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

Abstract

To provide a photosensitive composition whereby: when forming pixels by photolithography using the photosensitive composition after its storage, it is possible to suppress the generation of residues among the pixels and the peeling of the pixels and a method for producing the same; and a film, an optical filter, a solid state image sensor and an image display device each including the photosensitive composition.SOLUTION: A photosensitive composition contains a pigment, a polymerizable compound, a photopolymerization initiator, and a reactant of a polyalkyleneimine and an acid anhydride.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has grown significantly due to the widespread use of digital cameras and camera-equipped mobile phones. Color filters are used as key devices in displays and optical elements.

[0003] Color filters are manufactured using photosensitive compositions containing color materials. For example, Patent Document 1 describes an invention relating to a coloring composition for color filters containing a xanthene dye, polyethyleneimine, and a binder resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-041145 Summary of the Invention [Problem to be solved by the invention]

[0005] According to the studies of the present inventors, it has been found that in a photosensitive composition using a pigment as a colorant, the inclusion of a compound with a high amine value, such as polyethyleneimine, can suppress aggregation of the pigment during storage of the photosensitive composition, thereby improving storage stability. Further studies by the present inventors on such photosensitive compositions have revealed that there is room for further improvement in suppressing residues between pixels and preventing pixel peeling when pixels are formed by photolithography using the photosensitive composition after storage.

[0006] Therefore, an object of the present invention is to provide a photosensitive composition that can suppress the generation of residue between pixels and peeling of pixels when pixels are formed by photolithography using the photosensitive composition after storage, and a method for producing the same. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device using the photosensitive composition. [Means for solving the problem]

[0007] The present inventors have conducted further studies on photosensitive compositions containing a pigment, a polymerizable compound, a photopolymerization initiator, and a compound with a high amine value such as a polyalkyleneimine, and have concluded that, during storage of such photosensitive compositions, the compound with a high amine value such as a polyalkyleneimine reacts with the polymerizable compound, causing the polymerizable compound to have a high molecular weight, and the proportion of the polymerizable compound in the photosensitive composition decreases over time. Therefore, when pixels are formed by photolithography using the photosensitive composition after storage, residues are generated between pixels and peeling of the pixels is likely to occur. The present inventors further investigated the above-mentioned photosensitive composition and found that by further adding an acid anhydride, a compound with a high amine value, such as a polyalkyleneimine, reacts with the acid anhydride in the photosensitive composition, reducing the activity of the compound with a high amine value, such as a polyalkyleneimine, and thereby suppressing the reaction between the compound with a high amine value, such as a polyalkyleneimine, and a polymerizable compound during storage, and that even when pixels are formed by photolithography using the photosensitive composition after storage, the generation of residue between pixels and peeling of pixels can be suppressed, leading to the completion of the present invention.

[0008] <1> A pigment, a polymerizable compound; a photopolymerization initiator; a reaction product of a polyalkyleneimine with an acid anhydride; Including, Photosensitive composition. <2> the weight-average molecular weight of the reaction product of the polyalkyleneimine and the acid anhydride is 5000 or less; <1> The photosensitive composition according to claim 1. <3> A pigment, a polymerizable compound; a photopolymerization initiator; a reaction product of a compound having three or more amino groups in one molecule and an amine value of 2.7 mmol / g or more with an acid anhydride; Including, Photosensitive composition. <4> The compound having three or more amino groups in one molecule and an amine value of 2.7 mmol / g or more is a polyalkyleneimine. <3> The photosensitive composition according to claim 1. <5> The polyalkyleneimine is polyethyleneimine. <1> or <4> The photosensitive composition according to claim 1. <6> The molecular weight of the acid anhydride is 300 or less. <1> ~ <5> 1. The photosensitive composition according to any one of the above items. <7> The acid anhydride is a compound having 20 or less carbon atoms. <1> ~ <6> 1. The photosensitive composition according to any one of the above items. <8> The acid anhydride is a carboxylic acid anhydride. <1> ~ <7> 1. The photosensitive composition according to any one of the above items. <9> The pigment includes a phthalocyanine pigment. <1> ~ <8> 1. The photosensitive composition according to any one of the above items. <10> <1> A method for producing the photosensitive composition according to claim 1, a step of dispersing a pigment and a polyalkyleneimine in a solvent to prepare a dispersion; a step of mixing the dispersion, an acid anhydride, a polymerizable compound, and a photopolymerization initiator; A method for producing a photosensitive composition, comprising: <11> <3> A method for producing the photosensitive composition according to claim 1, a step of dispersing a pigment and a compound having three or more amino groups in one molecule and an amine value of 2.7 mmol / g or more in a solvent to prepare a dispersion; a step of mixing the dispersion, an acid anhydride, a polymerizable compound, and a photopolymerization initiator; A method for producing a photosensitive composition, comprising: <12> <1> ~ <9> A film obtained by using the photosensitive composition according to any one of the above items. <13> <12> An optical filter having the film according to claim 1. <14> <12> A solid-state imaging device having the film according to claim 1. <15> <12> An image display device having the film according to claim 1. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a photosensitive composition and a method for producing the same that can suppress the generation of residue between pixels and peeling of pixels when pixels are formed by photolithography using the photosensitive composition after storage.The present invention also provides a film, an optical filter, a solid-state imaging device, and an image display device using the photosensitive composition. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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.

[0011] <Photosensitive composition> A first aspect of the photosensitive composition of the present invention is A pigment, a polymerizable compound; a photopolymerization initiator; a reaction product of a polyalkyleneimine with an acid anhydride; The present invention is characterized in that it includes:

[0012] A second aspect of the photosensitive composition of the present invention is A pigment, a polymerizable compound; a photopolymerization initiator; a reaction product of a compound having three or more amino groups in one molecule and an amine value of 2.7 mmol / g or more with an acid anhydride; The present invention is characterized in that it includes:

[0013] According to the photosensitive composition of the present invention, when pixels are formed by photolithography using the photosensitive composition after storage, it is possible to suppress the generation of residue between pixels and peeling of pixels.

[0014] The photosensitive composition of the present invention is preferably used as a photosensitive composition for an optical filter. Examples of optical filters include color filters, near-infrared transmission filters, and near-infrared cut filters, and color filters are preferred. The photosensitive composition of the present invention is also preferably used for solid-state imaging devices. More specifically, it is preferably used as a photosensitive composition for optical filters used in solid-state imaging devices, and more preferably used as a photosensitive composition for forming colored pixels of color filters used in solid-state imaging devices.

[0015] 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, with green or cyan pixels being preferred, and green pixels being more preferred. The colored pixels of the color filter may be formed using a photosensitive composition containing a chromatic pigment.

[0016] 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 photosensitive composition containing a near-infrared absorbing pigment.

[0017] 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.

[0018] The photosensitive composition of the present invention can also be used as a light-shielding film.

[0019] The solids concentration of the photosensitive composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, 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.

[0020] Each component used in the photosensitive composition of the present invention will be described below.

[0021] <<Colorants>> The photosensitive composition of the present invention contains a colorant. In the present invention, a composition containing a pigment is used as the colorant. Examples of pigments include white pigments, black pigments, chromatic pigments, and near-infrared absorbing pigments. In this specification, the term "white pigment" includes not only pure white pigments but also light gray pigments close to white (e.g., off-white, light gray, etc.).

[0022] When the photosensitive 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 photosensitive 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 photosensitive composition, two or more chromatic pigments are used in combination, or a black pigment is used as the pigment.

[0023] 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. When the average primary particle diameter of the pigment is within the above range, the pigment has good dispersion stability in the photosensitive composition. 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. In addition, primary particles of the pigment refer to independent particles that are not aggregated.

[0024] The pigment used in the present invention preferably contains at least one selected from phthalocyanine pigments, azomethine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, pteridine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments, and pyrrolopyrrole pigments. It is more preferable to contain at least one selected from phthalocyanine pigments, diketopyrrolopyrrole pigments, and pyrrolopyrrole pigments. It is even more preferable to contain a phthalocyanine pigment, as this more significantly enhances the effects of the present invention. Furthermore, the phthalocyanine 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. Copper phthalocyanine pigments or zinc phthalocyanine pigments are preferred, and zinc phthalocyanine pigments are more preferred. The metal phthalocyanine pigment is preferably a halogenated phthalocyanine pigment, more preferably a halogenated copper phthalocyanine pigment or a halogenated zinc phthalocyanine pigment, and even more preferably a halogenated zinc phthalocyanine pigment.

[0025] Here, the halogenated phthalocyanine pigment refers to a phthalocyanine pigment having a halogen atom as a substituent. The copper phthalocyanine pigment refers to a phthalocyanine pigment having a copper atom as a central metal. The zinc phthalocyanine pigment refers to a phthalocyanine pigment having a zinc atom as a central metal. The aluminum phthalocyanine pigment refers to a phthalocyanine pigment having an aluminum atom as a central metal.

[0026] Specific examples of metal phthalocyanine pigments include green pigments such as CI Pigment Green 7, 36, 58, 59, 62, and 63, and blue pigments such as CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6.

