270] (polymerizable compound) M-1: Compound of the following structure [ka] M-2: Compound of the following structure [ka] M-3: KAYARAD DPHA (Nippon Kayaku Co., Ltd.) M-4: Compound of the following structure [ka]

[0271] (Photopolymerization initiator) I-1: Irgacure OXE02 (BASF, oxime compound) I-2 to I-5: Compounds of the following structure [ka]

[0272] (resin) B-1 to B-10: Resins B-1 to B-10 described above

[0273] (surfactant) W-1: FZ-2122 (DuPont Toray Specialty Materials Co., Ltd., silicone surfactant) W-2: BYK-330 (BYK-Chemie, silicone surfactant) W-3: KF-6001 (Shin-Etsu Chemical Co., Ltd., silicone surfactant) W-4: PolyFox PF6320 (OMNOVA, fluorochemical surfactant) W-5: Megafac F-554 (DIC Corporation, fluorine-based surfactant)

[0274] (polymerization inhibitor) In-1: p-Methoxyphenol

[0275] (solvent) SA-1, SA-2, SA-3, SA-4, SA-5, SB-1, SB-2, SB-3, SB-4, SB-5, SB-6: Solvents mentioned above SA-1, SA-2, SA-3, SA-4, SA-5, SB-1, SB-2, SB-3, SB-4, SB-5, SB-6

[0276] <Evaluation of pigment dispersibility> (initial average particle size) The average particle size of the pigment in the resin composition immediately after production was measured using a particle size distribution analyzer (MT3300EXII, manufactured by Microtrack Bell Co., Ltd., measurement principle: laser diffraction / scattering method). The initial average particle size was evaluated according to the following criteria. In practice, a score of 3 or greater on the following criteria is preferred. -Evaluation criteria- 5: Average particle size of pigment ≦70nm 4: 70nm<average particle size of pigment≦100nm 3: 100nm<average particle size of pigment≦150nm 2: 150nm<average particle size of pigment≦200nm 1: Average particle size of pigment > 200 nm

[0277] (Variation rate of average particle size) The average particle size of the pigment (hereinafter referred to as average particle size 1) of the resin composition immediately after production was measured using a particle size distribution analyzer (MT3300EXII, manufactured by Microtrack Bell Co., Ltd., measurement principle: laser diffraction / scattering method). Next, each resin composition was stored at 5°C for 9 months, and then the average particle size of the pigment (hereinafter referred to as average particle size 2) was measured again using a particle size distribution analyzer (MT3300EXII, manufactured by Microtrack Bell Corporation, measurement principle: laser diffraction / scattering method). The rate of variation of the average particle size was calculated using the following formula, and the rate of variation of the average particle size was evaluated according to the following criteria. In practice, a score of 3 or more according to the following criteria is preferable. Fluctuation rate of average particle size (%) = ((average particle size 2 / average particle size 1)-1) x 100 -Evaluation criteria- 5: Variation rate of average particle size <10% 4: 10%≦Average particle size fluctuation rate<20% 3: 20%≦Average particle size fluctuation rate<50% 2: 50%≦Average particle size variation rate<100% 1: Variation rate of average particle size ≥ 100%

[0278] <Evaluation of film thickness uniformity> The resin composition immediately after production was spin-coated onto an 8-inch (203.2 mm) silicon wafer to form a film with an average thickness of 400 nm. The thickness of the film formed on the silicon wafer was measured using an optical film thickness meter F-50 (Filmetrics, Inc.). Measurements were taken at 10 points from one end of the silicon wafer to the other, and the values ​​of |average film thickness - maximum film thickness| (absolute value of the difference between the average film thickness and the maximum film thickness) and |average film thickness - minimum film thickness| (absolute value of the difference between the average film thickness and the minimum film thickness) were calculated. The larger of the values ​​of |average film thickness - maximum film thickness| and |average film thickness - minimum film thickness| (hereinafter referred to as Δt) was used to evaluate film thickness uniformity according to the following criteria. In practice, a score of 3 or higher on the following criteria is preferable. 5: Δt<3nm 4:3nm≦Δt<5nm 3: 5nm≦Δt<10nm 2: 10nm≦Δt<20nm 1: Δt≧20nm

[0279] [Table 29]

[0280] [Table 30]

[0281] [Table 31]

[0282] As shown in the above table, the resin compositions of the examples had good dispersibility and film thickness uniformity.

