Photosensitive resin composition, cured film, color filter, solid-state imaging element, and image display device

Abstract

The present invention provides a photosensitive resin composition comprising: a colorant, a resin, a polymerizable compound, a photopolymerization initiator, a UV absorber, and a solvent. The photosensitive resin composition comprises: a colorant containing at least one phthalocyanine pigment selected from Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4, and the colorant contains at least 50% by mass of the phthalocyanine pigment; and the UV absorber contains 0.1 to 10% by mass of the total solids content of the photosensitive resin composition. The present invention also provides a cured film, a color filter, a solid-state imaging element, and an image display device formed using the photosensitive resin composition.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition containing at least one phthalocyanine pigment selected from Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4. The present invention also relates to a cured film, color filter, solid-state imaging element, and image display device formed using the photosensitive resin composition. Background Art

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

[0003] Known color filters include additive color filters with red, green, and blue pixels, and subtractive color filters with cyan, magenta, and yellow pixels. Pixels of each color in the color filter are manufactured using a photosensitive resin composition containing a colorant.

[0004] Paragraphs 0123 to 0130 of Patent Document 1 describe a cyan photosensitive coloring composition comprising a pigment dispersion containing a color index pigment blue 15:3, an acrylic resin solution, a photopolymerizable monomer, a photopolymerization initiator, a leveling agent solution, and a solvent.

[0005] Patent Document 2 describes a photosensitive colored resin composition for color filters. The composition contains a color index pigment Green 7, a blue colorant, a yellow colorant, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. Paragraph 0113 of Patent Document 2 describes the use of pigment blue 15:3, pigment blue 15:4, and pigment blue 15:6 as blue colorants.

[0006] Previous technical literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2017-142372

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2018-045189 Summary of the Invention

[0010] Technical issues to be solved by the invention

[0011] Typically, a color filter has pixels of various colors. A color filter having pixels of these various colors is manufactured by sequentially forming pixels of each color. For example, in the case of forming a color filter having pixels of various colors by a photolithography method using a photosensitive resin composition, the pixels of each color are subjected to the following operation to manufacture the color filter: a photosensitive resin composition layer is formed on a support using a photosensitive resin composition, followed by pattern-like exposure of the photosensitive resin composition layer, followed by development to remove the unexposed portion of the photosensitive resin composition layer to form a pattern (pixel). Therefore, the photosensitive resin composition of another color formed in the next process can also be applied to the pixel (hereinafter also referred to as the first pixel) formed in the previous process. The photosensitive resin composition of another color applied to the pixel (first pixel) formed in the previous process is removed by the development process during pattern formation, but if the curability of the first pixel is insufficient, the colorant contained in the photosensitive resin composition of another color applied to the first pixel may move to the first pixel side and produce a mixed color. Therefore, pixels formed using photosensitive resin compositions are expected to minimize color mixing with pixels of other hues. Furthermore, pixels used in color filters are also required to have excellent spectral characteristics and light resistance. Furthermore, these characteristics have led to a demand for higher levels of juxtaposition in recent years.

[0012] However, cyan pixel-forming photosensitive resin compositions have not been thoroughly studied to date. Conventional cyan pixel-forming photosensitive resin compositions have been difficult to form cured films that achieve the high levels of spectral properties, light resistance, and suppression of color mixing with pixels of other hues required in recent years, suitable for cyan. Furthermore, the present inventors' research has revealed that the compositions described in Patent Documents 1 and 2 have room for further improvement in these properties.

[0013] Therefore, an object of the present invention is to provide a photosensitive resin composition, a cured film, a color filter, a solid-state imaging element, and an image display device that can form a cured film having spectral characteristics suitable for developing cyan, excellent light resistance, and capable of suppressing the occurrence of color mixing with pixels of other hues.

[0014] Means for solving technical problems

[0015] The present inventors have conducted in-depth research and found that by increasing the content of at least one phthalocyanine pigment selected from Color Index (CI) Pigment Blue 15:3 and CI Pigment Blue 15:4 in the colorant contained in the photosensitive resin composition, it is possible to improve the cured film having spectral characteristics suitable for cyan. In addition, the present inventors conducted further research on the cured film obtained using the photosensitive resin composition and found that there is still room for improvement in light resistance. The present inventors conducted further research and found that by using a colorant containing 50% by mass or more of at least one phthalocyanine pigment selected from CI Pigment Blue 15:3 and CI Pigment Blue 15:4, and containing 0.1 to 10% by mass of an ultraviolet absorber in the total solid content of the photosensitive resin composition, it is possible to form a cured film having spectral characteristics suitable for cyan, excellent light resistance, and the ability to suppress the generation of color mixing with pixels of other hues, thereby completing the present invention. The present invention provides the following.

[0016] <1> A photosensitive resin composition comprising: a colorant, a resin, a polymerizable compound, a photopolymerization initiator, an ultraviolet absorber, and a solvent, wherein:

[0017] The colorant contains at least one phthalocyanine pigment selected from the group consisting of Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4, and the colorant contains 50% by mass or more of the phthalocyanine pigment.

[0018] The ultraviolet absorber is contained in an amount of 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition.

[0019] <2> The photosensitive resin composition according to <1>, wherein the average secondary particle size of the phthalocyanine pigment is 50 to 100 nm.

[0020] <3> The photosensitive resin composition according to <1> or <2>, further comprising 10% by mass or more of a colorant based on the total solid content of the photosensitive resin composition.

[0021] <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the resin contains a resin having an amine value of 25 to 60 mgKOH / g.

[0022] <5> The photosensitive resin composition according to <4>, wherein the resin having an amine value of 25 to 60 mgKOH / g is a (meth)acrylic resin.

[0023] <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the resin contains an alkali-soluble resin.

[0024] <7> The photosensitive resin composition according to any one of <1> to <6>, further comprising 1 to 200 parts by mass of an ultraviolet absorber based on 100 parts by mass of the photopolymerization initiator.

[0025] <8> The photosensitive resin composition according to any one of <1> to <7>, further comprising 0.1 to 100 parts by mass of an ultraviolet absorber based on 100 parts by mass of the polymerizable compound.

[0026] <9> The photosensitive resin composition according to any one of <1> to <8> Zhennanguan, which is used for forming pixels of a color filter.

[0027] <10> The photosensitive resin composition according to <9>, which is used for forming a cyan pixel.

[0028] <11> The photosensitive resin composition according to any one of <1> to <10>, which is used for a solid-state imaging element.

[0029] <12> A cured film obtained from the photosensitive resin composition according to any one of <1> to <11>.

[0030] <13> A color filter comprising the cured film according to <12>.

[0031] <14> A solid-state imaging element comprising the cured film according to <12>.

[0032] <15> The solid-state imaging element according to <14>, wherein the cured film is a cyan pixel, and the solid-state imaging element further includes a yellow pixel and a magenta pixel.

[0033] <16> An image display device comprising the cured film according to <12>.

[0034] Effects of the Invention

[0035] According to the present invention, there can be provided a photosensitive resin composition, a cured film, a color filter, a solid-state imaging element, and an image display device capable of forming a cured film having spectral characteristics suitable for developing cyan, excellent light resistance, and capable of suppressing color mixing with pixels of other hues. DETAILED DESCRIPTION

[0036] Hereinafter, the contents of the present invention will be described in detail.

[0037] In this specification, “to” means that the numerical values described before and after “to” are included as the lower limit and the upper limit.

[0038] Regarding the notation of groups (atomic groups) in this specification, noting whether or not substituted includes both groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0039] As used herein, "exposure" encompasses, unless otherwise specified, exposure using light and drawing using particle beams such as electron beams and ion beams. Examples of light typically used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams.

[0040] In this specification, “(meth)acrylate” means both or either acrylate and methyl acrylate, “(meth)acrylic acid” means both or either acrylic acid and methacrylic acid, and “(meth)acryloyl” means both or either acryloyl and methacryloyl.

[0041] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0042] In this specification, the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by GPC (gel permeation chromatography).

[0043] In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition.

[0044] In this specification, the pigment refers to a compound that is not easily soluble in a solvent.

[0045] In this specification, the term "step" refers not only to an independent step but also to a step that achieves the intended effect of the step even if it cannot be clearly distinguished from other steps.

[0046] <Photosensitive resin composition>

[0047] The photosensitive resin composition of the present invention contains:

[0048] A colorant, a resin, a polymerizable compound, a photopolymerization initiator, an ultraviolet absorber, and a solvent, wherein the photosensitive resin composition is characterized in that:

[0049] The colorant contains at least one phthalocyanine pigment selected from the group consisting of Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4, and the colorant contains 50% by mass or more of the phthalocyanine pigment.

[0050] The ultraviolet absorber is contained in an amount of 0.1 to 10% by mass in the total solid content of the photosensitive resin composition.

[0051] The photosensitive resin composition of the present invention can form a cured film having spectral properties suitable for developing cyan, excellent light resistance, and suppressed color mixing with pixels of other hues. In particular, it can form a cured film having high average transmittance for light in the wavelength range of 400-530 nm and low average transmittance for light in the wavelength range of 610-700 nm. By using a colorant containing 50% or more by mass of at least one phthalocyanine pigment selected from CI Pigment Blue 15:3 and CI Pigment Blue 15:4, a cured film having spectral properties suitable for developing cyan can be formed. Furthermore, by using a colorant containing 50% or more of the aforementioned phthalocyanine pigment and containing 0.1-10% by mass of the aforementioned ultraviolet absorber in the total solids content of the photosensitive resin composition, a cured film having excellent light resistance and suppressed color mixing with pixels of other hues can be formed.

[0052] When a cured film having a thickness of 0.4 to 1.0 μm is formed, the photosensitive resin composition of the present invention preferably has an average transmittance of light with a wavelength of 400 to 530 nm in the thickness direction of the film of 70% or more, more preferably 80% or more, and even more preferably 85% or more. Furthermore, the minimum transmittance of light with a wavelength of 400 to 530 nm in the thickness direction of the film is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more. Furthermore, the average transmittance of light with a wavelength of 610 to 700 nm in the thickness direction of the film is preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less. Furthermore, the maximum transmittance of light with a wavelength of 610 to 700 nm in the thickness direction of the film is preferably 40% or less, more preferably 30% or less, and even more preferably 25% or less.

[0053] When a cured film having a thickness of 0.4 to 1.0 μm is formed, the photosensitive resin composition of the present invention preferably has a transmittance peak in the wavelength range of 400 to 530 nm in the transmission spectrum of light having a wavelength range of 400 to 700 nm in the thickness direction of the film. Furthermore, it is preferred that a wavelength at which the transmittance reaches 50% of the peak value (hereinafter, this wavelength is also referred to as λ) exists in the wavelength range of 540 to 600 nm. T50 ). In addition, it is preferred that there is a wavelength in the wavelength range of 560 to 620 nm where the transmittance reaches 20% of the peak value (hereinafter, this wavelength is also referred to as λ T20 ). T50 It preferably exists in the wavelength range of 545 to 595 nm, and more preferably exists in the wavelength range of 550 to 590 nm. T20It is preferably present in the wavelength range of 565 to 615 nm, and more preferably in the wavelength range of 560 to 610 nm. T20 and λ T50 The difference (λ T20 -λ T50 ) is preferably 5 to 80 nm, more preferably 7 to 50 nm, and further preferably 10 to 30 nm.

[0054] The transmittance of the obtained cured film can be appropriately adjusted by changing the content of at least one phthalocyanine pigment selected from CI Pigment Blue 15:3 and CI Pigment Blue 15:4 contained in the colorant and the content of the colorant in the photosensitive resin composition.

[0055] The photosensitive resin composition of the present invention can be preferably used as a photosensitive resin composition for forming pixels of a color filter, and can be more preferably used as a photosensitive resin composition for forming cyan pixels of a color filter.

[0056] The photosensitive resin composition of the present invention can be preferably used as a photosensitive resin composition for an image display device. More specifically, it can be preferably used as a photosensitive resin composition for forming pixels of a color filter for an image display device, and more preferably as a photosensitive resin composition for forming cyan pixels of a color filter for an image display device. The type of image display device is not particularly limited, but examples thereof include display devices such as organic electroluminescent display devices having an organic semiconductor element as a light source.

[0057] Furthermore, the photosensitive resin composition of the present invention can also be used as a photosensitive resin composition for solid-state imaging devices. More specifically, it can be preferably used as a photosensitive resin composition for forming pixels of a color filter for a solid-state imaging device, and more preferably as a photosensitive resin composition for forming cyan pixels of a color filter for a solid-state imaging device.

[0058] The thickness of the cured film and pixel formed from the photosensitive resin composition of the present invention is preferably 0.5 to 3.0 μm. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and further preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and further preferably 1.8 μm or less. Furthermore, the line width (pattern size) of the pixel formed from the photosensitive resin composition of the present invention is preferably 2.0 to 10.0 μm. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and further preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, and further preferably 2.75 μm or more.

[0059] Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

[0060] Colorants

[0061] The photosensitive resin composition of the present invention contains a colorant. The colorant used in the photosensitive resin composition of the present invention contains at least one phthalocyanine pigment selected from CI Pigment Blue 15:3 and CI Pigment Blue 15:4. Hereinafter, CI Pigment Blue 15:3 and CI Pigment Blue 15:4 are also collectively referred to as specific phthalocyanine pigments.

[0062] The average secondary particle size of the specific phthalocyanine pigment is preferably 50 to 100 nm because it improves visible light transmittance and easily produces a cured film having spectral characteristics suitable for cyan. From the perspective of light resistance, the lower limit is preferably 55 nm or greater, more preferably 60 nm or greater. From the perspective of spectral characteristics, the upper limit is preferably 95 nm or less, more preferably 90 nm or less.