[0027] The pigments used in the present invention will be described in more detail below.

[0028] (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. Specific examples of these include the following:

[0029] 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).

[0030] In addition, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule can also be used as a green pigment. Specific examples include the compounds described in International Publication No. 2015 / 118720. In addition, 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, aluminum phthalocyanine compounds described in Japanese Patent Application Laid-Open No. 2020-070426, and core-shell pigments described in Japanese Patent Application Laid-Open No. 2020-076995 can also be used as green pigments.

[0031] 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.

[0032] Furthermore, azobarbituric acid nickel complex having the following structure can also be used as a yellow pigment. [ka]

[0033] Further, as yellow pigments, compounds described in JP-A-2017-201003, compounds described in JP-A-2017-197719, compounds described in paragraphs 0011 to 0062 and 0137 to 0276 of JP-A-2017-171912, compounds described in paragraphs 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913, compounds described in paragraphs 0011 to 0062 and 0139 to 0190 of JP-A-2017-171914, and compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915 can be used. , quinophthalone compounds described in paragraphs 0011 to 0034 of JP 2013-054339 A, quinophthalone compounds described in paragraphs 0013 to 0058 of JP 2014-026228 A, isoindoline compounds described in JP 2018-062644 A, quinophthalone compounds described in JP 2018-203798 A, quinophthalone compounds described in JP 2018-062578 A, quinophthalone compounds described in Japanese Patent No. 6432076 A, quinophthalone compounds described in JP 2018-155881 A, JP 2018-1117 A 57, 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, quinophthalone compounds described in JP 2013-209435 A, quinophthalone compounds described in JP 2013-181015 A Quinophthalone compounds, quinophthalone compounds described in JP 2013-061622 A, quinophthalone compounds described in JP 2013-032486 A, quinophthalone compounds described in JP 2012-226110 A, quinophthalone compounds described in JP 2008-074987 A, quinophthalone compounds described in JP 2008-081565 A, quinophthalone compounds described in JP 2008-074986 A, quinophthalone compounds described in JP 2008-074985 A, quinophthalone compounds described in JP 2008-050420 A,Quinophthalone compounds described in JP 2008-031281 A, JP 48-032765 A, JP 2019-008014 A, quinophthalone compounds described in Japanese Patent No. 6607427 A, compounds described in Korean Patent Publication No. 10-2014-0034963 A, compounds described in Japanese Patent Publication No. 2017-095706 A, compounds described in Taiwan Patent Application Publication No. 201920495 A, compounds described in Japanese Patent No. 6607427 A, compounds described in Japanese Patent Publication No. 2020-033525 A, compounds described in Japanese Patent Publication No. 2020-033524 A, compounds described in Japanese Patent Publication No. 2020-033523 A Compounds described in JP 2020-033522 A, compounds described in JP 2020-033521 A, compounds described in WO 2020 / 045200 A, compounds described in WO 2020 / 045199 A, compounds described in WO 2020 / 045197 A, azo compounds described in JP 2020-093994 A, perylene compounds described in JP 2020-083982 A, perylene compounds described in WO 2020 / 105346 A, quinophthalone compounds described in JP 2020-517791 A, compounds represented by the following formula (QP1), and compounds represented by the following formula (QP2) can also be used. Furthermore, polymerized versions of these compounds are also preferably used from the viewpoint of improving color value. [ka]

[0034] 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]

[0035] In formula (QP2), Y1 ~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.

[0036] As red pigments, 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 A, diketopyrrolopyrrole compounds described in WO 2012 / 102399 A, diketopyrrolopyrrole compounds described in WO 2012 / 117965 A, brominated diketopyrrolopyrrole compounds described in JP 2020-085947 A, naphthol azo compounds described in JP 2012-229344 A, and Red pigments described in Japanese Patent Publication No. 119, Japanese Patent No. 6525101, brominated diketopyrrolopyrrole compounds described in paragraph 0229 of JP 2020-090632, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140741, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, perylene compounds described in JP 2020-079396, diketopyrrolopyrrole compounds described in paragraphs 0025 to 0041 of JP 2020-066702, etc. can also be used. In addition, as a red pigment, a compound 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 can also be used.

[0037] For the diffraction angles that various pigments preferably have, please refer to the descriptions in Japanese Patent Nos. 6561862, 6413872, 6281345, JP 2020-026503 A, and JP 2020-033526 A, the contents of which are incorporated herein by reference. It is also preferable to use a pyrrolopyrrole pigment in which the crystallite size 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 to set the physical properties of the pyrrolopyrrole pigment as described in paragraphs 0028 to 0073 of Japanese Patent No. 2020-097744 A.

[0038] Two or more chromatic pigments may be used in combination. For example, when the photosensitive composition of the present invention is used to form green pixels in a color filter, it is preferable to use a green pigment and a yellow pigment in combination. As the green pigment, CI Pigment Green 7, 36, 58, 59, and 63 are preferred, and CI Pigment Green 58 is more preferred. As the yellow pigment, CI Pigment Yellow 129, 138, 139, 150, 185, 215, 215, 231, and 233 are preferred, and CI Pigment Yellow 185 is more 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 photosensitive composition contains two or more chromatic pigments and exhibits a black color through the combination of two or more chromatic pigments, the photosensitive composition of the present invention can be preferably used as a photosensitive 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 black pigments can be used. Examples of inorganic black pigments include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is a black particle containing titanium atoms, and low-order titanium oxide or titanium oxynitride is preferred. Titanium black can be surface-modified as needed to improve dispersibility, suppress aggregation, etc. 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. Specific examples of inorganic black pigments include CI Pigment Black 1 and 7. It is preferable that titanium black have small individual particle sizes and small average primary particle sizes. Specifically, the average primary particle size is preferably 10 to 45 nm. 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. Regarding the dispersion, see 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] Examples of organic black pigments include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. Examples of bisbenzofuranone compounds include those described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234, and are available, for example, as "Irgaphor Black" manufactured by BASF. Examples of perylene compounds include those described in paragraphs 0016 to 0020 of JP-A-2017-226821, CI Pigment Black 31, 32, and the like.

[0046] (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 max is 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 photosensitive composition containing the near-infrared absorbing pigment.

[0047] 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. At least one selected from pyrrolopyrrole compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, and naphthalocyanine compounds is preferred, a pyrrolopyrrole compound or a squarylium compound is more preferred, and a pyrrolopyrrole compound is particularly preferred.

[0048] The photosensitive composition of the present invention may contain a dye as a coloring material. The dye is not particularly limited, and known dyes can be used. Examples of the dye include chromatic dyes, black dyes, and near-infrared absorbing dyes.

[0049] The photosensitive composition of the present invention can use, as a colorant, a thiazole compound described in JP 2012-158649 A, an azo compound described in JP 2011-184493 A, an azo compound described in JP 2011-145540 A, a triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, a xanthene compound described in JP 2020-117638 A, a phthalocyanine compound described in WO 2020 / 174991, an isoindoline compound described in JP 2020-160279 A, ​​or a salt thereof.

[0050] The content of the colorant in the total solid content of the photosensitive composition is preferably 30 to 80% by mass. The lower limit is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit is preferably 75% by mass or less, more preferably 70% by mass or less.

[0051] The content of the pigment in the total solid content of the photosensitive composition is preferably 30 to 80% by mass. The lower limit is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit is preferably 75% by mass or less, more preferably 70% by mass or less.

[0052] The content of the phthalocyanine pigment in the pigment is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% 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.

[0053] The content of the chromatic pigment in the pigment is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and even more preferably 50 to 100% by mass.

[0054] The content of the dye in the total solid content of the photosensitive composition is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 10% by mass or less. The content of the dye in the photosensitive 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, relative to 100 parts by mass of the pigment.

[0055] It is also preferred that the photosensitive composition of the present invention is substantially free of dyes. In this specification, "substantially free of dyes" means that the dye content of the total solid content of the photosensitive composition is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably free of dyes.

[0056] <<Polymerizable compounds>> The photosensitive composition of the present invention contains a polymerizable compound. The polymerizable compound is preferably 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 is preferably a radically polymerizable compound.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] Furthermore, the polymerizable compound may also be a trifunctional (meth)acrylate compound such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate, 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.).

[0061] 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.

[0062] 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.).

[0063] 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.

[0064] 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]

[0065] 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.

[0066] 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]

[0067] 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.).

[0068] The content of the polymerizable compound in the total solid content of the photosensitive 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.

[0069] <<Photopolymerization initiator>> The photosensitive composition of the present invention 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 region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0070] 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 compounds, 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, benzyl dimethyl ketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, hexaarylbiimidazole compound, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound, or 3-aryl-substituted coumarin compound, more preferably a compound selected from oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, and even more preferably an oxime compound. In addition, examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173, the compounds described in Japanese Patent No. 6301489, and the MATERIAL STAGE 37 to 60pp, vol. 19, No. 3, 2019, peroxide-based photopolymerization initiators described, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A, aminoacetophenone-based initiators having an oxazolidine group described in JP 2020-055992 A, oxime-based photopolymerization initiators described in JP 2013-190459 A, polymers described in JP 2020-172619 A, and the like, the contents of which are incorporated herein by reference.