[0283] (Example 1001) An underlayer film-forming composition was applied by spin coating onto a support having a diameter of 8 inches (=203.2 mm) on which a silicon photodiode had been formed, and heated at 220°C for 5 minutes using a hot plate to form an underlayer film with a thickness of 5 nm. A green resin composition was applied by spin coating onto the support with the underlayer film so that the film thickness after formation was 0.4 μm. Next, the film was heated at 100°C for 2 minutes using a hot plate. Next, an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Inc.) was used to apply 1000 mJ / cm 2 The green resin composition was exposed to light through a 1.4 μm square Bayer pattern mask at an exposure dose of 1000 kJ / cm. Next, puddle development was performed using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 60 seconds. The green resin composition was then rinsed with a spin shower and further washed with pure water. The green resin composition was then patterned by heating at 200°C for 5 minutes using a hot plate to form green pixels. Similarly, the red resin composition and the blue resin composition were patterned using a similar process using a 1.4 μm square dot pattern mask to sequentially form red and blue pixels, thereby forming a color filter having green, red, and blue pixels. In this color filter, the green pixels were formed in a Bayer pattern, and adjacent regions, the red and blue pixels were formed in a dot pattern. The resulting color filter was incorporated into a solid-state imaging device according to a known method. This solid-state imaging device exhibited favorable image recognition capabilities. The green resin composition used was the resin composition of Example 141. The red resin composition used was the resin composition of Example 75. The resin composition of Example 82 was used as the blue resin composition.

[0284] In the above, a KrF scanner exposure device (FPA-6300ES6a, manufactured by Canon Inc.) was used to irradiate light with a wavelength of 248 nm at 200 mJ / cm through a mask with a side length of 0.7 μm. 2 Even when the exposure was performed with irradiation at an exposure amount of 1000 ppm, a solid-state imaging device with good image performance similar to that described above was obtained.

[0285] (Composition for forming lower layer film) The composition for forming the underlayer film was prepared by mixing the materials shown below in the ratios shown below and filtering the mixture through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.). -Composition of the composition for forming the underlayer film- Resin A...0.7 parts by mass Surfactant A: 0.8 parts by mass Propylene glycol monomethyl ether acetate (PGMEA) 98.5 parts by mass

[0286] Details of each material are as follows: Resin A: Cyclomer P (ACA) 230AA (manufactured by Daicel Corporation, acid value = 30 mg KOH / g, weight average molecular weight 15,000, PGME solution with a solid content of 54% by mass) Surfactant A: A 0.2 mass % PGMEA solution of the compound with the following structure (weight average molecular weight 14,000, the percentage of repeating units is mol %, a fluorochemical surfactant) [ka]

Claims

1. Contains a pigment, a resin, and a solvent, The pigment comprises an organic pigment, the resin includes at least one selected from a resin having an acid value of 5 to 200 mgKOH / g and a resin having an amine value of 5 to 300 mgKOH / g; a resin composition, wherein the solvent contains an ether-based solvent represented by formula (1); 【Chemical 1】 In formula (1), R １ represents a hydrocarbon group, and R ２ ~R ６ each independently represents a hydrogen atom or a hydrocarbon group.

2. 2. The resin composition according to claim 1, wherein the ether solvent represented by formula (1) is at least one selected from anisole, phenetole, 4-methylanisole, 3-methylanisole, and 2-methylanisole.

3. 3. The resin composition according to claim 1, wherein the solvent contains 1 to 100% by mass of an ether-based solvent represented by formula (1).

4. 3. The resin composition according to claim 1, wherein the solvent contains 1 to 50% by mass of an ether-based solvent represented by formula (1).

5. The resin composition according to any one of claims 1 to 4, wherein the resin composition contains 0.5 mass% or more of the ether-based solvent represented by the formula (1).

6. The resin composition according to any one of claims 1 to 5, wherein the solvent comprises an ether-based solvent represented by the formula (1) and a solvent other than the ether-based solvent represented by the formula (1).

7. The resin composition according to claim 6, wherein the solvent other than the ether-based solvent represented by formula (1) includes propylene glycol monomethyl ether acetate.

8. The resin composition according to claim 7, comprising 100 to 9900 parts by mass of propylene glycol monomethyl ether acetate per 100 parts by mass of the ether solvent represented by the formula (1).

9. The resin composition according to any one of claims 6 to 8, wherein the solvent other than the ether-based solvent represented by formula (1) includes a ketone-based solvent.

10. The resin includes a resin having an acid value of 5 to 200 mg KOH / g, The organic pigment includes at least one selected from a phthalocyanine pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, an isoindoline pigment, an azo pigment, an azomethine pigment, a quinophthalone pigment, a dioxazine pigment, and a pteridine pigment. The resin composition according to any one of claims 1 to 9.

11. A method for producing the resin composition according to any one of claims 1 to 10, comprising a step of dispersing a pigment containing an organic pigment in the presence of a resin containing at least one selected from a resin having an acid value of 5 to 200 mgKOH / g and a resin having an amine value of 5 to 300 mgKOH / g, and a solvent containing an ether-based solvent represented by formula (1); 【Chemistry 2】 In formula (1), R １ represents a hydrocarbon group, and R ２ ~R ６ each independently represents a hydrogen atom or a hydrocarbon group.

12. A method for producing a film, comprising the step of applying the resin composition according to any one of claims 1 to 10 to a support.

13. A method for producing an optical filter, comprising the method for producing the film according to claim 12.

14. A method for manufacturing a solid-state imaging device, comprising the method for manufacturing a film according to claim 12.

15. A method for manufacturing an image display device, comprising the method for manufacturing the film according to claim 12.

Images