[0063] In addition, in this specification, about the average secondary particle size of pigment, the size of the secondary particles of pigment is measured directly from an electron microscope photograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the secondary particles of each pigment are measured, and the average is used as the particle size of its pigment. Then, for each of 100 pigments, the volume of each pigment is obtained with a cube similar to the particle size obtained, and the volume average particle size is used as the average secondary particle size.

[0064] The colorant used in the photosensitive resin composition of the present invention contains 50% by mass or more of a specific phthalocyanine pigment, preferably 55% by mass or more of a specific phthalocyanine pigment, more preferably 60% by mass or more of a specific phthalocyanine pigment, and even more preferably 65% by mass or more of a specific phthalocyanine pigment. The upper limit may be 100% by mass, 95% by mass or less, or 90% by mass or less.

[0065] The colorant used in the photosensitive resin composition of the present invention may be a colorant containing both CI Pigment Blue 15:3 and CI Pigment Blue 15:4 as specific phthalocyanine pigments, or may contain only one of them. When the photosensitive resin composition of the present invention contains CI Pigment Blue 15:3, the coating properties of the photosensitive resin composition are easily improved. When the photosensitive resin composition of the present invention contains CI Pigment Blue 15:4, the storage stability of the photosensitive resin composition and the heat resistance of the obtained cured film are easily improved. Furthermore, when the colorant used in the photosensitive resin composition of the present invention contains CI Pigment Blue 15:3 and CI Pigment Blue 15:4, the mass ratio of CI Pigment Blue 15:3 to CI Pigment Blue 15:4 is preferably 10 to 1000 parts by mass of CI Pigment Blue 15:4 relative to 100 parts by mass of CI Pigment Blue 15:3, more preferably 25 to 400 parts by mass, and even more preferably 50 to 200 parts by mass.

[0066] The colorant used in the photosensitive resin composition of the present invention may contain a colorant other than the above-mentioned specific phthalocyanine pigment (hereinafter also referred to as other colorants). When other colorants are contained, it is possible to expect better light resistance and improved color separation from pixels of other colors. When the colorant used in the photosensitive resin composition of the present invention further contains other colorants, the content of the other colorants in the colorant is preferably less than 50% by mass, more preferably less than 45% by mass, more preferably less than 40% by mass, more preferably less than 35% by mass, and particularly preferably less than 30% by mass. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more.

[0067] Furthermore, the colorant used in the photosensitive resin composition of the present invention preferably contains substantially no other colorants. This aspect can also increase light transmittance and achieve pixels with higher sensitivity. Furthermore, the colorant containing substantially no other colorants means that the content of other colorants in the colorant is less than 0.5% by mass, preferably less than 0.1% by mass, and more preferably contains no other colorants.

[0068] As other coloring agents, color coloring agents such as red coloring agents, green coloring agents, blue coloring agents, yellow coloring agents, purple coloring agents, and orange coloring agents can be enumerated, preferably green coloring agents, blue coloring agents, and yellow coloring agents. From the perspective of easily obtaining more excellent light resistance, yellow coloring agents are more preferred. Other coloring agents can be pigments or dyes. Pigments and dyes can be used in combination. Furthermore, the pigment can be any one of an inorganic pigment or an organic pigment. Furthermore, the pigment can use a material in which a part of an inorganic pigment or an organic-inorganic pigment is replaced by an organic chromogenic group. By replacing a part of an inorganic pigment or an organic-inorganic pigment by an organic chromogenic group, hue design can be easily performed. As pigments, the pigments shown below can be enumerated.

[0069] CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 、125、126、127、128、129、137、138、139、147、148、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、231、232(methine series), 233(quinoline series), etc. (the above are yellow pigments),

[0070] CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (the above are orange pigments),

[0071] CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294 (xanthene series, Organo Ultramarine, Bluish Red), 295 (azo series), 296 (azo series), etc. (the above are red pigments),

[0072] CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (the above are green pigments),

[0073] CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane series), 61 (xanthene series), etc. (the above are purple pigments),

[0074] CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo series), 88 (methine series), etc. (the above are blue pigments).

[0075] Furthermore, as green pigments, zinc phthalocyanine halides containing an average of 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms per molecule can also be used. Specific examples include compounds described in International Publication No. 2015 / 118720. Furthermore, as green pigments, compounds described in the specification of 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 Publication No. 2019-008014, and phthalocyanine compounds described in Japanese Patent Application Publication No. 2018-180023 can also be used.

[0076] Furthermore, as a blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

[0077] As yellow pigments, compounds described in Japanese Patent Application Laid-Open No. 2017-201003, compounds described in Japanese Patent Application Laid-Open No. 2017-197719, compounds described in paragraphs 0011 to 0062 and 0137 to 0276 of Japanese Patent Application Laid-Open No. 2017-171912, compounds described in paragraphs 0010 to 0062 and 0138 to 0295 of Japanese Patent Application Laid-Open No. 2017-171913, compounds described in paragraphs 0011 to 0062 and 0139 to 0190 of Japanese Patent Application Laid-Open No. 2017-171914, compounds described in paragraphs 0010 to 0062 and 0139 to 0190 of Japanese Patent Application Laid-Open No. 2017-171915, 5, the compounds described in paragraphs 0142 to 0222, the quinophthalone compounds described in paragraphs 0011 to 0034 of Japanese Patent Application Laid-Open No. 2013-054339, the quinophthalone compounds described in paragraphs 0013 to 0058 of Japanese Patent Application Laid-Open No. 2014-026228, the isoindoline compounds described in Japanese Patent Application Laid-Open No. 2018-062644, the quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2018-203798, the quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2018-062578, the quinophthalone compounds described in Japanese Patent No. 6432077, the quinophthalone compounds described in Japanese Patent No. 6432076 Quinophthalone compounds, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2018-155881, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2018-111757, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2018-040835, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2017-197640, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2016-145282, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2014-085565, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2014-021139, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-209614 compounds, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-209435, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-181015, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-061622, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-054339, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-032486, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2012-226110, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-074987, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-081565,Quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-074986, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-074985, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-050420, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-031281, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 48-032765, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2019-008014, compounds represented by the following formula (QP1), compounds represented by the following formula (QP2).

[0078] [Chemical Formula 1]

[0079]

[0080] 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.

[0081] [Chemical Formula 2]

[0082]

[0083] In formula (QP2), Y 1 ~Y 3 Each independently represents a halogen atom. n and m represent integers of 0 to 6, and p represents an integer of 0 to 5. (n+m) is 1 or greater. Specific examples of the compound represented by formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.

[0084] As red pigments, diketopyrrolopyrrole compounds in which at least one bromine atom is substituted as described in Japanese Patent Application Laid-Open No. 2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 102399, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 117965, and naphthol azo compounds described in Japanese Patent Application Laid-Open No. 2012-229344 can also be used. In addition, as red pigments, compounds having a structure in which an aromatic ring group formed by introducing a group bonded to an oxygen atom, a sulfur atom, or a nitrogen atom into the aromatic ring and bonded to a diketopyrrolopyrrole skeleton can also be used.

[0085] As dye, there is no particular limitation, and known dyes can be used. For example, dyes such as pyrazole azo system, anilino azo system, triarylmethane system, anthraquinone system, anthrapyridine quinone system, benzylidene system, oxonol system, pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothiazine system, pyrrolopyrazole azomethine system, xanthene system, phthalocyanine system, benzopyran system, indigo system, pyrromethene system can be enumerated. In addition, the thiazole compounds described in Japanese Unexamined Patent Publication No. 2012-158649, the azo compounds described in Japanese Unexamined Patent Publication No. 2011-184493, and the azo compounds described in Japanese Unexamined Patent Publication No. 2011-145540 can also be preferably used. Furthermore, as yellow dyes, quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339 and quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228 can also be used.

[0086] Other colorants may be pigment polymers. Pigment polymers have two or more pigment structures in one molecule, preferably three or more pigment structures. The upper limit is not particularly limited, but can also be set to 100 or less. The multiple color pigment structures in one molecule can be the same pigment structure or different pigment structures. The weight average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and further preferably 6000 or more. The upper limit is more preferably 30000 or less, and further preferably 20000 or less. Pigment polymers can also use compounds described in Japanese Patent Application Publication No. 2011-213925, Japanese Patent Application Publication No. 2013-041097, Japanese Patent Application Publication No. 2015-028144, Japanese Patent Application Publication No. 2015-030742, International Publication No. 2016 / 031442, etc.

[0087] The content of the colorant in the total solid content of the photosensitive resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0088] <<Resin>>

[0089] The photosensitive resin composition of the present invention contains a resin. The resin is incorporated, for example, to disperse particles of a pigment or the like in the composition or as a binder. Resins used primarily to disperse particles or the like in the composition are also referred to as dispersants. However, these uses of the resin are merely examples, and the resin may be used for purposes other than these.

[0090] Examples of the resin include (meth)acrylic resins, (meth)acrylamide resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, silicone resins, polyimide resins, and polyurethane resins.

[0091] The weight average molecular weight (Mw) of the resin is preferably 2,000 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 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more.

[0092] The photosensitive resin composition of the present invention also preferably contains a resin with an amine value. This allows for fine dispersion of the pigment, enabling the formation of pixels (patterns) with minimal defects even when using the photosensitive resin composition to form fine pixels (patterns). The amine value of the resin is preferably 25 to 60 mgKOH / g, more preferably 26 to 59 mgKOH / g, and even more preferably 27 to 58 mgKOH / g. Resins with an amine value are preferably used as dispersants for the specific phthalocyanine pigments described above.

[0093] To achieve both high resolution and pigment dispersibility in the photosensitive resin composition, the acid value of the amine-containing resin is preferably 0 to 250 mgKOH / g. The upper limit is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less. To improve alkali solubility and facilitate improved resolution, the lower limit is preferably 5 mgKOH / g or more, and more preferably 10 mgKOH / g or more. Furthermore, the acid value of the amine-containing resin may be 0 mgKOH / g. When the acid value of the amine-containing resin is 0 mgKOH / g, excellent pigment dispersion stability is achieved.

[0094] The number average molecular weight of the resin having an amine value is preferably 500 to 50,000, more preferably 3,000 to 30,000.

[0095] As resins having an amine value, (meth) acrylic resins, polyimide resins, polyester resins, polyether resins, polyamide resins, etc. can be mentioned. In view of the good transparency and heat resistance of the resin, (meth) acrylic resins are preferred. Specific examples of basic resins include vinyl monomers containing N,N-disubstituted amino groups, copolymers of (meth) acrylic acid alkyl ester monomers and other vinyl monomers, etc. As vinyl monomers containing N,N-disubstituted amino groups, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, or N,N-diethylaminoethyl (meth)acrylamide can be mentioned. Examples of the alkyl (meth)acrylate monomer include (meth)acrylates obtained by reacting an unsaturated monocarboxylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, or lauryl (meth)acrylate with an alkyl alcohol having 1 to 18 carbon atoms. Examples of other vinyl monomers include nitro group-containing vinyl monomers such as (meth)acrylonitrile, aromatic vinyl monomers such as styrene, α-methylstyrene, or benzyl (meth)acrylate, hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or polyethylene glycol (meth)acrylate, amide group-containing vinyl monomers such as (meth)acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, or diacetoneacrylamide, and N-hydroxymethyl (meth)acrylate. vinyl monomers such as (hydroxymethyl)acrylamide or dimethylol(meth)acrylamide, alkoxymethyl-containing vinyl monomers such as N-methoxymethyl(meth)acrylamide or N-butoxymethyl(meth)acrylamide, olefins such as ethylene, propylene or isoprene, dienes such as chloroprene or butadiene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether, and fatty acid vinyl esters such as vinyl acetate or vinyl propionate.

[0096] Examples of commercially available resins having an amine value include DISPERBYK 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, and BYK-LPN6919 (all BYK Japan KK), SOLSPERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan Limited.), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), etc.

[0097] The photosensitive resin composition of the present invention preferably contains an alkali-soluble resin. By including an alkali-soluble resin in the photosensitive resin composition of the present invention, the developability of the photosensitive resin composition can be improved, and when the photosensitive resin composition of the present invention is used to form a pattern using a photolithography method, the generation of development residue can be effectively suppressed. Examples of the alkali-soluble resin include resins having an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, with a carboxyl group being preferred. The alkali-soluble resin may contain only one acid group or two or more acid groups. In addition, the alkali-soluble resin can also be used as a dispersant.

[0098] The alkali-soluble resin preferably contains repeating units having an acid group in a side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in a side chain based on all repeating units in the resin. The upper limit of the content of repeating units having an acid group in 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 in a side chain is preferably 10 mol% or more, more preferably 20 mol% or more.

[0099] The alkali-soluble resin is preferably an alkali-soluble resin having a polymerizable group. Examples of the polymerizable group include a (meth)allyl group and a (meth)acryloyl group. The alkali-soluble resin having a polymerizable group is preferably a resin containing repeating units having a polymerizable group in a side chain and repeating units having an acid group in a side chain.

[0100] The alkali-soluble resin also preferably contains repeating units 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 also be referred to as "ether dimers").

[0101] [Chemical Formula 3]

[0102]

[0103] 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.

[0104] [Chemical Formula 4]

[0105]

[0106] 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 of Japanese Patent Application Laid-Open No. 2010-168539, the contents of which are incorporated herein.

[0107] As specific examples of the ether dimer, reference can be made to the description in paragraph 0317 of JP-A-2013-029760, for example, the contents of which are incorporated herein.