[0071] 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).

[0072] 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, compounds described in JP 2000-066385 A, compounds described in JP-T-2004-534797 A, compounds described in JP-A-2006-342166 A, compounds described in JP-A-2017-019766 A, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP 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, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (all manufactured by BASF), TR-PBG-304 and TR-PBG-327 (manufactured by Tronley), and Adeka Optomer N-1919 (manufactured by ADEKA Corporation; photopolymerization initiator 2 described in JP 2012-014052 A).In addition, it is also preferable to use, as the oxime compound, a compound that is not colored 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).

[0073] 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, Japanese Patent No. 6636081 A, and Korean Patent Publication No. 10-2016-0109444 A.

[0074] 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.

[0075] 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.

[0076] 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).

[0077] 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.

[0078] 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.

[0079] 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. An acyl group and a nitro group are preferred, an acyl group is more preferred, 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.

[0080] 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 X1 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 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; However, R X10 ~R X14 At least one of the groups is an electron-withdrawing group.

[0081] 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, an acyl group is more preferred, and a benzoyl group is even more preferred.

[0082] 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.

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

[0084] 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.

[0085] [ka] [ka] [ka]

[0086] 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.

[0087] 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, thereby obtaining 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 photosensitive 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.

[0088] The content of the photopolymerization initiator in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 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.

[0089] <<Specific reactants>> The photosensitive composition of the present invention contains a reaction product of a polyalkyleneimine with an acid anhydride, or a reaction product of an acid anhydride with a compound having three or more amino groups in one molecule and an amine value of 2.7 mmol / g or more.

[0090] Hereinafter, the reaction product of a polyalkyleneimine and an acid anhydride will also be referred to as reactant A. Furthermore, the reaction product of an acid anhydride and a compound having three or more amino groups per molecule and an amine value of 2.7 mmol / g or more will also be referred to as reactant B. Furthermore, reactant A and reactant B together will also be referred to as a specific reactant. Furthermore, a compound having three or more amino groups per molecule and an amine value of 2.7 mmol / g or more will also be referred to as amine compound b. Furthermore, the polyalkyleneimine related to reactant A and amine compound b related to reactant B (a compound having three or more amino groups per molecule and an amine value of 2.7 mmol / g or more) will also be referred to as a specific amine compound.

[0091] Here, polyalkyleneimine refers to a polymer obtained by ring-opening polymerization of alkyleneimine. The polyalkyleneimine is preferably a polymer having 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, further preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms. Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred.

[0092] The molecular weight of the polyalkyleneimine related to reactant A is preferably 100 or more, more preferably 200 or more, and even 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 polyalkyleneimine 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 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 molecular weight cannot be measured by viscosity method or measurement by viscosity method is difficult, the number average molecular weight value measured in polystyrene equivalent by GPC (gel permeation chromatography) method is used.

[0093] The amine value of the polyalkyleneimine is preferably 2.7 mmol / g or more, more preferably 5 mmol / g or more, even more preferably 10 mmol / g or more, and particularly preferably 15 mmol / g or more, as calculated by the method described in the Examples below.

[0094] The polyalkyleneimine is preferably polyethyleneimine. 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 amount of primary amino groups, secondary amino groups, and tertiary amino groups. Commercially available polyethyleneimine products include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).

[0095] The molecular weight of the amine compound b in reactant B is preferably 100 or more, more preferably 200 or more, and even 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 amine compound b, if the molecular weight can be calculated from the structural formula, the molecular weight of amine compound b is the value calculated from the structural formula. On the other hand, if the molecular weight of amine compound b cannot be calculated from the structural formula or is difficult to calculate, 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 is difficult to measure, 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 is difficult to measure, the number average molecular weight value measured in terms of polystyrene by GPC (gel permeation chromatography) method is used.

[0096] The amine value of the amine compound b is 2.7 mmol / g or more, preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more. The amine value of the amine compound b was calculated by the method described in the Examples below.

[0097] The number of amino groups contained in the amine compound b is 3 or more, preferably 4 or more, more preferably 6 or more, and even more preferably 10 or more.

[0098] Amine compound b is preferably a compound having a primary amino group, more preferably a compound containing a primary amino group and a tertiary amino group, and even more preferably a compound containing a primary amino group, a secondary amino group, and a tertiary amino group.

[0099] The amino group of the amine compound b may be a cyclic amino group. The cyclic amino group may be an aliphatic cyclic amino group such as a piperidino group, or an aromatic cyclic amino group such as a pyridyl group. The cyclic amino group is preferably a cyclic amino group having a 5- or 6-membered ring structure, more preferably a cyclic amino group having a 6-membered ring structure, and even more preferably an aliphatic cyclic amino group having a 6-membered ring structure. The cyclic amino group preferably has a hindered amine structure, and particularly preferably a 6-membered hindered amine structure. The hindered amine structure preferably has substituents such as alkyl groups on two carbon atoms in the ring structure adjacent to the nitrogen atom of the cyclic amino group. Examples of cyclic amino groups having a hindered amine structure include a 1,2,2,6,6-pentamethylpiperidyl group, a 2,2,6,6-tetramethylpiperidyl group, a 1,2,6,6-trimethylpiperidyl group, a 2,6-dimethylpiperidyl group, a 1-methyl-2,6-di(t-butyl)piperidyl group, a 2,6-di(t-butyl)piperidyl group, a 1,2,2,5,5-pentamethylpyrrolidyl group, a 2,2,5,5-tetramethylpyrrolidyl group, etc. Among these, a 1,2,2,6,6-pentamethylpiperidyl group or a 2,2,6,6-tetramethylpiperidyl group is preferred, and a 1,2,2,6,6-pentamethylpiperidyl group is more preferred.

[0100] Amine compound b is preferably a polyalkyleneimine, more preferably a polyethyleneimine, and 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 amount of primary, secondary, and tertiary amino groups.

[0101] The amine compound b may also be a compound having a cyclic amino group. Examples of such compounds include compounds having the following structures. Commercially available products include ADK STAB LA-52, LA-57, LA-63P, and LA-68 (all manufactured by ADEKA CORPORATION). [ka]

[0102] A resin having an amino group on the side chain can also be used as the amine compound b. A compound having the structure shown below can also be used as the amine compound b. [ka]

[0103] Examples of the acid anhydride in the specific reactant include carboxylic acid anhydrides and sulfonic acid anhydrides, with carboxylic acid anhydrides being preferred. Examples of the carboxylic acid anhydride include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides, with aliphatic carboxylic acid anhydrides being preferred.

[0104] The molecular weight of the acid anhydride is preferably 300 or less, and more preferably 80-300.

[0105] The acid anhydride is preferably a compound having 20 or less carbon atoms, and more preferably a compound having 5 to 15 carbon atoms, because this allows for a high level of both reactivity with the polyalkyleneimine or amine compound b and heat resistance of the acid anhydride.

[0106] Specific examples of acid anhydrides include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, isobutyric anhydride, butyric anhydride, 2-methylbutyric anhydride, pivalic anhydride, isovaleric anhydride, valeric anhydride, 2-methylvaleric anhydride, 3-methylvaleric anhydride, 4-methylvaleric anhydride, hexanoic anhydride, 2-methylhexanoic anhydride, 3-methylhexanoic anhydride, 4-methylhexanoic anhydride, 5-methylhexanoic anhydride, heptanoic anhydride, 2-methylheptanoic anhydride, 3-methylheptanoic anhydride, 4-methylheptanoic anhydride, 5-methylheptanoic anhydride, 6-methylheptanoic anhydride, 3-phenylpropionic anhydride, phenylacetic anhydride, methacrylic anhydride, acrylic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, and glutaric anhydride; Aromatic carboxylic acid anhydrides such as benzoic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride; Examples include sulfocarboxylic acid anhydrides such as 2-sulfobenzoic acid anhydride.

[0107] Commercially available acid anhydrides include Rikacid MH, Rikacid HNA-100, Rikacid OSA, and Rikacid DDSA (all manufactured by New Japan Chemical Co., Ltd.).

[0108] The specific reactant is preferably a compound containing a structure represented by any one of formulas (1) to (3). In formulas (1) to (3), * represents a bond, R represents a divalent linking group, and M represents a hydrogen atom or a counter ion. The counter ion may be an alkali metal ion (Li + , Na + , K. +Examples of the hydrocarbon group include an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion. R preferably has 2 to 20 carbon atoms, more preferably 2 to 15, even more preferably 2 to 10, and particularly preferably 2 to 6. R is preferably a group containing a hydrocarbon group, and more preferably a hydrocarbon group. The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Specific examples of the hydrocarbon group include an alkylene group, an alkenylene group, and an arylene group, and preferably an alkylene group or an alkenylene group, and more preferably an alkylene group. The alkylene group may be linear, branched, or cyclic. The divalent group represented by R may have a ring structure. [ka]

[0109] The weight average molecular weight of the specific reactant is preferably 5000 or less, more preferably 2000 or less, because this can suppress the generation of development residues. The lower limit is preferably 100 or more, more preferably 200 or more.

[0110] Furthermore, when the specific reactant is the above-mentioned reactant A, the weight-average molecular weight of reactant A is preferably 5000 or less, more preferably 2000 or less, because this can suppress the generation of development residues. The lower limit is preferably 100 or more, more preferably 200 or more.

[0111] The mixing ratio of polyalkyleneimine and acid anhydride to obtain reaction product A is preferably 1 to 50 parts by mass of acid anhydride per 100 parts by mass of polyalkyleneimine. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less.

[0112] The mixing ratio of amine compound b and acid anhydride to obtain reaction product B is preferably 1 to 50 parts by mass of acid anhydride per 100 parts by mass of amine compound b. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

[0113] The photosensitive composition of the present invention may contain a specific amine compound that has not reacted with an acid anhydride. Furthermore, the photosensitive composition of the present invention may contain an acid anhydride that has not reacted with a specific amine compound. Furthermore, when the photosensitive composition contains a specific amine compound that has not reacted with an acid anhydride, the content of the acid anhydride in the photosensitive composition is preferably 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and particularly preferably 0.001% by mass or less.

[0114] The total content of the specific amine compound, acid anhydride, and specific reactant in the total solid content of the photosensitive composition of the present invention is preferably 1 to 20 parts by mass. The lower limit is preferably 1.5% by mass or more, more preferably 2% by mass or more, and even more preferably 2.5% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less.

[0115] The total content of the specific amine compound, acid anhydride, and specific reactant is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more. The upper limit is preferably 35 parts by mass or less, more preferably 20% by mass or less, and even more preferably 10 parts by mass or less.

[0116] <<Resin>> The photosensitive composition of the present invention preferably contains a resin. The resin is blended, for example, to disperse pigments or the like in the photosensitive composition or as a binder. Resins used primarily to disperse pigments are also called dispersants. However, these uses of resins are merely examples, and resins can also be used for purposes other than these.

[0117] 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.

[0118] Examples of the resin include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin. Further, the resins described in paragraphs 0041 to 0060 of JP-A No. 2017-206689, the resins described in paragraphs 0022 to 0071 of JP-A No. 2018-010856, the resins described in JP-A No. 2017-057265, the resins described in JP-A No. 2017-032685, the resins described in JP-A No. 2017-075248, the resins described in JP-A No. 2017-066240, the resins described in JP-A No. 2017-173787 It is also possible to use the resins described in JP 2016-222891 A, the blocked polyisocyanate resins described in JP 2020-122052 A, the resins described in JP 2020-111656 A, the resins described in JP 2020-139021 A, and the resins described in JP 2017-138503 A containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain.

[0119] The photosensitive 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.

[0120] 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.

[0121] 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").

[0122] [ka]

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] The photosensitive 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.

[0129] 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).

[0130] The photosensitive 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.

[0131] 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.

[0132] 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.

[0133] 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).

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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]

[0140] 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]

[0141] 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]

[0142] 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

[0143] In formula (Ac-2), L 11 is preferably —COO—.

[0144] 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]

[0145] 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 in which a hydrocarbon group is combined with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and a hydrocarbon group or a group in which a hydrocarbon group is combined with -O- is preferred.

[0146] 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 formed by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and a hydrocarbon group is preferred.

[0147] 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.

[0148] 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.

[0149] 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 %.

[0150] 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.

[0151] 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.

[0152] The photosensitive composition of the present invention preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). 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.

[0153] 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.

[0154] Furthermore, resins such as the above-mentioned block copolymers and acidic graft resins can also be used as dispersants.

[0155] Further, the dispersant includes the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, resins described in JP-A-2018-087939, polyethyleneimine having a polyester side chain described in WO 2016 / 104803, block copolymers described in WO 2019 / 125940, block polymers having an acrylamide structural unit described in JP-A-2020-066687, block polymers having an acrylamide structural unit described in JP-A-2020-066688, dispersants described in WO 2016 / 104803, and resins described in JP-A-2019-095548.

[0156] 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.

[0157] The content of the resin in the total solid content of the photosensitive composition is preferably 5 to 40% by mass, with the lower limit being preferably 10% by mass or more, and the upper limit being 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 photosensitive composition is preferably 5 to 40% by mass, with the lower limit being preferably 10% by mass or more, and the upper limit being 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.

[0158] <<Pigment derivatives>> The photosensitive composition of the present invention may contain a pigment derivative, such as a compound having a structure in which an acid group or a basic group is bonded to a dye skeleton.

[0159] 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.

[0160] 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 X6 The alkyl group and aryl group represented by may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.

[0161] 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.

[0162] 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.

[0163] Specific examples of the pigment derivatives include compounds described in the examples below, compounds described in JP-A-56-118462, compounds described in JP-A-63-264674, compounds described in JP-A-01-217077, compounds described in JP-A-03-009961, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds described in JP-A-03-045662, compounds described in JP-A-04-285669, and the like. compounds described in JP-A-06-145546, compounds described in JP-A-06-212088, compounds described in JP-A-06-240158, compounds described in JP-A-10-030063, compounds described in JP-A-10-195326, compounds described in paragraphs 0086 to 0098 of WO 2011 / 024896, compounds described in paragraphs 0063 to 0094 of WO 2012 / 102399, Compounds described in paragraph 0082 of JP-A No. 2017 / 038252, compounds described in paragraph 0171 of JP-A No. 2015-151530, compounds described in paragraphs 0162 to 0183 of JP-A No. 2011-252065, compounds described in JP-A No. 2003-081972, compounds described in Japanese Patent No. 5299151, compounds described in JP-A No. 2015-172732, compounds described in JP-A No. 2014-199308, compounds described in JP-A No. 2014 Examples of the compounds include compounds described in JP-A-2014-085562, compounds described in JP-A-2014-035351, compounds described in JP-A-2008-081565, compounds described in JP-A-2019-109512, compounds described in JP-A-2019-133154, diketopyrrolopyrrole compounds having a thiol linking group described in WO 2020 / 002106, and isoindoline compounds or salts thereof described in JP-A-2020-160279.

[0164] The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, relative to 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.

[0165] <<Compounds with cyclic ether groups>> The photosensitive 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.

[0166] The epoxy compound may be 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.

[0167] 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).

[0168] The content of the compound having a cyclic ether group in the total solid content of the photosensitive 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, the total amount thereof is preferably within the above range.

[0169] <<Curing accelerator>> The photosensitive 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 photosensitive composition is preferably from 0.3 to 8.9 mass %, more preferably from 0.8 to 6.4 mass %.

[0170] <<Surfactants>> The photosensitive 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. For details of the surfactant, reference can be made to the surfactants described in paragraphs 0238 to 0245 of WO 2015 / 166779, the contents of which are incorporated herein by reference.

[0171] 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 photosensitive composition.

[0172] 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, R-01, and R- 40, R-40-LM, R-41, R-41-LM, RS-43, R-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), 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 Examples include PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA), Ftergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, and FTX-218 (all manufactured by NEOS Corporation).

[0173] The fluorosurfactant may be an acrylic compound having a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved, causing the fluorine atom to volatilize. 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.

[0174] 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.

[0175] 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 %.

[0176] 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.

[0177] 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.

[0178] 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, a represents 1 or 2, and X a+ is a valent metal ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH4 + Represents.

[0179] 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.).

[0180] Examples of silicone surfactants include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419 OIL (manufactured by Dow-Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, and KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, and BYK-UV3510 (manufactured by BYK-Chemie).

[0181] Furthermore, the silicone surfactant may also be a compound having the following structure: [ka]

[0182] The content of the surfactant in the total solid content of the photosensitive 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 preferably falls within the above range.

[0183] <<Solvent>> The photosensitive composition of the present invention may contain a solvent. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the photosensitive composition. The solvent is preferably an organic solvent. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details, see paragraph 0223 of WO 2015 / 166779, the contents of which are incorporated herein by reference. Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether ... Examples of suitable methyl alcohols include ethylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol or 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, the amount can be reduced to 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).

[0184] In the present invention, it is preferable to use an organic solvent with a low metal content. The metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, organic solvents with mass ppt (parts per trillion) levels may be used, and such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).

[0185] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0186] The organic solvent may contain isomers (compounds with the same number of atoms but different structures), and may contain only one type of isomer or multiple types of isomers.

[0187] The organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

[0188] The content of the solvent in the photosensitive composition is preferably 10 to 95% by mass. The upper limit is preferably 92.5% by mass or less, and more preferably 90% by mass or less. From the viewpoint of coatability, the lower limit is preferably 20% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, still more preferably 75% by mass or more, and even more preferably 80% by mass or more.