[0108] Regarding the alkali-soluble resin, reference can be made to the description in paragraphs 0558 to 0571 of Japanese Patent Application Publication No. 2012-208494 (paragraphs 0685 to 0700 of the corresponding specification of U.S. Patent Application Publication No. 2012 / 0235099), the description in paragraphs 0076 to 0099 of Japanese Patent Application Publication No. 2012-198408, and the description in Japanese Patent Application Publication No. 2018-105911, the contents of which are incorporated into this specification.

[0109] The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is preferably 50 mgKOH / g or higher, more preferably 70 mgKOH / g or higher. The upper limit is preferably 400 mgKOH / g or lower, more preferably 300 mgKOH / g or lower, and even more preferably 200 mgKOH / g or lower.

[0110] In the photosensitive resin composition of the present invention, a resin having a maleimide structure can also be used as a resin. In this specification, a maleimide structure refers to a structure derived from a maleimide compound. Examples of maleimide compounds include maleimide and N-substituted maleimides. Examples of N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, and laurylmaleimide.

[0111] The resin having a maleimide structure is preferably a resin containing a repeating unit having a maleimide structure. The maleimide structure may be contained in the main chain of the repeating unit or in a side chain of the repeating unit. The maleimide structure is preferably contained in the main chain of the repeating unit because it facilitates the formation of a cured film with suppressed color unevenness.

[0112] The photosensitive resin composition of the present invention also preferably contains a resin i (hereinafter also referred to as resin i) containing a repeating unit derived from a compound represented by formula (I) (hereinafter also referred to as repeating unit i1-1). The photosensitive resin composition of the present invention containing resin i facilitates obtaining a cured film with suppressed color unevenness. The content of repeating unit i1-1 in all repeating units of resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more.

[0113] [Chemical Formula 5]

[0114]

[0115] Where, Xi 1 represents O or NH, preferably O.

[0116] Ri 1 represents a hydrogen atom or a methyl group.

[0117] Li 1 Represents a divalent linking group. Examples of the divalent linking group include hydrocarbon groups, heterocyclic groups, -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these. Examples of the hydrocarbon group include alkyl groups and aryl groups. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, sulfur atoms, and the like. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic ring or a condensed ring. The hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include alkyl groups, aryl groups, hydroxyl groups, halogen atoms, and the like.

[0118] Ri 10 Represents a substituent. As Ri 10 The substituent represented by ⁻¹ includes the substituents Ti shown below, and is preferably a hydrocarbon group, and more preferably an alkyl group which may have an aryl group as a substituent.

[0119] m represents an integer of 0 to 2, preferably 0 or 1, more preferably 0.

[0120] p represents an integer of 0 or greater, preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, further preferably 0 or 1, and particularly preferably 1.

[0121] (Substituent Ti)

[0122] Examples of the substituent Ti include a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORti 1 、-CORti 1 、-COORti 1 、-OCORti 1 、-NRti 1 Rti 2 、-NHCORti 1 、-CONRti 1 Rti 2 、-NHCONRti 1 Rti 2 、-NHCOORti 1 、-SRti 1 、-SO2Rti 1 、-SO2ORti 1 、-NHSO2Rti 1 or -SO2NRti 1 Rti 2 .Rti 1 and Rti 2 Rti represents independently a hydrogen atom, a hydrocarbon group or a heterocyclic group. 1 With Rti 2 They may be bonded to form a ring.

[0123] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0124] Examples of the hydrocarbon group include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, preferably linear or branched, and more preferably branched.

[0125] The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic, but is preferably linear or branched.

[0126] The number of carbon atoms in the alkynyl group is preferably 2 to 30, more preferably 2 to 25. The alkynyl group may be linear, branched, or cyclic, but is preferably linear or branched.

[0127] The aryl group has preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.

[0128] The heterocyclic group may be a monocyclic ring or a condensed ring. The heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 ring atoms. The number of heteroatoms constituting the heterocyclic group's ring is preferably 1 to 3. The heteroatoms constituting the heterocyclic group's ring are preferably nitrogen, oxygen, or sulfur atoms. The number of carbon atoms constituting the heterocyclic group's ring is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.

[0129] The hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described above for the substituent Ti.

[0130] The compound represented by formula (I) is preferably a compound represented by the following formula (I-1).

[0131] [Chemical Formula 6]

[0132]

[0133] Xi 1 represents O or NH, preferably O.

[0134] Ri 1 represents a hydrogen atom or a methyl group.

[0135] Ri 2 、Ri 3 and Ri 11 Each independently represents a hydrocarbon group.

[0136] Ri 2 and Ri 3 The hydrocarbon group represented by is preferably an alkylene group or an arylene group, more preferably an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. 11 The hydrocarbon group represented is preferably an alkyl group optionally substituted with an aryl group, more preferably an alkyl group substituted with an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. When the alkyl group is substituted with an aryl group, the number of carbon atoms in the alkyl group refers to the number of carbon atoms in the alkyl moiety.

[0137] Ri 12 Represents a substituent. As Ri 12 Examples of the substituent represented by include the above-mentioned substituent Ti.

[0138] n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.

[0139] m represents an integer of 0 to 2, is preferably 0 or 1, and more preferably 0.

[0140] p1 represents an integer of 0 or greater, preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, further preferably 0 to 1, and particularly preferably 0.

[0141] q1 represents an integer of 1 or greater, preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1.

[0142] The compound represented by formula (I) is preferably a compound represented by the following formula (III).

[0143] [Chemical Formula 7]

[0144]

[0145] In the formula, Ri 1 Represents a hydrogen atom or a methyl group, Ri 21 and Ri 22 Each independently represents an alkylene group, and n represents an integer of 0 to 15. 21 and Ri 22 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. n is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.

[0146] Examples of the compound represented by formula (I) include ethylene oxide- or propylene oxide-modified (meth)acrylates of p-cumylphenol, and examples of commercially available products include ARONIX M-110 (manufactured by TOAGOSEI CO., LTD.).

[0147] Resin i preferably further contains a repeating unit derived from an alkyl (meth)acrylate (hereinafter also referred to as a repeating unit i1-2). When resin i further has a repeating unit i1-2, the effect of improving the solvent solubility of the photosensitive resin composition can be obtained. The number of carbon atoms in the alkyl portion of the alkyl (meth)acrylate is preferably 3 to 10, more preferably 3 to 8, and further preferably 3 to 6. Preferred specific examples of the alkyl (meth)acrylate include n-butyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl acrylate, etc., and n-butyl (meth)acrylate is preferred because it is easy to obtain better solvent solubility. The content of the repeating unit i 1-2 in all the repeating units of resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more.

[0148] Resin I preferably further contains repeating units having an acid group. This embodiment improves the developability of the photosensitive resin composition. The content of repeating units having an acid group in all repeating units of Resin I is preferably 5 mol% or greater, more preferably 10 mol% or greater, and even more preferably 15 mol% or greater. The upper limit is preferably 60 mol% or less, more preferably 50 mol% or less. Resin I containing repeating units having an acid group may also be an alkali-soluble resin.

[0149] Resin i preferably further contains repeating units having a group containing an ethylenically unsaturated bond. The content of repeating units having a group containing an ethylenically unsaturated bond in all repeating units of resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less.

[0150] The photosensitive resin composition of the present invention also preferably contains a resin having an aromatic carboxyl group (hereinafter also referred to as resin Ac). By using resin Ac, a cured film can be formed that is less likely to discolor the pigment during development and has excellent developability.

[0151] In resin Ac, the aromatic carboxyl group may be contained in the main chain of the repeating unit or in the side chain of the repeating unit. For the reason that the above-mentioned effects can be more significantly achieved, the aromatic carboxyl group is preferably contained in the main chain of the repeating unit. Although the details are unclear, it is speculated that the presence of the aromatic carboxyl group near the main chain can further enhance these properties. In this specification, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In the aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.

[0152] The resin Ac is preferably a resin containing at least one repeating unit selected from the repeating unit represented by the formula (b-1) and the repeating unit represented by the formula (b-10).

[0153] [Chemical Formula 8]

[0154]

[0155] In formula (b-1), Ar 1 represents a group containing an aromatic carboxyl group, L 1 Indicates -COO- or -CONH-, L 2 represents a divalent linking group.

[0156] In formula (b-10), Ar 10 represents a group containing an aromatic carboxyl group, L 11 Indicates -COO- or -CONH-, L 12represents a trivalent linking group, P 10 represents a polymer chain.

[0157] First, the formula (b-1) is described. In the formula (b-1), as the compound containing Ar 1 Examples of the aromatic carboxyl group include structures derived from aromatic tricarboxylic anhydride and structures derived from aromatic tetracarboxylic anhydride. Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds of the following structures.

[0158] [Chemical Formula 9]

[0159]

[0160] In the above formula, Q 1 It 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).

[0161] [Chemical Formula 10]

[0162]

[0163] As containing Ar 1 Specific examples of the aromatic carboxyl group represented by include a group represented by formula (Ar-1), a group represented by formula (Ar-2), a group represented by formula (Ar-3), and the like.

[0164] [Chemical Formula 11]

[0165]

[0166] In formula (Ar-1), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.

[0167] In formula (Ar-2), 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.

[0168] In formula (Ar-3), 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 further preferably 1. However, at least one of n3 and n4 is an integer of 1 or greater.

[0169] In formula (Ar-3), Q 1 It 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).

[0170] In formula (b-1), L 1 represents -COO- or -CONH-, preferably represents -COO-.

[0171] In formula (b-1), L 2 The divalent linking group represented by alkylene, arylene, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and a group formed by combining two or more of these. The number of carbon atoms of the alkylene is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The alkylene and arylene groups may have substituents. Examples of the substituents include hydroxyl groups and the like. L 2 The divalent linking group represented by is preferably -OL 2a -O- represented by the group. 2a Examples include alkylene groups; arylene groups; groups formed by combining an alkylene group and an arylene group; and groups formed by combining at least one selected from an alkylene group and an arylene group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15. The alkylene group may be linear, branched, or cyclic. Alkylene and arylene groups may have substituents. Examples of substituents include hydroxyl groups.

[0172] Next, the formula (b-10) is described. In the formula (b-10), as the compound containing Ar 10 The aromatic carboxyl group represented by 1 The meanings are the same as those in the preceding text, and the preferred ranges are also the same.

[0173] In formula (b-10), L 11 represents -COO- or -CONH-, preferably represents -COO-.

[0174] In formula (b-10), as L 12 The trivalent linking group represented by is exemplified by hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups formed by combining two or more of these. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be any of linear, branched, and cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include hydroxyl groups and the like. L 12The trivalent linking group represented is preferably a group represented by the following formula (L12-1), more preferably a group represented by formula (L12-2).

[0175] [Chemical Formula 12]

[0176]

[0177] L 12a and L 12b represent trivalent linking groups, X 1 represents S, *1 represents L in formula (b-10) 11 The bonding position of *2 indicates the bonding position with P of formula (b-10) 10 bonding position.

[0178] As L 12a and L 12b Examples of the trivalent linking group represented by 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-.

[0179] In formula (b-10), P 10 Represents a polymer chain. 10 The polymer chain represented preferably has at least one repeating unit selected from the group consisting of poly(meth)acrylic acid repeating units, polyether repeating units, polyester repeating units, and polyol repeating units. 10 The weight average molecular weight is preferably 500 to 20,000. The lower limit is preferably 1,000 or more. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and further preferably 3,000 or less. 10 When the weight average molecular weight is within the above range, the dispersibility of the pigment in the composition is good. When the resin having an aromatic carboxyl group is a resin having a repeating unit represented by formula (b-10), the resin can be preferably used as a dispersant.

[0180] The photosensitive resin composition of the present invention also preferably uses a resin having a structure represented by formula (OP1) (hereinafter also referred to as resin OP). This resin can be preferably used as a dispersant.

[0181] [Chemical Formula 13]

[0182]

[0183] Where Rp 4 represents a polyether residue and / or polyester residue having a number average molecular weight of 400 to 30,000 and having an ethylenically unsaturated bond-containing group, and y represents a number of 1 or 2.

[0184] Rp 4The number average molecular weight of Rp is more preferably 400 to 10,000, and further preferably 400 to 3,000. 4 When the number average molecular weight of the pigment is within the above range, the dispersibility of the pigment is good, and these resins can be preferably used as dispersants.

[0185] As Rp 4 Examples of the polyether residue and / or polyester residue having an ethylenically unsaturated bond-containing group include polyether residues and / or polyester residues having a styryl group, a (meth)acryloyl group, a cyanoacryloyl group, a vinyl ether group, and the like.

[0186] Rp 4 Preferred is a group represented by the following formula (Rp-1).

[0187] -Rp 12 -O-Rp 13 -(O-Rp 14 ) S

[0188] Where Rp 12 represents an alkylene group, Rp 13 represents a polyol residue with a valence of 3 or more, Rp 14 represents a (meth)acryloyl group or a cyanoacryloyl group, and s represents 2 or more.

[0189] Rp 12 An alkylene group having 8 or less carbon atoms is preferred. In addition, from the viewpoint of pigment dispersibility, s is preferably 2 or more. In this case, Rp 14 Different groups may be used. s is more preferably 2 to 5, and 2 is particularly preferred.

[0190] As Rp 13 Examples of the trivalent or higher polyols include glycerol, propanol, pentaerythritol, dipentaerythritol, etc. In particular, trivalent to hexavalent polyols are preferred.

[0191] In resin OP, Rp 4 It can be a single phosphate ester or multiple phosphate esters composed of different Rp 4 Furthermore, the resin OP may be only a resin in which y in the formula (OP1) is 1, or a mixture of a resin in which y in the formula (OP1) is 1 and a resin in which y in the formula (OP1) is 2. Furthermore, if Rp of the compound represented by the formula (OP1) is 4 A polycaprolactone residue having a number average molecular weight of 400 to 10,000 (more preferably 400 to 3,000) is preferred because the pigment dispersibility becomes good.

[0192] The photosensitive resin composition of the present invention may contain a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and alkaline dispersants (alkaline resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of base groups. As the acidic dispersant (acidic resin), when the total amount of the amount of acid groups and the amount of base groups is set to 100 mol%, a resin in which the amount of acid groups is 70 mol% or more is preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Furthermore, the alkaline dispersant (alkaline resin) refers to a resin in which the amount of base groups is greater than the amount of acid groups. As the alkaline dispersant (alkaline resin), when the total amount of the amount of acid groups and the amount of base groups is set to 100 mol%, a resin in which the amount of basic groups exceeds 50 mol%. The base group possessed by the alkaline dispersant is preferably an amino group.

[0193] The resin used as the dispersant is preferably a resin having the above-mentioned amine value.

[0194] The resin used as the dispersant is also preferably a grafted resin. For details of the grafted resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, and the contents are incorporated herein.

[0195] The resin used as a dispersant is also preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. As a polyimine-based dispersant, a resin having a main chain and a side chain, and having a basic nitrogen atom in at least one of the main chain and the side chain, is preferably used, wherein the main chain contains a partial structure having a functional group with a pKa of 14 or less, and the number of atoms in the side chain is 40 to 10,000. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. For polyimine-based dispersants, reference can be made to paragraphs 0102 to 0166 of Japanese Patent Application Laid-Open No. 2012-255128, and the contents are incorporated into this specification.

[0196] The resin used as a dispersant is also preferably a resin having a structure in which multiple polymer chains are bonded to a core. Examples of such resins include dendrimers (including star polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

[0197] The resin used as a dispersant is also preferably a resin containing a repeating unit having a group containing an ethylenically unsaturated bond on the side chain. Among all the repeating units of the resin, the content of the repeating unit having a group containing an ethylenically unsaturated bond on the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and further preferably 20 to 70 mol%. In addition, the dispersant can also use the resin described in Japanese Patent Application Laid-Open No. 2018-087939.

[0198] Dispersants are also commercially available, and specific examples thereof include the DISPERBYK series manufactured by BYK Japan KK, the SOLSPERSE series manufactured by Lubrizol Japan Limited, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Inc. Furthermore, the products described in paragraph 0129 of Japanese Patent Application Laid-Open No. 2012-137564 and the products described in paragraph 0235 of Japanese Patent Application Laid-Open No. 2017-194662 can also be used as dispersants.

[0199] The resin content in the total solids content of the photosensitive resin composition is preferably 10 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more.

[0200] Furthermore, the content of the alkali-soluble resin in the resin contained in the photosensitive resin composition of the present invention is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and even more preferably 30 to 100% by mass.

[0201] The content of the resin having an amine value in the photosensitive resin composition of the present invention is preferably 0 to 100% by mass. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and the lower limit is preferably 10% by mass or more, even more preferably 20% by mass or more.

[0202] Furthermore, when the photosensitive resin composition of the present invention contains a dispersant as a resin, the content of the dispersant is preferably 10 to 100 parts by mass relative to 100 parts by mass of the specific phthalocyanine pigment. The upper limit is preferably 80 parts by mass or less, more preferably 60 parts by mass or less. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. Furthermore, the content of the resin having an amine value in the dispersant is preferably 0 to 100% by mass, more preferably 10 to 100% by mass, and even more preferably 20 to 100% by mass. Furthermore, the content of the dispersant in the resin is preferably 10 to 100% by mass. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less. The lower limit is preferably 20% by mass or more, and even more preferably 30% by mass or more.

[0203] <<Polymerizable compounds>>

[0204] The photosensitive resin composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by free radicals, acid, or heat can be used. In the present invention, the polymerizable compound is preferably a compound having a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include vinyl, (meth)allyl, and (meth)acryloyl groups. The polymerizable compound used in the present invention is preferably a free radical polymerizable compound.

[0205] The polymerizable compound may be in any chemical form, such as a monomer, prepolymer, or oligomer, with monomers being preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. The lower limit is preferably 150 or more, more preferably 250 or more.

[0206] From the viewpoint of the temporal stability of the photosensitive resin composition and the light resistance of the cured film obtained, the group containing an ethylenically unsaturated bond of the monomeric polymerizable compound (hereinafter referred to as C=C value) is preferably 2 to 14 mmol / g. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and further preferably 5 mmol / g or more. The upper limit is preferably 12 mmol / g or less, further preferably 10 mmol / g or less, and further preferably 8 mmol / g or less. The C=C value of the group containing an ethylenically unsaturated bond is calculated by dividing the number of groups containing an ethylenically unsaturated bond contained in one molecule of the group containing an ethylenically unsaturated bond by the molecular weight of the polymerizable compound.

[0207] The polymerizable compound is preferably a compound containing three 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. Furthermore, the polymerizable compound is preferably a tri- to pentafunctional (meth)acrylate compound, more preferably a tri- to hexafunctional (meth)acrylate compound. Specific examples of polymerizable compounds include compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraphs 0254 to 0257 of JP-A-2008-292970, paragraphs 0034 to 0038 of JP-A-2013-253224, paragraph 0477 of JP-A-2012-208494, JP-A-2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, and Japanese Patent No. 2017-194662, the contents of which are incorporated into this specification.

[0208] Preferred polymerizable compounds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ESTER A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, compounds manufactured by SARTOMER). Company, Inc. manufactures and markets SR454 and SR499). In addition, as the polymerizable compound, diglycerol EO (ethylene oxide)-modified (meth)acrylate (commercially available as M-460; manufactured by TOAGOSEI CO., LTD.), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARADHDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by TAISEI FINE CHEMICAL CO., LTD.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL CO., LTD. manufacturing) and so on.

[0209] Furthermore, as polymerizable compounds, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, isocyanurate ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate are also preferably used. Examples of 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.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0210] The polymerizable compound can also use a polymerizable compound having an acid group. By using a polymerizable compound having an acid group, the polymerizable compound of the unexposed portion can be easily removed during development, thereby suppressing the generation of development residues. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like, preferably a carboxyl group. Commercially available products of polymerizable compounds having an acid group include ARONIX M-305, M-510, M-520, and ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.). The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and 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 for manufacturing and handling.

[0211] The polymerizable compound may also be a polymerizable compound having a caprolactone structure. Examples of polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

[0212] A polymerizable compound having an alkyleneoxy group can also be used. 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 trifunctional to hexafunctional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available polymerizable compounds having an alkyleneoxy group include, for example, SR-494, a tetrafunctional (meth)acrylate having 4 ethyleneoxy groups, manufactured by SARTOMER Company, Inc., and KAYARAD TPA-330, a trifunctional (meth)acrylate having 3 isobutyleneoxy groups.

[0213] The polymerizable compound may also contain a fluorene skeleton. Examples of commercially available polymerizable compounds containing a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers containing a fluorene skeleton).

[0214] As the polymerizable compound, it is also preferable to use a compound that does not substantially contain environmentally regulated substances such as toluene. Examples of commercially available products of these compounds include KAYARAD DPHA LT and KAYARAD DPEA-12LT (manufactured by Nippon Kayaku Co., Ltd.).

[0215] Preferred polymerizable compounds include polyurethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765; and carbamate compounds having an ethylene oxide skeleton such as those described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418. Furthermore, polymerizable compounds having an amino structure or a thioether structure in the molecule such as those described in JP-A-63-277653, JP-A-63-260909, and JP-B-01-105238 are also preferred. Furthermore, commercially available polymerizable compounds such as 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, and LINC-202UA (manufactured by KYOEISHA CHEMICAL CO., LTD.) can also be used.

[0216] The content of the polymerizable compound in the total solids content of the photosensitive resin composition is preferably 0.1 to 50% by mass. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and even more preferably 40% by mass or less. The polymerizable compound may be used alone or in combination of two or more. When two or more are used in combination, their total preferably falls within the above range.

[0217] <<Photopolymerization initiator>>

[0218] The photosensitive resin 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, compounds that are photosensitized to light in the ultraviolet to visible range are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0219] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound. More preferred are compounds selected from the group consisting of oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, and even more preferred are oxime compounds. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and Japanese Patent No. 6301489, the contents of which are incorporated into the present specification.

[0220] Examples of commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Examples of commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Examples of commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (both manufactured by BASF).

[0221] 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 JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. The compounds described in Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Laid-Open No. 2000-066385, the compounds described in Japanese Patent Application Laid-Open No. 2000-080068, the compounds described in Japanese Patent Application Laid-Open No. 2004-534797, the compounds described in Japanese Patent Application Laid-Open No. 2006-342166, the compounds described in Japanese Patent Application Laid-Open No. 2017-019766, Compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Unexamined Publication No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Examples of commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, a photopolymerization initiator 2 described in Japanese Patent Application Laid-Open No. 2012-014052). Furthermore, as the oxime compound, a non-coloring compound or a highly transparent compound that is less susceptible to discoloration is preferably used.As commercially available products, ADEKA ARKLS NCI-730, NCI-831, NCI-930 (all manufactured by ADEKA CORPORATION) and the like may be mentioned.

[0222] 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 compounds described in JP-A-2014-137466.

[0223] As the photopolymerization initiator, an oxime compound having a carbazole ring and a naphthalene ring as the skeleton of at least one benzene ring can also be used. Specific examples of these oxime compounds include the compounds described in International Publication No. 2013 / 083505.

[0224] 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.

[0225] As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Laid-Open No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Laid-Open No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent Application No. 4223071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

[0226] 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 International Publication No. 2015 / 036910.

[0227] Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0228] [Chemical Formula 14]

[0229]

[0230] [Chemical Formula 15]

[0231]

[0232] The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the range of 360 to 480 nm. Furthermore, from the viewpoint of sensitivity, the molar absorptivity of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, further preferably 2000 to 300,000, and particularly preferably 5000 to 200,000. The molar absorptivity of the compound can be measured using a known method. For example, it is preferably measured using ethyl acetate at a concentration of 0.01 g / L using a spectrophotometer (Varian, Inc., Cary-5 spectrophotometer).

[0233] As the photopolymerization initiator, a difunctional or trifunctional or higher-functional photoradical polymerization initiator can also be used. By using such a photoradical polymerization initiator, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, thereby achieving good sensitivity. Furthermore, when using a compound with an asymmetric structure, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, thereby improving the temporal stability of the colored composition. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and compounds described in JP-A-2013-522445 ( E) and compound (G), Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Unexamined Patent Application Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Unexamined Patent Application Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, and the oxime compound described in Japanese Patent No. 6469669.

[0234] The content of the photopolymerization initiator in the total solids content of the photosensitive resin composition is preferably 0.1 to 30% 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 20% by mass or less, more preferably 15% by mass or less. A single photopolymerization initiator may be used alone, or two or more may be used in combination. When two or more are used in combination, their total preferably falls within the above range.

[0235] <<UV absorber>>

[0236] The photosensitive resin composition of the present invention contains an ultraviolet absorber. The ultraviolet absorber is preferably a compound having a maximum absorption wavelength in the wavelength range of 300 to 380 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 320 to 380 nm. Furthermore, the molar absorption coefficient of the ultraviolet absorber at a wavelength of 365 nm is preferably 5000 L·mol -1 cm -1 More than 10000 L·mol -1 cm -1 More than, more preferably 30000 L·mol -1 cm -1 The upper limit is preferably 100,000 L·mol, for example. -1 cm -1 the following.

[0237] Examples of ultraviolet absorbers include conjugated diene compounds, methyl dibenzoyl compounds, triazine compounds, benzotriazole compounds, benzophenone compounds, salicylate compounds, coumarin compounds, acrylonitrile compounds, benzodithiazole compounds, cinnamic acid compounds, α-β unsaturated ketones, and quinolone compounds. Conjugated diene compounds, benzotriazole compounds, and triazine compounds are preferred because they can easily provide better light resistance.

[0238] The conjugated diene compound is preferably a compound represented by the following formula (UV-1).

[0239] [Chemical Formula 16]

[0240]

[0241] In formula (UV-1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 With R 2 They can be the same or different. 1 and R 2 At least one of them is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. 1 and R 2 Can be used with R 1 and R 2 The nitrogen atoms to which the bond is attached together form a cyclic amino group. Examples of the cyclic amino group include piperidinyl, morpholinyl, pyrrolidinyl, hexahydroazepinoyl, and piperazinyl. 1 and R 2Each independently represents preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms.

[0242] In formula (UV-1), R 3 and R 4 Each independently represents an electron-withdrawing group. 3 and R 4 Preferably, each independently represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, or a sulfamoyl group, and more preferably represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, or a sulfamoyl group. 3 and R 4 Can bond with each other to form a cyclic electron-withdrawing group. 3 With R 4 Examples of the cyclic electron-withdrawing group formed by bonding to each other include a 6-membered ring containing two carbonyl groups.

[0243] From the formula (UV-1) R 1 、R 2 、R 3 and R 4 At least one of the monomers may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may also be a copolymer with other monomers.

[0244] For a description of the substituents of the ultraviolet absorber represented by formula (UV-1), reference can be made to paragraphs 0024 to 0033 of Japanese Patent Application Laid-Open No. 2009-265642, which are incorporated herein by reference. Specific examples of the ultraviolet absorber represented by formula (UV-1) include compounds having the following structures and compounds described in paragraphs 0034 to 0036 of Japanese Patent Application Laid-Open No. 2009-265642. Commercially available ultraviolet absorbers represented by formula (UV-1) include UV-503 (manufactured by Daito Chemical Co., Ltd.).