[0189] Furthermore, from the viewpoint of environmental regulations, the photosensitive composition of the present invention preferably contains substantially no environmentally restricted substances. In the present invention, "substantially free of environmentally restricted substances" means that the content of environmentally restricted substances in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These 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 photosensitive composition and may be mixed into the photosensitive 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. When a radically polymerizable compound is contained, a polymerization inhibitor or the like may be added prior to 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 the raw materials, the stage of the product obtained by reacting the raw materials (e.g., a resin solution or a polyfunctional monomer solution after polymerization), or the stage of the photosensitive composition prepared by mixing these compounds.

[0190] <<Silane coupling agents>> The photosensitive 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.

[0191] The content of the silane coupling agent in the total solid content of the photosensitive 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.

[0192] <<Ultraviolet absorber>> The photosensitive composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include those described in paragraphs 0038 to 0052 of JP 2009-217221 A, paragraphs 0052 to 0072 of JP 2012-208374 A, paragraphs 0317 to 0334 of JP 2013-068814 A, and paragraphs 0061 to 0080 of JP 2016-162946 A, the contents of which are incorporated herein by reference. Commercially available UV absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), the Tinuvin series and Uvinul series manufactured by BASF, and the Sumisorb series manufactured by Sumika Chemtex Co., Ltd. Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil & Fats (The Chemical Daily, February 1, 2016). The UV absorber may also be the compound described in paragraphs 0049-0059 of Japanese Patent No. 6268967, the compound described in paragraphs 0059-0076 of International Publication No. 2016 / 181987, or the thioaryl-substituted benzotriazole UV absorber described in International Publication No. 2020 / 137819. The content of the UV absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. The ultraviolet absorbent may be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount thereof is preferably in the above range.

[0193] <<Antioxidants>> The photosensitive composition of the present invention may contain an antioxidant. Examples of antioxidants include phenolic compounds, phosphite ester compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the position adjacent to the phenolic hydroxy group (ortho position) are preferred. As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred.

[0194] The phenolic antioxidant is preferably a compound containing a structure represented by the following formula (A-1), and more preferably a compound containing two or more structures represented by formula (A-1) in one molecule. The upper limit of the number of structures represented by formula (A-1) in one molecule is preferably 8 or less, and more preferably 6 or less. [ka] R in the formula 1 ~R 4 each independently represents a hydrogen atom or a substituent, and R 1 ~R 4 At least one of represents a hydrocarbon group having one or more carbon atoms, and the wavy line represents a bond to another atom or atomic group in the antioxidant.

[0195] In formula (A-1), R 1 ~R 4 Examples of the substituent represented by include the groups described below in the description of the substituent T. 1 ~R 4At least one of the groups represents a hydrocarbon group having one or more carbon atoms. The hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, even more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be a linear, branched, or cyclic aliphatic hydrocarbon group, but is preferably a branched aliphatic hydrocarbon group. Specifically, the hydrocarbon group is preferably a linear, branched, or cyclic alkyl group, and more preferably a branched alkyl group. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include the groups described below in the section on the substituent T.

[0196] In formula (A-1), R 2 and R 3 At least one of R is preferably a hydrocarbon group having one or more carbon atoms, 2 and R 3 is more preferably a hydrocarbon group having one or more carbon atoms, and R 2 and R 3 is a hydrocarbon group having one or more carbon atoms, and R 2 and R 3 It is more preferable that at least one of R is a branched alkyl group. 2 and R 3 It is more preferred that one of R is a branched alkyl group and the other is a linear or branched alkyl group, 2 and R 3 It is particularly preferred that one of R is a branched alkyl group and the other is a linear alkyl group. 2 and R 3 Most preferably, one of them is a tert-butyl group and the other is a methyl group.

[0197] Examples of the substituent T include the groups shown below. (substituent T) Alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 30 carbon atoms), alkynyl groups (preferably alkynyl groups having 2 to 30 carbon atoms), aryl groups (preferably aryl groups having 6 to 30 carbon atoms), amino groups (preferably amino groups having 0 to 30 carbon atoms), alkoxy groups (preferably alkoxy groups having 1 to 30 carbon atoms), aryloxy groups (preferably aryloxy groups having 6 to 30 carbon atoms), heteroaryloxy groups, acyl groups (preferably acyl groups having 1 to 30 carbon atoms), group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms a phenylamino group), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably having 1 to 30 carbon atoms), an arylsulfonyl group (preferably having 6 to 30 carbon atoms), a heteroarylsulfonyl group (preferably having 1 to 30 carbon atoms), Examples of the substituent include alkylsulfinyl groups (preferably having 1 to 30 carbon atoms), alkylsulfinyl groups (preferably having 1 to 30 carbon atoms), arylsulfinyl groups (preferably having 6 to 30 carbon atoms), heteroarylsulfinyl groups (preferably having 1 to 30 carbon atoms), ureido groups (preferably having 1 to 30 carbon atoms), phosphoric acid amide groups (preferably having 1 to 30 carbon atoms), hydroxy groups, mercapto groups, halogen atoms, cyano groups, alkylsulfino groups, arylsulfino groups, hydrazino groups, imino groups, heteroaryl groups (preferably having 1 to 30 carbon atoms), and tetrahydrofuranyl groups. When these groups can be further substituted, they may further have a substituent. Examples of the further substituent include the groups described above for the substituent T.

[0198] The phenolic antioxidant is preferably a compound represented by formula (A-2). [ka] R in the formula 1 ~R 4 each independently represents a hydrogen atom or a substituent, and R 1 ~R 4 At least one of represents a hydrocarbon group having one or more carbon atoms; 1 represents an n-valent group, where n is an integer of 1 or more.

[0199] In formula (A-2), R 1 ~R 4 Examples of the substituent represented by include the groups described above for the substituent T. 1 ~R 4 At least one of R represents a hydrocarbon group having one or more carbon atoms. The preferred range of the hydrocarbon group is the same as the range described above. 2 and R 3 At least one of R is preferably a hydrocarbon group having one or more carbon atoms, 2 and R 3 is more preferably a hydrocarbon group having one or more carbon atoms, and R 2 and R 3 is a hydrocarbon group having one or more carbon atoms, and R 2 and R 3 It is more preferable that at least one of R is a branched alkyl group. 2 and R 3 It is more preferred that one of R is a branched alkyl group and the other is a linear or branched alkyl group, 2 and R 3 It is particularly preferred that one of R is a branched alkyl group and the other is a linear alkyl group. 2 and R 3 Most preferably, one of them is a tert-butyl group and the other is a methyl group.

[0200] L 1Examples of the n-valent group represented by include a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR-, -CO-, -COO-, -OCO-, -SO2-, and a group consisting of a combination thereof. R represents a hydrogen atom, an alkyl group, or an aryl group. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned substituent T. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or fused ring. The heterocyclic group may be a single ring or a condensed ring. Heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples of n-valent groups include the following structural units or groups formed by combining two or more of the following structural units (which may form a ring structure). R represents a hydrogen atom, an alkyl group, or an aryl group. In the following, * represents a linking hand.

[0201] [ka]

[0202] In formula (A-2), n represents an integer of 1 or more, preferably an integer of 1 to 8, more preferably an integer of 2 to 6, and even more preferably an integer of 2 to 4.

[0203] Specific examples of phenolic antioxidants include the following compounds. Commercially available phenolic antioxidants can also be used. Typical commercially available products include ADK STAB AO-20, 30, 40, 50, 60, 70, and 80 (all manufactured by ADEKA CORPORATION). Dihydric phenol compounds such as methylhydroquinone can also be used as the phenolic antioxidant. [ka] [ka]

[0204] The antioxidant is preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be used. The antioxidant can also be a compound described in Korean Patent Publication No. 10-2019-0059371.

[0205] Additionally, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants can also be used as antioxidants. Examples of hindered amine-based antioxidants include ADK STAB LA-52, LA-57, LA-63P, and LA-68 (all manufactured by ADEKA Corporation). Examples of phosphorus-based antioxidants include phosphite ester compounds. Commercially available products include ADK STAB PEP-8, PEP-36, HP-10, 2112, 1178, and TPP (all manufactured by ADEKA Corporation), and Irgafos 168 (manufactured by BASF). Examples of sulfur-based antioxidants include thioether compounds. Commercially available products include ADK STAB AO-412S, AO-503, and AO-26 (all manufactured by ADEKA Corporation), and Irganox PS 802 FL (manufactured by BASF).

[0206] The antioxidant is preferably a phenol-based antioxidant, since it is possible to form a film having excellent heat resistance and light resistance.

[0207] The content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20 mass %, more preferably 0.3 to 15 mass %. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount is preferably within the above range.

[0208] <<Polymerization inhibitor>> The photosensitive 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 photosensitive 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.

[0209] <<Other ingredients>> In the present invention, the photosensitive composition may optionally contain a sensitizer, a curing accelerator, a filler, a thermal curing accelerator, a plasticizer, and other auxiliary agents (e.g., conductive particles, 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 to 0104 and 0107 to 0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. Furthermore, the photosensitive 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 the compounds described in WO 2014 / 021023, WO 2017 / 030005, and JP 2017-008219 A. Commercially available latent antioxidants include ADEKA ARCLES GPA-5001 (manufactured by ADEKA Corporation).