[0245] [Chemical Formula 17]

[0246]

[0247] The methyldibenzoyl compound is preferably a compound represented by the following formula (UV-2).

[0248] [Chemical Formula 18]

[0249]

[0250] In formula (UV-2), R101 and R 102 Each independently represents a substituent, and m1 and m2 each independently represent an integer of 0 to 4.

[0251] As R 101 and R 102 The substituents represented by include halogen atoms, cyano groups, nitro groups, alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, arylthio groups, heteroarylthio groups, -NR U1 R U2 、-COR U3 、-COOR U4 、-OCOR U5 、-NHCOR U6 、-CONR U7 R U8 、-NHCONR U9 R U10 、-NHCOOR U11 、-SO2R U12 、-SO2OR U13 、-NHSO2R U14 and-SO2NR U15 R U16 . R U1 ~R U16 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group.

[0252] R 101 and R 10 The substituents represented by 2 are preferably each independently an alkyl group or an alkoxy group. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of alkyl groups include linear, branched, and cyclic groups, preferably linear or branched, more preferably branched. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkoxy group is preferably linear or branched, more preferably branched.

[0253] In formula (UV-2), preferably R 101 and R 102 A combination in which one of the groups is an alkyl group and the other is an alkoxy group.

[0254] m1 and m2 each independently represent 0 to 4. m1 and m2 each independently represent preferably 0 to 2, more preferably 0 to 1, and particularly preferably 1.

[0255] Specific examples of the compound represented by formula (UV-2) include avobenzone (AVOBENZONE) and the like.

[0256] The triazine compound is preferably a compound represented by the following formula (UV-3-1), (UV-3-2) or (UV-3-3).

[0257] [Chemical Formula 19]

[0258]

[0259] Where R d1 Each of the following independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group, alkenyl group, aryl group, alkylaryl group, and aralkyl group may have a substituent. Examples of the substituent include those described above for the substituent Ti.

[0260] Where R d2 ~R d9 Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group, alkenyl group, aryl group, alkylaryl group, and aralkyl group may have a substituent. Examples of the substituent include the groups described above for the substituent Ti.

[0261] Specific examples of triazine compounds include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. -bis(hydroxyphenyl)triazine compounds such as bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, etc. Examples of commercially available triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (all manufactured by BASF).

[0262] The benzotriazole compound is preferably a compound represented by the following formula (UV-4).

[0263] [Chemical Formula 20]

[0264]

[0265] Where R e1 ~R e3 Each of the following independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group, alkylaryl group, and aralkyl group may have a substituent. Examples of the substituent include the groups described for the substituent Ti above, with an alkoxycarbonyl group having 1 to 9 carbon atoms being preferred.

[0266] Specific examples of the benzotriazole compound include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole. triazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, etc. Commercially available products include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 326, TINUVIN 328, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 171, and TINUVIN 1130 (all manufactured by BASF). MYUA series manufactured by MIYOSHI OIL & FAT CO., LTD. can also be used as the benzotriazole compound.

[0267] Examples of the benzophenone compound include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Commercially available benzophenone compounds include UVINULA, UVINUL 3049, and UVINUL 3050 (all manufactured by BASF).

[0268] Examples of the salicylate compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0269] Examples of the coumarin compound include coumarin-4, 4-hydroxycoumarin, and 7-hydroxycoumarin.

[0270] Examples of the acrylonitrile compound include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.

[0271] The content of the ultraviolet absorber in the total solid content of the photosensitive resin composition is 0.1 to 10% by mass. The upper limit is preferably 9.5% by mass or less, more preferably 9% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. As long as the content of the ultraviolet absorber is 0.1% by mass or more, the light resistance of the obtained cured film can be improved. Furthermore, as long as the content of the ultraviolet absorber is 10% by mass or less, a cured film in which the occurrence of color mixing with pixels of other hues is suppressed can be formed. In addition, when pixels are formed using a photolithography method using a photosensitive resin composition, the resolution of the photosensitive resin composition can also be improved, and pixels with good rectangularity can also be formed.

[0272] The photosensitive resin composition of the present invention preferably contains 1 to 200 parts by mass of a UV absorber per 100 parts by mass of the photopolymerization initiator. This embodiment achieves both higher resolution and light resistance. The upper limit of the UV absorber content is preferably 190 parts by mass or less, more preferably 170 parts by mass or less. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more.

[0273] The photosensitive resin composition of the present invention preferably contains 0.1 to 100 parts by mass of a UV absorber per 100 parts by mass of the polymerizable compound. This embodiment achieves both higher resolution and light resistance. The upper limit of the UV absorber content is preferably 80 parts by mass or less, more preferably 50 parts by mass or less. The lower limit is preferably 1 part by mass or more, more preferably 5 parts by mass or more.

[0274] The photosensitive resin composition of the present invention may contain only one ultraviolet absorber or two or more ultraviolet absorbers. When the photosensitive resin composition of the present invention contains two or more ultraviolet absorbers, the total amount thereof is within the above range.

[0275] <<Solvent>>

[0276] The photosensitive resin composition of the present invention contains a solvent. The solvent is generally not limited as long as the solubility of the components and the coatability of the photosensitive resin composition are satisfied. Examples of the solvent include organic solvents. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details, please refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein. Furthermore, cyclic alkyl-substituted ester solvents and cyclic alkyl-substituted ketone solvents are also preferably used. Specific examples of the organic solvent 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, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N'-dimethylpropionamide, 3-butoxy-N,N'-dimethylpropionamide, etc. However, for environmental reasons, it may be desirable to reduce the content of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents (for example, it may be 50 parts per million (ppm) or less, 10 ppm or less, or even 1 ppm or less, relative to the total amount of the organic solvent).

[0277] In the present invention, it is preferred to use an organic solvent with a low metal content. For example, the metal content of the organic solvent is preferably 10 parts per billion (ppb) or less. If necessary, organic solvents with a ppt (parts per trillion) mass content can be used. Such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

[0278] Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation or thin film distillation) 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 is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0279] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The isomers may be one type or multiple types.

[0280] The peroxide content in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0281] The content of the solvent in the photosensitive resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.

[0282] Furthermore, from the perspective of environmental regulation, the photosensitive resin composition of the present invention preferably contains substantially no environmentally regulated substances. In the present invention, "substantially free of environmentally regulated substances" means that the content of environmentally regulated substances in the photosensitive resin composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmentally regulated substances under REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) system, and VOC (Volatile Organic Compounds) regulations, and their usage and handling methods are strictly regulated. During the production of the various components used in the photosensitive resin composition, these compounds may be used as solvents or may be incorporated into the photosensitive resin composition as residual solvents. From the perspective of human safety and environmental considerations, the amount of these substances should be minimized.

[0283] As a method for reducing environmentally controlled substances, there can be cited a method of heating or reducing the inside of the system to a point above the boiling point of the environmentally controlled substances and distilling the environmentally controlled substances from the inside of the system to reduce the amount. In addition, when a small amount of environmentally controlled substances is distilled, it is also effective to azeotropize with a solvent having the same boiling point as these solvents in order to improve efficiency. In addition, when containing a compound with free radical polymerizability, in order to suppress the free radical polymerization reaction during the reduced pressure distillation and cross-linking between molecules, a polymerization inhibitor or the like can also be added and reduced pressure distillation can be performed. These distillation removal methods can be performed at any stage, such as the stage of the product of the raw material reaction (such as the resin solution and the multifunctional monomer solution after polymerization) or the stage of the photosensitive resin composition produced by mixing these compounds.

[0284] <<Pigment derivatives>>

[0285] The photosensitive resin composition of the present invention may contain a pigment derivative. The pigment derivative is used as a dispersing aid for the pigment. Examples of the pigment derivative include compounds having a structure in which a portion of the chromophore is substituted with an acid group or a basic group.

[0286] As the chromophore constituting the pigment derivative, there can be mentioned a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, a perylene skeleton, a perylene skeleton, a thioindigo skeleton, an isoindoline skeleton, an isoindolinone skeleton, a quinophthalone skeleton, a reducing skeleton, a metal complex skeleton, etc., preferably a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton and a phthalocyanine skeleton, and more preferably an azo skeleton and a benzimidazolone skeleton.

[0287] Examples of the acid group possessed by the pigment derivative include carboxyl groups, sulfonic acid groups, phosphoric acid groups, and salts thereof. Examples of the atom or atomic group constituting the salt include alkali metal ions (Li + 、Na + , K + etc.), alkaline earth metal ions (Ca 2+ Mg 2+ etc.), ammonium ion, imidazolium ion, pyridinium ion, phosphonium ion, etc.

[0288] Examples of the base group possessed by the pigment derivative include amino, pyridyl, and salts thereof, ammonium salts, and phthalimidomethyl. Examples of the amino group include -NH2, dialkylamino, alkylarylamino, diarylamino, and cyclic amino groups. Examples of the atom or atomic group constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0289] As the pigment derivative, a pigment derivative having excellent visual transparency (hereinafter also referred to as a transparent pigment derivative) can also be used. The maximum value (εmax) of the molar absorption coefficient of the transparent pigment derivative in the wavelength range of 400 to 700 nm is preferably 3000 L·mol -1 cm -1 Below, more preferably 1000 L·mol -1 cm -1 Below, more preferably 100 L·mol -1 cm -1 Below. The lower limit of εmax is, for example, 1 L·mol -1 cm -1 Above, it can also be 10L·mol -1 cm -1 above.

[0290] Specific examples of the pigment derivatives include Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 01-217077, Japanese Patent Application Laid-Open No. 03-009961, Japanese Patent Application Laid-Open No. 03-026767, Japanese Patent Application Laid-Open No. 03-153780, Japanese Patent Application Laid-Open No. 03-045662, Japanese Patent Application Laid-Open No. 04-285669, Japanese Patent Application Laid-Open No. 06-145546, Japanese Patent Application Laid-Open No. 06-212088, Japanese Patent Application Laid-Open No. 06-240158, Japanese Patent Application Laid-Open No. 10-030063, Japanese Patent Application Laid-Open No. 10-195326, and International Publication No. 2011 / 024 Compounds described in paragraphs 0086 to 0098 of International Publication No. 2012 / 102399, paragraphs 0063 to 0094 of International Publication No. 2017 / 038252, paragraph 0171 of JP-A-2015-151530, paragraphs 0162 to 0183 of JP-A-2011-252065, JP-A-2003-081972, Japanese Patent No. 5299151, JP-A-2015-172732, JP-A-2014-199308, JP-A-2014-085562, JP-A-2014-035351, and JP-A-2008-081565.

[0291] The content of the pigment derivative is preferably 1 to 30 parts by mass per 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or greater, more preferably 3 parts by mass or greater. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. A single pigment derivative may be used, or two or more may be used in combination. When two or more pigment derivatives are used in combination, their total amount preferably falls within the above range.

[0292] <<Compounds having epoxy groups>>

[0293] The photosensitive resin composition of the present invention can contain a compound having an epoxy group (hereinafter also referred to as an epoxy compound). As the epoxy compound, a compound having one or more epoxy groups in one molecule can be mentioned, preferably a compound having two or more epoxy groups. The epoxy compound preferably has 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be set to 10 or less, or can be set to 5 or less. The lower limit of the number of epoxy groups is preferably two or more. As the epoxy compound, the compounds described in paragraphs 0034 to 0036 of Japanese Patent Application Publication No. 2013-011869, paragraphs 0147 to 0156 of Japanese Patent Application Publication No. 2014-043556, paragraphs 0085 to 0092 of Japanese Patent Application Publication No. 2014-089408, and the compounds described in Japanese Patent Application Publication No. 2017-179172 can also be used. These contents are incorporated into this specification.

[0294] The epoxy compound may be a low molecular weight compound (e.g., a molecular weight of less than 2000, or even less than 1000) or a high molecular weight compound (e.g., a molecular weight of 1000 or greater, or a weight average molecular weight of 1000 or greater in the case of a polymer). The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

[0295] Examples of commercially available epoxy compounds include EHPE3150 (manufactured by Daicel Corporation) and EPICLON N-695 (manufactured by DIC Corporation).

[0296] The epoxy compound content in the total solids content of the photosensitive resin composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or greater, and more preferably 1% by mass or greater. The upper limit is preferably 15% by mass or less, and even more preferably 10% by mass or less. The photosensitive resin composition may contain only one epoxy compound or two or more. When containing two or more epoxy compounds, their total amount preferably falls within the above range.

[0297] <<Furyl-containing compounds>>

[0298] The photosensitive resin composition of the present invention preferably contains a compound containing a furan group (hereinafter also referred to as a furan group-containing compound). According to this embodiment, a photosensitive resin composition having excellent curability at low temperatures can be obtained.

[0299] The furanyl-containing compound contains a furanyl group (a group formed by removing one hydrogen atom from furan), and its structure is not particularly limited. As the furanyl-containing compound, the compounds described in paragraphs 0049 to 0089 of JP-A-2017-194662 can be used. Furthermore, compounds described in JP-A-2000-233581, JP-A-1994-271558, JP-A-1994-293830, JP-A-1996-239421, JP-A-1998-508655, JP-A-2000-001529, JP-A-2003-183348, JP-A-2006-193628, JP-A-2007-186684, JP-A-2010-265377, JP-A-2011-170069, and the like can also be used.

[0300] The furan group-containing compound may be a monomer or a polymer. A polymer is preferred for reasons such as improving the durability of the resulting cured film. In the case of a polymer, the weight-average molecular weight is preferably 2,000 to 70,000. The upper limit is preferably 60,000 or less, more preferably 50,000 or less. The lower limit is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more. The polymeric furan group-containing compound is a component corresponding to the resin in the photosensitive resin composition of the present invention.

[0301] Examples of monomeric furanyl group-containing compounds (hereinafter also referred to as furanyl group-containing monomers) include compounds represented by the following formula (fur-1).

[0302] [Chemical Formula 21]

[0303]

[0304] Where Rf 1 represents a hydrogen atom or a methyl group, Rf 2 represents a divalent linking group.

[0305] As Rf 2 Examples of the divalent linking group represented include alkylene, arylene, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations of two or more thereof. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15 carbon atoms. The alkylene group may be linear, branched, or cyclic. The arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 10 carbon atoms. The alkylene and arylene groups may have substituents. Examples of the substituents include hydroxyl groups.

[0306] The furan group-containing monomer is preferably a compound represented by the following formula (fur-1-1).

[0307] [Chemical Formula 22]

[0308]

[0309] Where Rf 1 represents a hydrogen atom or a methyl group, Rf 11 Indicates -O- or -NH-, Rf 12 represents a single bond or a divalent linking group. 12 Examples of the divalent linking group represented include alkylene, arylene, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations of two or more thereof. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15 carbon atoms. The alkylene group may be linear, branched, or cyclic. The arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 10 carbon atoms. The alkylene and arylene groups may have substituents. Examples of the substituents include hydroxyl groups.

[0310] Specific examples of furanyl-containing monomers include compounds having the following structures. 1 represents a hydrogen atom or a methyl group.

[0311] [Chemical Formula 23]

[0312]

[0313] As a polymer-type furan group-containing compound (hereinafter also referred to as a furan group-containing polymer), a resin containing a repeating unit containing a furan group is preferred, and a resin containing a repeating unit derived from a compound represented by the above formula (fur-1) is more preferred. The concentration of the furan group in the furan group-containing polymer is preferably 0.5 to 6.0 mmol per 1 g of the furan group-containing polymer, and more preferably 1.0 to 4.0 mmol. If the concentration of the furan group is 0.5 mmol or more, preferably 1.0 mmol or more, it is easy to form pixels having excellent solvent resistance and the like. As long as the concentration of the furan group is 6.0 mmol or less, and preferably 4.0 mmol or less, the temporal stability of the photosensitive resin composition is good.

[0314] In addition to repeating units containing furan groups, furanyl-containing polymers may also contain repeating units containing acid groups and / or repeating units containing polymerizable groups. Examples of the acid groups include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. Examples of polymerizable groups include groups containing ethylenically unsaturated bonds such as vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. When the furanyl-containing polymer contains repeating units containing acid groups, its acid value is preferably 10 to 200 mgKOH / g, and more preferably 40 to 130 mgKOH / g.

[0315] When the furan group-containing polymer contains a repeating unit having a polymerizable group, it is easier to form pixels having excellent solvent resistance and the like.

[0316] The furan group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of JP-A-2017-194662.

[0317] The content of the furanyl-containing compound in the total solid content of the photosensitive resin composition is preferably 0.1 to 70 mass%. The lower limit is preferably 2.5 mass% or more, more preferably 5.0 mass% or more, and even more preferably 7.5 mass% or more. The upper limit is preferably 65 mass% or less, more preferably 60 mass% or less, and even more preferably 50 mass% or less. Furthermore, when a furanyl-containing polymer is used as the furanyl-containing compound, the content of the furanyl-containing polymer in the resin contained in the photosensitive resin composition is preferably 0.1 to 100 mass%. The lower limit is preferably 10 mass parts or more, more preferably 15 mass parts or more. The upper limit is preferably 90 mass parts or less, more preferably 80 mass parts or less, and even more preferably 70 mass parts or less. The furanyl-containing compound may be only one or two or more. When there are two or more, the total amount is preferably within the above range.

[0318] <<Silane coupling agent>>

[0319] The photosensitive resin composition of the present invention may contain a silane coupling agent. In the present invention, a silane coupling agent refers to a silane compound having a hydrolyzable group and functional groups other than the hydrolyzable group. Furthermore, a hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can produce a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, and the like, preferably alkoxy groups. That is, the silane coupling agent preferably includes a compound having an alkoxysilyl group. Furthermore, 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, urea groups, thioether groups, isocyanate groups, phenyl groups, and the like, preferably amino groups, (meth)acryloyl groups, and epoxy groups. Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604, and the contents thereof are incorporated into the present specification.

[0320] The content of the silane coupling agent in the total solids content of the photosensitive resin composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be present in a single species or in two or more species. When two or more species are present, the total amount is preferably within the above range.

[0321] <<Curing accelerator>>

[0322] The photosensitive resin composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include polyfunctional thiol compounds having two or more mercapto groups in the molecule. Polyfunctional thiol compounds may be added to improve stability, odor, resolution, developability, adhesion, etc. Polyfunctional thiol compounds are preferably secondary alkane thiols, and more preferably compounds represented by formula (T1).

[0323] Formula (T1)

[0324] [Chemical Formula 24]

[0325]

[0326] (In formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)

[0327] In formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, and particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.

[0328] Furthermore, the curing accelerator may also include hydroxymethyl compounds (e.g., compounds exemplified as crosslinking agents in paragraph 0246 of Japanese Patent Application Laid-Open No. 2015-034963), amines, phosphonium salts, amidine salts, amide compounds (e.g., curing agents described in paragraph 0186 of Japanese Patent Application Laid-Open No. 2013-041165), base generators (e.g., ionic compounds described in Japanese Patent Application Laid-Open No. 2014-055114), cyanate compounds (e.g., For example, the compound described in paragraph 0071 of Japanese Patent Application Laid-Open No. 2012-150180), alkoxysilane compounds (for example, the alkoxysilane compound having an epoxy group described in Japanese Patent Application Laid-Open No. 2011-253054), onium salt compounds (for example, the compound exemplified as the acid generator in paragraph 0216 of Japanese Patent Application Laid-Open No. 2015-034963, the compound described in Japanese Patent Application Laid-Open No. 2009-180949), etc.

[0329] The content of the curing accelerator in the total solid content of the photosensitive resin composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.

[0330] <<Polymerization Inhibitor>>

[0331] The photosensitive resin composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, guanidine salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solids content of the photosensitive resin composition is preferably 0.0001 to 5% by mass.

[0332] <<Surfactants>>

[0333] The photosensitive resin composition of the present invention may contain a surfactant. Examples of surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. Examples of surfactants include those described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which are incorporated herein by reference.

[0334] In the present invention, the surfactant is preferably a fluorinated surfactant. Including a fluorinated surfactant in the photosensitive resin composition can further enhance liquid properties (particularly fluidity) and improve liquid conservation. Furthermore, it can form a cured film with minimal thickness variations.

[0335] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorine-based surfactants having a fluorine content within this range are effective from the perspectives of uniformity of coating film thickness and liquid conservation, and also have good solubility in the photosensitive resin composition.

[0336] Examples of the fluorine-based surfactant include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-041318 (paragraphs 0060 to 0064 of the corresponding WO 2014 / 017669), and surfactants described in paragraphs 0117 to 0132 of JP-A-2011-132503, the contents of which are incorporated herein. Examples of commercially available fluorochemical surfactants include MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, and MFS-330 (all manufactured by DIC Corporation), FLUORAD FC430, FC431, and 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, and KH-40 (all manufactured by AGC Inc.), and PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), etc.

[0337] Furthermore, as for fluorine-based surfactants, polymers of vinyl ether compounds containing fluorine atoms having a fluorinated alkyl or fluorinated alkylene ether group and a hydrophilic vinyl ether compound are also preferably used. These fluorine-based surfactants include the fluorine-based surfactants described in Japanese Patent Application Laid-Open No. 2016-216602, which are incorporated herein by reference.

[0338] Fluorine-based surfactants can also be block polymers. Fluorine-based surfactants can also preferably be fluorine-containing polymers containing repeating units derived from a (meth)acrylate compound having fluorine atoms and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy or propyleneoxy groups). Examples of fluorine-based surfactants used in the present invention include those described in paragraphs 0016 to 0037 of JP-A-2010-032698 or the following compounds.

[0339] [Chemical Formula 25]

[0340]

[0341] The weight average molecular weight of the compound is preferably 3000 to 50000, for example, 14000. In the compound, % indicating the ratio of the repeating unit is mol %.

[0342] Furthermore, fluoropolymers having a group containing an ethylenically unsaturated bond in a side chain can also be used as fluorochemical surfactants. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, and MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K manufactured by DIC Corporation. Furthermore, the compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Laid-Open No. 2015-117327 can also be used as fluorochemical surfactants.

[0343] Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid 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 Japan Lubrizol Corporation), NCW-101, NCW-1001, and NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

[0344] Examples of the silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF-6001, and KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK-Chemie Corporation).

[0345] The content of the surfactant in the total solid content of the photosensitive resin composition is preferably 0.001% to 5.0% by mass, more preferably 0.005% to 3.0% by mass. The surfactant may be a single surfactant or two or more surfactants. When two or more surfactants are present, the total amount is preferably within the above range.

[0346] <<Antioxidants>>

[0347] The photosensitive resin composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant may be used. Preferred phenol compounds include hindered phenol compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Furthermore, the antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. Furthermore, as the antioxidant, a phosphorus-based antioxidant may be preferably used.

[0348] The content of the antioxidant in the total solid content of the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. One antioxidant may be used alone, or two or more may be used. When two or more antioxidants are used, the total amount is preferably within the above range.

[0349] <<Other ingredients>>

[0350] The photosensitive resin composition of the present invention may contain a sensitizer, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.) as needed. By appropriately containing these ingredients, the physical properties of the film can be adjusted. These ingredients can be, for example, described in paragraphs 0183 and later of Japanese Unexamined Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Unexamined Patent Application Publication No. 2008-250074, and these contents are incorporated into this specification. In addition, the photosensitive resin composition of the present invention may contain a potential antioxidant as needed. As a potential antioxidant, a compound in which the site having the function of an antioxidant is protected by a protecting group can be cited, and the compound is heated at 100 to 250° C., or heated at 80 to 200° C. in the presence of an acid / salt-based catalyst, whereby the protecting group is separated and acts as an antioxidant. As a potential antioxidant, the compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 can be cited. As a commercially available product of a potential antioxidant, ADEKA ARKLS GPA-5001 (manufactured by ADEKA Corporation) can be cited. Furthermore, as described in Japanese Patent Application Publication No. 2018-155881, CI Pigment Yellow 129 can be added for the purpose of improving weather resistance.

[0351] To adjust the refractive index of the resulting cured film, the photosensitive resin composition of the present invention may contain a metal oxide. Examples of the metal oxide include TiO2, ZrO2, Al2O3, and SiO2. The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

[0352] The photosensitive resin composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraphs 0036 to 0037 of Japanese Patent Application Laid-Open No. 2017-198787, the compounds described in paragraphs 0029 to 0034 of Japanese Patent Application Laid-Open No. 2017-146350, the compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of Japanese Patent Application Laid-Open No. 2017-129774, and the compounds described in paragraphs 0049 to 0052 of Japanese Patent Application Laid-Open No. 201 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 JP-A-2017-186546. The compounds described in paragraphs 0034 to 0047 of the publication, the compounds described in paragraphs 0019 to 0041 of JP-A-2015-025116, the compounds described in paragraphs 0101 to 0125 of JP-A-2012-145604, the compounds described in paragraphs 0018 to 0021 of JP-A-2012-103475, the compounds described in paragraphs 0019 to 0041 of JP-A-2011 The compounds described in paragraphs 0015 to 0018 of JP-A-257591, the compounds described in paragraphs 0017 to 0021 of JP-A-2011-191483, the compounds described in paragraphs 0108 to 0116 of JP-A-2011-145668, the compounds described in paragraphs 0103 to 0153 of JP-A-2011-253174, and the like.

[0353] The photosensitive resin composition of the present invention preferably contains free metals not bound or coordinated to pigments or the like, preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 10 ppm or less, and particularly preferably substantially no metals. This embodiment can be expected to achieve effects such as stabilization of pigment dispersibility (suppression of aggregation), improved spectral properties associated with improved dispersibility, stabilization of curable components, suppression of conductivity fluctuations associated with the elution of metal atoms and metal ions, and improved display properties. In addition, the effects described in Japanese Patent Publication No. 2012-153796, Japanese Patent Publication No. 2000-345085, Japanese Patent Publication No. 2005-200560, Japanese Patent Publication No. 08-043620, Japanese Patent Publication No. 2004-145078, Japanese Patent Publication No. 2014-119487, Japanese Patent Publication No. 2010-083997, Japanese Patent Publication No. 2017-090930, Japanese Patent Publication No. 2018-025612, Japanese Patent Publication No. 2018-025797, Japanese Patent Publication No. 2017-155228, Japanese Patent Publication No. 2018-036521, etc. can also be obtained. Examples of the above-mentioned 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 resin composition of the present invention preferably contains free halogens not bound or coordinated to pigments, etc., at a content of 100 ppm or less, more preferably 50 ppm or less, even more preferably 10 ppm or less, and particularly preferably contains substantially no halogens. Examples of halogens include F, Cl, Br, I, and their anions. Methods for reducing the free metal or halogen content in the photosensitive resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.

[0354] The photosensitive resin composition of the present invention also preferably contains substantially no terephthalate, where “substantially no” means that the content of terephthalate in the total amount of the photosensitive resin composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0355] The water content of the photosensitive resin composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

[0356] The photosensitive resin composition of the present invention can be used with viscosity adjusted for purposes such as adjusting the film surface shape (flatness, etc.) and film thickness. The viscosity value can be appropriately selected as needed, but is preferably 0.3 mPa·s to 50 mPa·s, and more preferably 0.5 mPa·s to 20 mPa·s at 25°C. Viscosity can be measured, for example, using a viscometer RE85L (rotor: 1°34' x R24, measuring range: 0.6 to 1200 mPa·s) manufactured by TOKI SANGYO CO., LTD., at 25°C.