[0210] The photosensitive 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.

[0211] The photosensitive 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 provide effects such as stabilization of pigment dispersibility (prevention of aggregation), improvement of spectral characteristics due to improved dispersibility, stabilization of curable components, prevention of fluctuations in conductivity due to elution of metal atoms and metal ions, and improvement of 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 photosensitive composition of the present invention preferably contains 100 ppm or less of free halogens not bonded or coordinated to pigments, etc., 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 photosensitive composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with ion-exchange resins.

[0212] The photosensitive composition of the present invention is also preferably substantially free of terephthalic acid esters. Here, "substantially free" means that the content of terephthalic acid esters in the total amount of the photosensitive composition is 1,000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0213] From the viewpoint of environmental regulations, the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts may be restricted. When the content of the above-mentioned compounds in the photosensitive composition of the present invention is reduced, the content of perfluoroalkyl sulfonic acids (particularly perfluoroalkyl sulfonic acids having a perfluoroalkyl group with 6 to 8 carbon atoms) and their salts, and perfluoroalkyl carboxylic acids (particularly perfluoroalkyl carboxylic acids having a perfluoroalkyl group with 6 to 8 carbon atoms) and their 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 solids content of the photosensitive composition. The photosensitive composition of the present invention may be substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. For example, by using a compound that can replace perfluoroalkyl sulfonic acid and its salt, and a compound that can replace perfluoroalkyl carboxylic acid and its salt, a photosensitive composition that is substantially free of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt 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 does not preclude the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt. The photosensitive composition of the present invention may contain perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt, within the maximum allowable range.

[0214] <<Containment Container>> The container for storing the photosensitive 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 photosensitive 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 photosensitive composition, and prevent deterioration of the components.

[0215] <Method for preparing photosensitive composition> The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photosensitive composition, all components may be simultaneously dissolved and / or dispersed in a solvent to prepare the photosensitive composition, or, if necessary, each component may be prepared as two or more appropriate solutions or dispersions, which are mixed at the time of use (coating) to prepare the photosensitive composition.

[0216] A first aspect of the method for producing a photosensitive composition of the present invention includes a step (first step) of dispersing a pigment and a polyalkyleneimine in a solvent to prepare a dispersion; a step (second step) of mixing the dispersion, an acid anhydride, a polymerizable compound, and a photopolymerization initiator; It is preferred that it contains

[0217] A second aspect of the method for producing a photosensitive composition of the present invention includes a step (first step) of dispersing a pigment and a compound (amine compound b) having three or more amino groups in one molecule and an amine value of 2.7 mmol / g or more in a solvent to prepare a dispersion; a step (second step) of mixing the dispersion, an acid anhydride, a polymerizable compound, and a photopolymerization initiator; It is preferred that it contains

[0218] According to the first aspect of the method for producing a photosensitive composition, in the second step, the polyalkyleneimine and the acid anhydride contained in the dispersion react with each other to produce a reaction product of the polyalkyleneimine and the acid anhydride.

[0219] According to the second aspect of the method for producing a photosensitive composition, in the second step, the amine compound b contained in the dispersion reacts with the acid anhydride to produce a reaction product of the amine compound b and the acid anhydride. Examples of the amine compound b include the materials described above.

[0220] In the first embodiment of the method for producing a photosensitive composition, the ratio of polyalkyleneimine to pigment in the first step is preferably 1 to 30 parts by mass of polyalkyleneimine per 100 parts by mass of pigment. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less. The lower limit is preferably 2 parts by mass or more, more preferably 3 parts by mass or more. The first step is preferably carried out by further adding a resin (dispersant). That is, the dispersion is preferably prepared by dispersing the pigment, polyalkyleneimine, and resin in a solvent. The resin (dispersant) is preferably a resin having an acid group, more preferably a graft resin having an acid group. The ratio of resin to pigment is preferably 10 to 100 parts by mass of resin per 100 parts by mass of pigment. The upper limit is preferably 70 parts by mass or less, more preferably 50 parts by mass or less. The lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more. The first step may be carried out by further adding a pigment derivative.

[0221] In the first embodiment of the method for producing a photosensitive composition, the amount of acid anhydride added in the second step is preferably 1 to 50 parts by mass per 100 parts by mass of polyalkyleneimine. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more.

[0222] In the second embodiment of the method for producing a photosensitive composition, the ratio of amine compound b to pigment in the first step is preferably 1 to 30 parts by mass of amine compound b per 100 parts by mass of pigment. The upper limit is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. The lower limit is preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more. In the second embodiment of the method for producing a photosensitive composition, the first step is also preferably carried out by further adding a resin (dispersant). That is, the dispersion is preferably prepared by dispersing the pigment, amine compound b, and resin in a solvent. The resin (dispersant) is preferably a resin having an acid group, more preferably a graft resin having an acid group. The ratio of resin to pigment is preferably 10 to 100 parts by mass of resin per 100 parts by mass of pigment. The upper limit is preferably 70 parts by mass or less, more preferably 50 parts by mass or less. The lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more. The first step may be carried out by further adding a pigment derivative.

[0223] In the second embodiment of the method for producing a photosensitive composition, the amount of acid anhydride added in the second step is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of amine compound b. The upper limit is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. The lower limit is preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more.

[0224] In the method for producing a photosensitive composition according to the first embodiment and the method for producing a photosensitive composition according to the second embodiment, the above-mentioned materials such as a resin, a surfactant, a silane coupling agent, a solvent, a polymerization inhibitor, and an ultraviolet absorber may be further added in the second step, if necessary.

[0225] When preparing a photosensitive composition, it is preferable to filter the photosensitive composition for the purpose of removing foreign matter and reducing defects. Any filter that has been conventionally used for filtration or the like can be used 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] <Membrane> The film of the present invention is a film obtained from the photosensitive composition of the present invention described above. The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0230] The film of the present invention can be used in color filters, near-infrared transmission filters, near-infrared cut filters, black matrices, light-shielding films, etc. The film of the present invention can be preferably used as a color pixel of a color filter. Examples of the color pixel include a red pixel, a green pixel, a blue pixel, a magenta pixel, a cyan pixel, and a yellow pixel, and the green pixel or cyan pixel is preferred, and the green pixel is more preferred.

[0231] When the film of the present invention is used as a green pixel of a color filter, the wavelength at which the film of the present invention has a light transmittance of 50% is preferably in the wavelength range of 470 to 520 nm, more preferably in the wavelength range of 475 to 520 nm, and even more preferably in the wavelength range of 480 to 520 nm. In particular, the wavelengths at which the light transmittance is 50% are preferably in both the wavelength range of 470 to 520 nm and the wavelength range of 575 to 625 nm. In this embodiment, the wavelength on the short wavelength side at which the light transmittance is 50% is preferably in the wavelength range of 475 to 520 nm, and more preferably in the wavelength range of 480 to 520 nm. Furthermore, the wavelength on the long wavelength side at which the light transmittance is 50% is preferably in the wavelength range of 580 to 620 nm, and more preferably in the wavelength range of 585 to 615 nm. A film having such spectral characteristics is preferably used as a green pixel.

[0232] When the film of the present invention is used as a near-infrared cut filter, the maximum absorption wavelength of the film of the present invention is preferably in the 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 1100 nm. The transmittance of the film 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 of the film 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 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.

[0233] When the film of the present invention is used as a near-infrared transmission filter, the film of the present invention preferably has any one of the following spectral characteristics (i1) to (i5). (i1): A film having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 640 nm and transmit light with a wavelength of over 750 nm. (i2): A film having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 750 nm and transmit light with a wavelength of over 850 nm. (i3): A film having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 830 nm and transmit light with a wavelength of more than 950 nm. (i4): A film having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength of more than 1050 nm. (i5): A film having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength of more than 1150 nm.

[0234] <Membrane manufacturing method> Next, a method for producing the film of the present invention will be described. The film of the present invention can be produced via a step of applying the photosensitive composition of the present invention. The film production method preferably further includes a step of forming a pattern (pixels). The method for forming the pattern (pixels) is preferably photolithography.

[0235] The pattern formation by the photolithography method preferably includes the steps of forming a photosensitive composition layer on a support using the photosensitive composition of the present invention, exposing the photosensitive composition layer to light in a pattern, and developing and removing the unexposed areas of the photosensitive composition layer to form a pattern (pixels). If necessary, a step of baking the photosensitive composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

[0236] In the step of forming a photosensitive composition layer, a photosensitive composition layer is formed on a support using the photosensitive 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 diffusion of substances, 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.

[0237] The photosensitive 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 coating 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 February 2005 by Sumibe Techno Research (particularly pages 115 to 133), and the methods described in JP 2003-262716 A, JP 2003-185831 A, JP 2003-261827 A, JP 2012-126830 A, and JP 2006-169325 A. Furthermore, for methods of applying photosensitive compositions, reference can be made to the descriptions in WO 2017 / 030174 and WO 2017 / 018419, the contents of which are incorporated herein by reference.