[0357] When the photosensitive resin composition of the present invention is used as a color filter for a liquid crystal display device, the voltage holding ratio of the liquid crystal display element having the color filter is preferably 70% or more, more preferably 90% or more. Known methods for obtaining a high voltage holding ratio can be appropriately combined. Typical methods include using high-purity raw materials (for example, reducing ionic impurities) and controlling the amount of acidic functional groups in the composition. The voltage holding ratio can be measured, for example, by the method described in paragraph 0243 of Japanese Patent Application Publication No. 2011-008004 and paragraphs 0123 to 0129 of Japanese Patent Application Publication No. 2012-224847.

[0358] Storage container

[0359] The container for storing the photosensitive resin composition of the present invention is not particularly limited, and known containers can be used. Furthermore, to prevent impurities from entering the raw materials or the photosensitive resin composition, a multilayer bottle having an inner wall composed of six layers of six different resins, or a bottle having a seven-layer structure of six different resins, is preferably used as the container. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351. Furthermore, to prevent metal from eluting from the inner wall of the container, improve the storage stability of the photosensitive resin composition, or inhibit deterioration of the components, the inner wall of the container is preferably made of glass or stainless steel.

[0360] <Method for preparing photosensitive resin composition>

[0361] The photosensitive resin composition of the present invention can be prepared by mixing the aforementioned components. When preparing the photosensitive resin composition, all components may be dissolved and / or dispersed simultaneously in a solvent to prepare the photosensitive resin composition. Alternatively, the photosensitive resin composition may be prepared by appropriately preparing two or more solutions or dispersions of the components as needed and mixing these solutions or dispersions at the time of use (during coating).

[0362] Furthermore, when preparing the photosensitive resin composition, it is preferred to include a process for dispersing the pigment. In the process for dispersing the pigment, compression, pressing, impact, shearing, cavitation, etc. can be cited as mechanical forces for dispersing the pigment. Specific examples of these processes include bead milling, sand milling, roller milling, ball milling, paint stirring, micro jetting, high-speed impellers, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, etc. Furthermore, in the pulverization of the pigment under sand milling (bead milling), it is preferred to process under the following conditions, which are to improve the pulverization efficiency by using microbeads with a small diameter and increasing the filling rate of the microbeads. Furthermore, it is preferred to remove coarse particles by filtration, centrifugation, etc. after the pulverization process. Furthermore, the pigment dispersion process and disperser described in "Dispersion Technology Encyclopedia, Published by JOHOKIKO CO., LTD., July 15, 2005," "Dispersion Technology and Industrial Practical Applications Focused on Suspensions (Solid / Liquid Dispersion Systems), Comprehensive Data Collection, Business Development Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Application Publication No. 2015-157893 can be preferably used. Furthermore, in the pigment dispersion process, particle refinement can be achieved through a salt milling step. For information on the raw materials, equipment, and processing conditions used in the salt milling step, reference can be made to the descriptions of, for example, Japanese Patent Application Publications Nos. 2015-194521 and 2012-046629.

[0363] When preparing a photosensitive resin composition, it is preferred to filter the photosensitive resin composition through a filter for the purpose of removing foreign matter or reducing defects. As a filter, any filter that has been used for filtering purposes can be used without particular limitation. For example, filters using materials such as fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high molecular weight polyolefin resins) can be cited. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0364] 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. As long as the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. Regarding the pore size value of the filter, the nominal value of the filter manufacturer can be referred to. Various filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (Formerly Nippon micro squirrel Co., Ltd.), KITZMICROFILTER CORPORATION, etc. can be used as the filter.

[0365] Furthermore, it is also preferable to use a fibrous filter material as the filter. Examples of fibrous filter materials include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include the SBP series (SBP008, etc.), TPR series (TPR002, TPR005, etc.), and SHPX series (SHPX003, etc.) manufactured by ROKI TECHNO CO., LTD.

[0366] When using filters, different filters (e.g., a first filter and a second filter) may be combined. In this case, filtration using each filter may be performed only once or twice or more. Furthermore, filters with different pore sizes within the above-mentioned range may be combined. Alternatively, the first filter may be used to filter only the dispersion, and after mixing the other components, filtration may be performed using the second filter.

[0367] <Cured film>

[0368] The cured film of the present invention is a cured film obtained from the photosensitive resin composition of the present invention described above. The cured film of the present invention can be preferably used as a colored pixel of a color filter. Cyan pixels are preferred as colored pixels. The thickness of the cured film of the present invention can be appropriately adjusted depending on the intended 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.

[0369] The cured film of the present invention preferably has an average transmittance of light with a wavelength of 400 to 530 nm in the thickness direction of the film of 70% or more, more preferably 80% or more, and even more preferably 85% or more. Furthermore, the minimum value of the transmittance of light with a wavelength of 400 to 530 nm in the thickness direction of the film is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more. Furthermore, the average transmittance of light with a wavelength of 610 to 700 nm in the thickness direction of the film is preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less. Furthermore, the maximum value of the transmittance of light with a wavelength of 610 to 700 nm in the thickness direction of the film is preferably 40% or less, more preferably 30% or less, and even more preferably 25% or less.

[0370] The cured film of the present invention preferably has a transmittance peak in the wavelength range of 400 to 530 nm in the transmission spectrum of light in the thickness direction of the film with respect to wavelengths in the range of 400 to 700 nm. Furthermore, it is preferred that a wavelength at which the transmittance reaches 50% of the peak value (hereinafter referred to as λ) be present in the wavelength range of 540 to 600 nm. T50 ). In addition, it is preferred that there is a wavelength in the wavelength range of 560 to 620 nm where the transmittance reaches 20% of the peak value (hereinafter, this wavelength is also referred to as λ T20 ). T50 It preferably exists in the wavelength range of 545 to 595 nm, and more preferably exists in the wavelength range of 550 to 590 nm. T20 It is preferably present in the wavelength range of 565 to 615 nm, and more preferably in the wavelength range of 560 to 610 nm. T 20 and λ T50 The difference (λ T20 -λ T50 ) is preferably 5 to 80 nm, more preferably 7 to 50 nm, and further preferably 10 to 30 nm.

[0371] Color Filters

[0372] Next, the color filter of the present invention will be described. The color filter of the present invention comprises the cured film of the present invention described above. More preferably, the pixels of the color filter comprise the cured film of the present invention. Even more preferably, the cyan pixels of the color filter comprise the cured film of the present invention. The color filter of the present invention can be used in solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), image display devices, and the like.

[0373] The thickness of the cured film of the present invention in the color filter of the present invention can be appropriately adjusted depending on the intended purpose. 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.

[0374] The pixel width of the color filter of the present invention is preferably 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or greater, more preferably 2.0 μm or greater. The upper limit is preferably 15.0 μm or less, more preferably 10.0 μm or less. Furthermore, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.

[0375] Each pixel included in the color filter of the present invention preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less. There is no regulation on the lower limit, but for example, it is preferably 0.1 nm or more. Regarding the surface roughness of the pixel, it can be measured, for example, using AFM (atomic force microscope) Dimension3100 manufactured by Veeco. In addition, the water contact angle on the pixel can be appropriately set to a preferred value, usually in the range of 50 to 110°. The contact angle can be measured, for example, using a contact angle meter CV-DT·A type (manufactured by Kyowa Interface Science Co., LTD.). In addition, the volume resistance value of the pixel is preferably high. Specifically, the volume resistance value of the pixel is preferably 10 9 Ω·cm or more, more preferably 10 11 Ω·cm or more. The upper limit is not specified, for example, it is preferably 10 14 The volume resistance value of a pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by ADVANTEST CORPORATION).

[0376] Furthermore, in the color filter of the present invention, a protective layer can be provided on the surface of the cured film of the present invention. By providing a protective layer, various functions such as oxidation resistance, low reflectivity, hydrophilicity / hydrophobicity, and shielding of light of specific wavelengths (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. As a method for forming the protective layer, a method of forming by coating a resin composition dissolved in an organic solvent, a chemical vapor deposition method, a method of bonding a formed resin with an adhesive material, etc. can be cited. As the component constituting the protective layer, (methyl) acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, polyurethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al2O3, Mo, SiO2, Si2N4, etc., can also contain two or more of these components. For example, in the case of a protective layer for the purpose of anti-oxidation, the protective layer preferably contains polyol resin, SiO2, Si2N4. And, in the case of a protective layer for the purpose of low reflection, it is preferred that the protective layer contains (methyl) acrylic resin and fluororesin.

[0377] When coating resin composition forms protective layer, as the coating method of resin combination, known methods such as spin coating, casting, screen printing, inkjet method can be used. Organic solvent contained in resin combination can use known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate etc.). When utilizing chemical vapor deposition to form protective layer, as chemical vapor deposition, known chemical vapor deposition (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used.

[0378] The protective layer may contain additives such as organic and inorganic particles, absorbers of specific wavelengths (e.g., ultraviolet rays, near infrared rays, etc.), refractive index regulators, antioxidants, adhesives, surfactants, etc. as needed. Examples of organic and inorganic particles include polymer particles (e.g., silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silicon dioxide, calcium carbonate, barium sulfate, etc. Known absorbers of specific wavelengths can be used. As ultraviolet absorbers and near infrared absorbers, the above-mentioned raw materials can be mentioned. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass relative to the total mass of the protective layer, and more preferably 1 to 60% by mass.

[0379] Furthermore, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Laid-Open No. 2017-151176 can also be used.

[0380] <Color filter manufacturing method>

[0381] The color filter of the present invention can be produced by forming a colored composition layer on a support using the photosensitive resin composition of the present invention, and patterning the photosensitive resin composition by photolithography.

[0382] Pattern formation using photolithography preferably includes the following steps: forming a photosensitive resin composition layer on a support using the photosensitive resin composition of the present invention; exposing the photosensitive resin composition layer in a pattern; and developing and removing unexposed portions of the photosensitive resin composition layer to form a pattern (pixels). Optionally, a step of baking the photosensitive resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

[0383] In the process of forming a photosensitive resin composition layer, a photosensitive resin composition of the present invention is used to form a photosensitive resin composition layer on a support. As a support, there is no particular limitation and it can be appropriately selected according to the purpose. For example, a glass substrate, a silicon substrate, etc. can be mentioned, preferably a silicon substrate. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. can be formed on the substrate. In addition, a black matrix is sometimes formed on the silicon substrate to isolate each pixel. In addition, a primer layer can also be provided on the silicon substrate to improve the adhesion to the upper layer, prevent the diffusion of the substance, or planarize the substrate surface.

[0384] As a method for applying the colored photosensitive composition, known methods can be used. Examples include a drop casting method; a slit coating method; a spray method; a roll coating method; a spin coating method; a cast coating method; a slit and spin method; a pre-wetting method (e.g., the method described in Japanese Patent Application Laid-Open No. 2009-145395); various printing methods such as inkjet printing (e.g., drop-on-demand, piezoelectric, and thermal), ejection printing such as nozzle jetting, flexographic printing, screen printing, gravure printing, reverse overprinting, and metal mask printing; transfer methods using a mold, etc.; and nanoimprinting. The applicable inkjet method is not particularly limited, and examples thereof include the method described in "Inkjet for General Use - Infinite Possibilities Emerging from Patents -" published in February 2005 by Sumitbe Techon Research Co., Ltd. (particularly pages 115 to 133), or methods described in Japanese Patent Application Publication Nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-169325. Furthermore, methods described in International Publication Nos. 2017 / 030174 and 2017 / 018419 can also be used for coating the photosensitive resin composition, and the contents of these publications are incorporated herein.

[0385] The photosensitive resin composition layer formed on the support can be dried (prebaked). Prebaking can also be performed when a cured film is produced by a low-temperature process. When prebaking is performed, the prebaking temperature is preferably 150°C or less, more preferably 120°C or less, and further preferably 110°C or less. The lower limit can be set to, for example, 50°C or more, or 80°C or more. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Prebaking can be performed on a hot plate, an oven, or the like.

[0386] Next, the photosensitive resin composition layer is exposed in a pattern (exposure step). For example, a stepper or scanner is used to expose the photosensitive resin composition layer through a mask having a predetermined mask pattern, thereby exposing the layer in a pattern. This allows the exposed portion to be cured.

[0387] Examples of radiation (light) that can be used for exposure include g-rays and i-rays. Furthermore, 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. Furthermore, light sources with a wavelength of 300 nm or more can also be used.

[0388] Moreover, during exposure, exposure can be performed by continuous light irradiation or by pulsed light irradiation (pulse exposure). In addition, pulse exposure refers to an exposure method in which exposure is performed by repeatedly irradiating light and pausing within a short period of time (for example, less than milliseconds). During pulse exposure, the pulse width is preferably less than 100 nanoseconds (ns), more preferably less than 50 nanoseconds, and further preferably less than 30 nanoseconds. The lower limit of the pulse width is not particularly limited, but can be set to more than 1 femtosecond (fs), and can also be set to more than 10 femtoseconds. The frequency is preferably more than 1kHz, more preferably more than 2kHz, and further preferably more than 4kHz. The upper limit of the frequency is preferably less than 50kHz, more preferably less than 20kHz, and further preferably less than 10kHz. The maximum instantaneous illumination is preferably 50,000,000W / m 2 More than 100000000 W / m 2 More than, more preferably 200000000 W / m 2 Furthermore, the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W / m 2 Below, more preferably 800000000 W / m 2 Below, more preferably 500000000 W / m 2 Below. Furthermore, pulse width refers to the duration of light irradiation during a pulse cycle. Furthermore, frequency refers to the number of pulse cycles per second. Furthermore, maximum instantaneous illuminance refers to the average illuminance during the duration of light irradiation during a pulse cycle. Furthermore, pulse cycle refers to the period of light irradiation and pause during pulse exposure, which is defined as one cycle.