[0238] The photosensitive 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.

[0239] Next, the photosensitive composition layer is exposed to light in a pattern (exposure step). For example, the photosensitive composition layer can be exposed to light in a pattern by using a stepper exposure machine or a scanner exposure machine through a mask having a predetermined mask pattern. This allows the exposed portion to be cured.

[0240] 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.

[0241] 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).

[0242] 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 2The 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.

[0243] Next, the unexposed portions of the photosensitive composition layer are developed and removed to form a pattern (pixels). The unexposed portions of the photosensitive composition layer can be developed and removed using a developer. As a result, the unexposed portions of the photosensitive 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.

[0244] 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 may be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) the developed solution with pure water. Rinsing is preferably performed by supplying a rinse solution to the developed photosensitive composition layer while rotating the support on which the developed photosensitive composition layer is formed. It is also preferable to perform this by moving the nozzle that dispenses 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. The same effect can also be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center to the periphery of the support.

[0245] 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.

[0246] <Optical filters> The optical filter of the present invention has the above-described film of the present invention. Types of optical filters include color filters, near-infrared cut filters, and near-infrared transmission filters, and a color filter is 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 its color pixel, and even more preferably has the film of the present invention as its green pixel.

[0247] 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 20 μm or less, more preferably 10 μm or less, and even more preferably 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.

[0248] The width of the pixels included in the optical filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and even more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.8 μm or less. The Young's modulus of the pixels is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

[0249] It is preferable that each pixel included in the optical filter has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. There is no specified lower limit, but it is preferably 0.1 nm or more, for example. The surface roughness of the pixel can be measured using, for example, an AFM (atomic force microscope) Dimension3100 manufactured by Veeco. Furthermore, the contact angle of water on the pixel can be set to an appropriate preferred value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT·A (manufactured by Kyowa Interface Science Co., Ltd.). It is also preferable that the volume resistance of the pixel is high. Specifically, the volume resistance of the pixel is 10 9 It is preferable that the resistance is Ω·cm or more, and 10 11 It is more preferable that the resistivity is Ω·cm or more. There is no upper limit, but for example, 10 14 It is preferably Ω·cm or less. The volume resistance of the pixel can be measured using an Ultra High Resistance Meter 5410 (manufactured by Advantest Corporation).

[0250] In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing a protective layer, various functions can be imparted, such as oxygen blocking, low reflectivity, hydrophilicity / hydrophobicity, and blocking of light of specific wavelengths (ultraviolet rays, near-infrared rays, etc.). The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Methods for forming the protective layer include a method of applying a composition for forming the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. Components constituting the protective layer 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, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyol resins, polyvinylidene chloride resins, melamine resins, urethane resins, aramid resins, polyamide resins, alkyd resins, epoxy resins, modified silicone resins, fluororesins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al2O3, Mo, SiO2, and Si2N4, and may contain two or more of these components. For example, in the case of a protective layer intended to block oxygen, the protective layer preferably contains a polyol resin, SiO2, and Si2N4. Furthermore, in the case of a protective layer intended to reduce reflectivity, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

[0251] The protective layer may contain additives such as organic or inorganic fine particles, absorbers of specific wavelengths of light (e.g., ultraviolet light, near-infrared light, etc.), refractive index modifiers, antioxidants, adhesives, and surfactants, as needed. Examples of organic or inorganic fine particles include polymeric fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known absorbers of specific wavelengths of light can be used. The content of these additives can be adjusted as needed, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, of the total mass of the protective layer.

[0252] Furthermore, as the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A No. 2017-151176 can also be used.

[0253] The optical filter may have a structure in which each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.

[0254] <Solid-state imaging element> The solid-state imaging device of the present invention has the above-described film of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations.

[0255] 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. The device protection film may further include a light-collecting means (e.g., a microlens, etc.; the same applies hereinafter) below the color filter (closer to the substrate), or a light-collecting means 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.

[0256] <Image display device> The image display device of the present invention has the above-described film of the present invention. 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]

[0257] 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.

[0258] <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

[0259] <Method for measuring amine value> The amine value was calculated by the following method. The measurement sample was dissolved in acetic acid, and the resulting solution was neutralized with a 0.1 mol / L perchloric acid / acetic acid solution using a potentiometric titrator (product name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). The inflection point of the titration pH curve was used as the titration endpoint, and the amine value was calculated using the following formula. B=Vs×0.1×f / w B: Amine value (mmol / g) Vs: Amount (mL) of 0.1 mol / L perchloric acid / acetic acid solution required for titration f: Potency of 0.1 mol / L perchloric acid / acetic acid solution w: Weight of the measurement sample (g) (solid content equivalent)

[0260] <Production of dispersion liquid> The materials listed in the table below were mixed in the amounts shown in the table below, and the mixture was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm in diameter) to prepare a dispersion. Then, a high-pressure disperser equipped with a pressure reduction mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), was used to mix the materials in the amounts shown in the table below at a pressure of 2000 kg / cm. 2 and a flow rate of 500 g / min. This dispersion process was repeated a total of 10 times to obtain a dispersion. The numerical values ​​in the blending amount column in the table below are in parts by mass.

[0261] [Table 1]

[0262] [Table 2]

[0263] [Table 3]

[0264] Details of the materials indicated by the abbreviations in the table above are as follows:

[0265] (pigment) PG7: CI Pigment Green 7 (halogenated copper phthalocyanine pigment, green pigment) PG36: CI Pigment Green 36 (halogenated copper phthalocyanine pigment, green pigment) PG58: CI Pigment Green 58 (halogenated zinc phthalocyanine pigment, green pigment) PG59: CI Pigment Green 59 (halogenated zinc phthalocyanine pigment, green pigment) PG63: CI Pigment Green 63 (halogenated aluminum phthalocyanine pigment, green pigment) PY129: CI Pigment Yellow 129 (azomethine pigment, yellow pigment) PY138: CI Pigment Yellow 138 (quinophthalone pigment, yellow pigment) PY139: CI Pigment Yellow 139 (isoindoline pigment, yellow pigment) PY150: CI Pigment Yellow 150 (azo pigment, yellow pigment) PY185: CI Pigment Yellow 185 (isoindoline pigment, yellow pigment) PY215: CI Pigment Yellow 215 (pteridine pigment, yellow pigment) PY231: CI Pigment Yellow 231 (yellow pigment) PY233: CI Pigment Yellow 233 (yellow pigment) PR254: CI Pigment Red 254 (red pigment) PB15:6: CI Pigment Blue 15:6 (blue pigment) PV23: CI Pigment Violet 23 (purple pigment)

[0266] (Dispersion aid) Syn-1: Compound having the following structure (hindered amine compound, Adekastab LA-52, manufactured by ADEKA Corporation) Syn-2: Compound having the following structure (hindered amine compound, Adekastab LA-57, manufactured by ADEKA Corporation) Syn-3: Compound having the following structure (hindered amine compound, Adekastab LA-63P, manufactured by ADEKA Corporation) Syn-4: Compound having the following structure (hindered amine compound, Adekastab LA-68, manufactured by ADEKA Corporation) Syn-5: Polyethyleneimine (Epomin SP-003, manufactured by Nippon Shokubai Co., Ltd.) Syn-6: Polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd.) Syn-7: Polyethyleneimine (Epomin SP-012, Nippon Shokubai Co., Ltd.) Syn-8: Polyethyleneimine (Epomin SP-018, Nippon Shokubai Co., Ltd.) Syn-9: Compound with the following structure Syn-10: Compound with the following structure Syn-11: Compound with the following structure Syn-12: Compound with the following structure Syn-13: Polyethyleneimine (Epomin SP-200, manufactured by Nippon Shokubai Co., Ltd.) Syn-14: Polyethyleneimine (Epomin P-1000, manufactured by Nippon Shokubai Co., Ltd.) [ka] [ka]

[0267] The physical properties of Syn-1 to Syn-14 are listed in the table below. Note that the physical properties of Syn-5, Syn-6, Syn-7, Syn-8, Syn-13, and Syn-14 are catalog values. Of these, the molecular weight values ​​of Syn-5, Syn-6, Syn-7, Syn-8, and Syn-13 are number-average molecular weight values ​​measured by the ebullient method (catalog value). The molecular weight value of Syn-14 is number-average molecular weight value measured by the viscosity method (catalog value). The molecular weight values ​​of Syn-3, Syn-4, and Syn-12 are number-average molecular weight values ​​measured by the GPC method. The molecular weight values ​​of Syn-1, Syn-2, Syn-9, Syn-10, and Syn-11 are calculated values ​​from the structural formula. [Table 4]

[0268] (pigment derivatives) YSyn-1: a compound with the following structure [ka] YSyn-2: Compound with the following structure [ka]

[0269] (dispersant) B-1: 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. Resin with acid groups, weight average molecular weight of 18,000, acid value of 82.1 mgKOH / g) [ka]

[0270] B-2: Resin shown in the table below (resin having acid groups, weight average molecular weight 8000, acid value 37 mgKOH / g, C=C value 0.22 mmol / g) [Table 5] The constituent units listed in the above table are as follows: [ka] [ka] [ka]

[0271] B-3: Resin with the following structure ((The numbers attached to the chain are the molar ratios, and the numbers attached to the side chains are the number of repeating units. Resin with acid groups, weight average molecular weight of 23,000, acid value of 67 mgKOH / g) [ka]

[0272] (solvent) S-1: Propylene glycol monomethyl ether acetate S-2: Diacetone alcohol S-3: Anisole S-4: Propylene glycol monomethyl ether S-5: Cyclohexanone S-6: Cyclopentanone S-7: 4-Methoxy-4-methyl-2-pentanone

[0273] <Production of Photosensitive Composition> Each photosensitive composition was produced by mixing the materials shown in the table below in the amounts shown in the table and filtering through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) The units of the values ​​shown in the column for the amount of blending in the table below are parts by mass. In the photosensitive compositions of Examples 1 to 85, at least a portion of the dispersing aids Syn-1 to Syn-14 (polyalkyleneimines or compounds having three or more amino groups per molecule and an amine value of 2.7 mmol / g or more) contained in Green Dispersions 1 to 30, Yellow Dispersion 9, Red Dispersion 1, or Blue Dispersions 1 to 7 reacts with acid anhydrides A-1 to A-7 during production, and the photosensitive compositions of Examples 1 to 85 contain these reaction products. The reaction product has at least one of the structures represented by Formulas (1) to (3) described in Paragraph 0108. The weight-average molecular weight of the reaction product in the photosensitive compositions of Examples 57 and 58 exceeds 5,000, while in the other examples, the weight-average molecular weight of the reaction product is 5,000 or less.

[0274] [Table 6] [Table 7]

[0275] [Table 8] [Table 9]

[0276] [Table 10] [Table 11]

[0277] Of the materials indicated by abbreviations in the table showing the formulation of the photosensitive composition, details other than the dispersion are as follows: The dispersion used was the dispersion described above.

[0278] (polymerizable monomer) M-1: Compound of the following structure [ka] M-2: A mixture of compounds having the following structure (a mixture of the compound on the left (a hexafunctional (meth)acrylate compound) and the compound on the right (a pentafunctional (meth)acrylate compound) in a molar ratio of 7:3) [ka] M-3: Compound of the following structure [ka] M-4: Compound of the following structure [ka]

[0279] (binder) B-2, B-3: Resins identical to the dispersants B-2 and B-3 described above C-1: Resin with the following structure (the number attached to the main chain is the molar ratio. Weight average molecular weight: 11,000) [ka] C-2: Resin with the following structure (the number attached to the main chain is the molar ratio. Weight average molecular weight: 14,000) [ka] C-3: Resin with the following structure (the number attached to the main chain is the molar ratio. Weight average molecular weight: 21,000) [ka]

[0280] C-4: Resin C-4 synthesized by the following method A flask equipped with a condenser and a stirrer was charged with 100 parts by weight of propylene glycol monomethyl ether acetate and purged with nitrogen. The mixture was heated to 80°C, and a mixed solution of 100 parts by weight of propylene glycol monomethyl ether acetate, 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. The temperature was maintained and polymerization was allowed to proceed for 2 hours. The temperature of the reaction solution was then raised to 100°C, and polymerization was allowed to continue for another 1 hour, yielding Resin C-4. The resulting Resin C-4 had a weight-average molecular weight of 12,200 and an acid value of 137 mgKOH / g.

[0281] C-5: Resin C-5 synthesized by the following method A flask equipped with a condenser and a stirrer was charged with 100 parts by weight of propylene glycol monomethyl ether acetate and purged with nitrogen. The mixture was heated to 80°C, and a mixed solution of 100 parts by weight of propylene glycol monomethyl ether acetate, 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 at that temperature. The temperature was maintained and polymerization was allowed to proceed for 2 hours. The temperature of the reaction solution was then raised to 100°C, and polymerization was allowed to continue for another 1 hour, yielding Resin C-5. The resulting Resin C-5 had a weight-average molecular weight of 18,500 and an acid value of 59 mgKOH / g.

[0282] (Photopolymerization initiator) I-1: Irgacure OXE02 (BASF, oxime compound) I-2 to I-5: Compounds of the following structure [ka]

[0283] (adhesion agent) AD-1: Compound with the following structure (silane coupling agent) [ka]

[0284] (surfactant) W-1: KF-6001 (silicone surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0285] (polymerization inhibitor) Q-1: p-Methoxyphenol

[0286] (acid anhydride) A-1: Succinic anhydride A-2: Itaconic anhydride A-3: Tetrahydrophthalic anhydride A-4: Rikacid MH (manufactured by New Japan Chemical Co., Ltd., compound having the following structure) [ka] A-5: Rikacid HNA-100 (manufactured by New Japan Chemical Co., Ltd., a mixture of compounds having the following structure) [ka] A-6: Rikacid OSA (manufactured by New Japan Chemical Co., Ltd., compound having the following structure) [ka] A-7: Rikacid DDSA (manufactured by New Japan Chemical Co., Ltd., compound having the following structure) [ka]

[0287] (additives) ADI-1: Adekastab AO-60 (phenolic antioxidant, manufactured by ADEKA Corporation) ADI-2: Adekastab AO-80 (phenolic antioxidant, manufactured by ADEKA Corporation) ADI-3: Methylhydroquinone ADI-4: Irgafos 168 (tris(2,4-t-butylphenyl) phosphite, a phosphoric acid antioxidant, manufactured by BASF) ) ADI-5: Irganox PS 802 FL (thioether compound, sulfur-based antioxidant, manufactured by BASF)

[0288] (solvent) S-1: Propylene glycol monomethyl ether acetate

[0289] <Evaluation of residue and peeling> Each photosensitive composition was stored in a thermostatic chamber at 45° C. for 3 days. An underlayer composition (CT-4000L, manufactured by Fujifilm Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the thickness after post-baking would be 0.1 μm, and the wafer was heated on a hot plate at 220°C for 300 seconds to form an underlayer, thereby obtaining a silicon wafer (support) with an underlayer. Next, the photosensitive composition after storage was applied to the silicon wafer with the underlayer by spin coating so that the film thickness after post-baking was 0.5 μm. Then, the wafer was heated at 100° C. for 2 minutes using a hot plate. Next, an i-line stepper exposure system FPA-3000i5+ (Canon Inc.) was used to expose the wafer to 1000 mJ / cm of light with a wavelength of 365 nm. 2 The silicon wafer on which the exposed coating film was formed was exposed through a mask with a 1.0 μm square dot pattern at an exposure dose of 1.0 μm. Next, the silicon wafer on which the exposed coating film was formed was subjected to puddle development at 23°C for 60 seconds using a 60% diluted solution of CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.). Further, a heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200°C to form a pattern (pixels). The silicon wafer on which the pixels were formed was observed under a scanning electron microscope (SEM) (magnification 10,000 times) and evaluated for residue and peeling according to the following evaluation criteria. The evaluation results are shown in the table below.

[0290] - Evaluation criteria for development residue - 5: No residue was found between pixels 4: A small amount of residue was observed only near the wall of the pixel. 3: Residue was found only near the wall of the pixel 2: Residue was found between pixels and on the wall surface. 1: The gaps between pixels were filled with residue

[0291] -Evaluation criteria for peeling- 5: The number of peeled pixels was less than 0.01% of the total number of pixels created. 4: The number of peeled pixels was between 0.01% and 0.1% of the total number of created pixels. 3: The number of peeled pixels was between 0.1% and 1% of the total number of created pixels. 2: The number of peeled pixels was between 1% and 10% of the total number of created pixels. 1: The number of peeled pixels was 10% or more of the total number of created pixels.

[0292] [Table 12]

[0293] As shown in the table above, the photosensitive compositions of the Examples were able to form films with reduced residue and peeling, even when aged photosensitive compositions were used. The films obtained from the photosensitive compositions of the Examples are suitable for use in optical filters, solid-state imaging devices, and image display devices.

[0294] Similar results are obtained when the surfactant is omitted from Example 1. Similar results are obtained when the polymerization inhibitor is omitted from Example 1.

Claims

1. A pigment, a polymerizable compound; a photopolymerization initiator; a reaction product of polyethyleneimine having an amine value of 15 mmol / g or more and a molecular weight of 2000 or less with a carboxylic acid anhydride having 5 to 15 carbon atoms; Including, The weight average molecular weight of the reaction product is 5000 or less. Photosensitive composition.

2. 2. The photosensitive composition according to claim 1, wherein the carboxylic acid anhydride has a molecular weight of 300 or less.

3. The photosensitive composition according to claim 1 or 2, wherein the pigment comprises a phthalocyanine pigment.

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

5. An optical filter comprising the film according to claim 4.

6. A solid-state imaging device comprising the film according to claim 4.

7. An image display device comprising the film according to claim 4.

Images