[0389] The irradiation dose (exposure dose) is preferably 0.03 to 2.5 J / cm 2 , more preferably 0.05 to 1.0 J / cm 2The oxygen concentration during exposure can be appropriately selected. In addition to exposure in the atmosphere, exposure can be performed in a low-oxygen environment 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 environment with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). Furthermore, the exposure illuminance can be appropriately set, typically from 1000 W / m 2 ~100000W / m 2 (For example, 5000W / m 2 、15000W / m 2 or 35000W / m 2 The oxygen concentration and exposure illuminance can be appropriately combined, for example, the oxygen concentration can be set to 10% by volume and the illuminance can be set to 10000 W / m 2 , oxygen concentration 35% by volume and illumination 20,000 W / m 2 wait.

[0390] Next, the unexposed portion of the photosensitive resin composition layer is removed by development to form a pattern (pixel). The unexposed portion of the photosensitive resin composition layer can be removed by development using a developer. As a result, the unexposed portion of the photosensitive resin composition layer in the exposure process is dissolved in the developer, and only the photocured portion remains. The temperature of the developer is preferably 20 to 30°C, for example. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removability of residues, the process of shaking off the developer every 60 seconds and then supplying a new developer can be repeated multiple times.

[0391] Developer can include organic solvents, alkaline developers, etc., and alkaline developers are preferably used. As alkaline developers, it is preferred to dilute the alkaline aqueous solution (alkaline developer) of the alkaline agent with pure water. As alkali agents, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and other organic alkaline compounds or inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate. From the perspective of environmental and safety aspects, the alkali agent is preferably a compound with a larger molecular weight. 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. Furthermore, the developer may further contain a surfactant. As the surfactant, the above-mentioned surfactants can be mentioned, preferably a nonionic surfactant. From the viewpoint of convenient transfer or storage, the developer can be temporarily prepared as a concentrated solution and diluted to the required concentration when used. The dilution ratio is not particularly limited, for example, it can be set in the range of 1.5 to 100 times. Furthermore, it is also preferred to wash (rinse) with pure water after development. Furthermore, it is preferred to rinse by supplying a rinsing liquid to the developed photosensitive resin composition layer while rotating the support on which the developed photosensitive resin composition layer is formed. Furthermore, it is also preferred to rinse by moving the nozzle that sprays the rinsing liquid from the center of the support to the peripheral portion of the support. At this time, when the nozzle moves from the center of the support to the peripheral portion, it can be moved while gradually reducing the movement speed of the nozzle. By rinsing in this way, the in-plane deviation of the rinsing can be suppressed. Furthermore, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the center of the support to the peripheral portion.

[0392] It is preferred that additional exposure treatment and heating treatment (post-baking) be performed after development and drying. Additional exposure treatment and post-baking are curing treatments after development for complete curing. The heating temperature during post-baking is preferably, for example, 100 to 240°C, more preferably 200 to 240°C. Post-baking can be performed continuously or intermittently on the developed film using a heating mechanism such as a hot plate or a convection oven (hot air circulation dryer), a high-frequency heater, etc. in a manner such that the above conditions are achieved. When additional exposure treatment is performed, the light used in the exposure is preferably light with a wavelength of 400nm or less. Furthermore, the additional exposure treatment can be performed by the method described in Korean Patent Gazette No. 10-2017-0122130.

[0393] Solid-state imaging devices

[0394] The solid-state imaging device of the present invention includes the cured film of the present invention. A preferred embodiment of the solid-state imaging device includes an embodiment in which the cured film of the present invention is a cyan pixel and further includes a yellow pixel and a magenta pixel.

[0395] The structure of the solid-state imaging element of the present invention is not particularly limited as long as it includes the cured film of the present invention and functions as a solid-state imaging element. Examples thereof include the following structures.

[0396] The imaging element has the following structure: a substrate has a plurality of photodiodes and a transfer electrode composed of polysilicon, etc., which constitute the light-receiving area of a solid-state imaging element (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.); a light-shielding film having an opening only for the light-receiving portion of the photodiode is provided on the photodiode and the transfer electrode; a device protection film composed of silicon nitride, etc., formed so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode is provided on the light-shielding film; and a color filter is provided on the device protection film. Alternatively, a structure may include a light-focusing mechanism (e.g., a microlens, etc., the same applies hereinafter) on the device protection film and below the color filter (on the side closer to the substrate), or a structure may include a light-focusing mechanism on the color filter. Furthermore, the color filter may have a structure in which each colored pixel is embedded in a space separated by partitions, such as a grid pattern. Preferably, the refractive index of the partitions in this case is lower than the refractive index of each colored pixel. Examples of imaging devices having such a structure include those described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, International Publication No. 2018 / 043654, and U.S. Patent Application Publication No. 2018 / 0040656. Imaging devices including the solid-state imaging element of the present invention can be used as digital cameras, electronic devices with imaging functions (such as mobile phones), in-vehicle cameras, and surveillance cameras.

[0397] <Image Display Device>

[0398] The image display device of the present invention comprises the cured film of the present invention described above. Examples of the image display device include liquid crystal display devices and organic electroluminescent display devices. The definition of an image display device or details of each image display device are described, for example, in "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)" and "Display Devices (written by Junsho Ibuki, published by Sangyo Tosho Publishing Co., Ltd. in 1989)." Furthermore, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. in 1994)." There are no particular limitations on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to liquid crystal display devices of various types described in the aforementioned "Next Generation Liquid Crystal Display Technology."

[0399] Example

[0400] Below, give embodiment and the present invention is further specifically described.The material, usage amount, ratio, processing content, processing procedure etc. shown in the following examples can be appropriately changed as long as it does not depart from the purpose of the present invention.Therefore, the scope of the present invention is not limited to the specific example shown below.

[0401] <Measurement of weight average molecular weight (Mw)>

[0402] The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (GPC) under the following conditions.

[0403] Column type: A column combining TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000

[0404] Developing solvent: tetrahydrofuran

[0405] Column temperature: 40°C

[0406] Flow rate (sample injection volume): 1.0 μL (sample concentration 0.1 mass %)

[0407] Device name: HLC-8220GPC manufactured by TOSOH CORPORATION

[0408] Detector: RI (refractive index) detector

[0409] Calibration curve base resin: polystyrene resin

[0410] <Acid value measurement method>

[0411] The sample was dissolved in a 9 / 1 (mass ratio) tetrahydrofuran / water mixture and the resulting solution was neutralized and titrated with a 0.1 mol / L sodium hydroxide aqueous solution at 25°C using a potentiometric titrator (product name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.). The inflection point of the titration pH curve was used as the titration endpoint, and the acid value was calculated using the following formula.

[0412] A=56.11×Vs×0.1×f / w

[0413] A: Acid value (mgKOH / g)

[0414] Vs: The amount of 0.1 mol / L sodium hydroxide solution required for titration (mL)

[0415] f: titration of 0.1 mol / l sodium hydroxide aqueous solution

[0416] w: Mass of the measured sample (g) (converted to solid content)

[0417] <Amine value measurement method>

[0418] The sample was dissolved in acetic acid and the resulting solution was neutralized and titrated with a 0.1 mol / L perchloric acid / acetic acid solution at 25°C using a potentiometric titrator (product name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.). The inflection point of the titration pH curve was used as the titration endpoint, and the amine value was calculated using the following formula.

[0419] B=56.11×Vs×0.1×f / w

[0420] B: Amine value (mgKOH / g)

[0421] Vs: The amount of 0.1 mol / L perchloric acid / acetic acid solution required for titration (mL)

[0422] f: titration of 0.1 mol / L perchloric acid / acetic acid solution

[0423] w: Mass of the measured sample (g) (converted to solid content)

[0424] <Method for measuring the average secondary particle size of pigments>

[0425] The average secondary particle size of the pigment was measured by directly measuring the size of the secondary particles of the pigment from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the secondary particles of each pigment were measured, and the average was used as the particle size of the pigment. Then, for each of 100 pigments, the volume of each pigment was calculated using a cube approximating the obtained particle size, and the volume average particle size was used as the average secondary particle size.

[0426] <Preparation of Photosensitive Resin Composition>

[0427] The colorants listed in the following table, the dispersants listed in the following table, and a portion of the solvents listed in the following table were mixed, 230 parts by mass of zirconia microbeads with a diameter of 0.3 mm were added, and a dispersion treatment was performed using a paint shaker for 5 hours. The microbeads were then separated by filtration to prepare a pigment dispersion having a solid content of 20% by weight.

[0428] Next, the resulting pigment dispersion was mixed with the residual solvent of the type listed in the table below, the post-addition resin of the type listed in the table below, the polymerizable compound of the type listed in the table below, the photopolymerization initiator of the type listed in the table below, and the UV absorber of the type listed in the table below to prepare a photosensitive resin composition. The following table shows the amount of each component in the photosensitive resin composition. The values for each component are in parts by mass. Also shown are the total content (mass %) of CI Pigment Blue 15:3 (PB15:3) and CI Pigment Blue 15:4 (PB15:4) in the colorant, the content (mass %) of the UV absorber in the total solids of the photosensitive composition, the content (mass %) of the UV absorber per 100 parts by mass of the photopolymerization initiator, and the content (mass %) of the UV absorber per 100 parts by mass of the polymerizable compound. The Yellow and Magenta compositions shown in the following table are the photosensitive resin compositions for color mixing evaluation described below.

[0429] [Table 1]

[0430]

[0431] [Table 2]

[0432]

[0433] In the above table, the raw materials described by abbreviations are as follows.

[0434] (colorant)

[0435] PB15:3: CI Pigment Blue 15:3 (average secondary particle size 68nm)

[0436] PB15:4: CI Pigment Blue 15:4 (average secondary particle size 71nm)

[0437] PcAl: Compound with the following structure (aluminum phthalocyanine, average secondary particle size 94 nm)

[0438] [Chemical Formula 26]

[0439]

[0440] PY150: CI Pigment Yellow 150 (average secondary particle size 81nm)

[0441] PG7: CI Pigment Green 7 (average secondary particle size 80nm)

[0442] PR122: CI Pigment Red 122 (average secondary particle size 67nm)

[0443] (Dispersant, post-added resin)

[0444] P1: DISPERBYK-2001 (manufactured by BYK Japan KK, acid value 19 mgKOH / g, amine value 29 mgKOH / g, acrylic resin)

[0445] P2: Efka PX 4300 (manufactured by BASF, amine value 57 mgKOH / g, acrylic resin)

[0446] P3: Resin with the following structure (weight average molecular weight = 10,000, acid value 31.5 mgKOH / g, amine value 0 mgKOH / g, the numerical value indicated on the main chain represents the molar ratio of the repeating unit.)

[0447] [Chemical Formula 27]

[0448]

[0449] P4: Resin with the following structure (weight average molecular weight = 24,000, acid value 52.5 mgKOH / g, amine value 0 mgKOH / g, the numerical value marked on the main chain represents the molar ratio of the repeating unit, and the numerical value marked on the side chain represents the number of repeating units.)

[0450] [Chemical Formula 28]

[0451]

[0452] P5: Resin with the following structure (weight average molecular weight = 21000, acid value 36.0 mgKOH / g, amine value 47 mgKOH / g, x = 48, y = 12, a / b / c / d / e = 36 / 4 / 35 / 1 / 24 (molar ratio))

[0453] [Chemical Formula 29]

[0454]

[0455] P6: Resin with the following structure (weight average molecular weight = 12000, acid value 195.4 mgKOH / g, amine value 0 mgKOH / g, the numerical value indicated on the main chain represents the molar ratio of the repeating unit.)

[0456] [Chemical formula 30]

[0457]

[0458] (Polymerizable compound)

[0459] M1: Compound with the following structure

[0460] [Chemical Formula 31]

[0461]

[0462] M2: A mixture of compounds of the following structures (compound on the left: compound on the right = 7:3 (mass ratio))

[0463] [Chemical Formula 32]

[0464]

[0465] M3: Compound with the following structure (l+m+n+o+p+q=12)

[0466] [Chemical Formula 33]

[0467]

[0468] M4: Compound with the following structure

[0469] [Chemical Formula 34]

[0470]

[0471] (Photopolymerization initiator)

[0472] I1: Compound with the following structure (α-amino ketone compound)

[0473] I2: Compound (oxime compound) having the following structure

[0474] [Chemical Formula 35]

[0475]

[0476] (UV absorber)

[0477] U1: Compound of the following structure (conjugated diene compound)

[0478] U2: Compound with the following structure (triazine compound)

[0479] U3: Compound with the following structure (benzotriazole compound)

[0480] [Chemical Formula 36]

[0481]

[0482] (Surfactant)

[0483] W1: Compound of the following structure (fluorinated surfactant, weight average molecular weight = 14,000, % indicating the ratio of repeating units is mol %)

[0484] [Chemical Formula 37]

[0485]

[0486] (Other additives)

[0487] X1: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (a compound or epoxy compound having the following structure)

[0488] [Chemical Formula 38]

[0489]

[0490] X2: Compound with the following structure (silane coupling agent)

[0491] [Chemical Formula 39]

[0492]

[0493] (Solvent)

[0494] S1: Propylene glycol monomethyl ether acetate

[0495] S2: Propylene glycol monomethyl ether

[0496] <Evaluation>

[0497] (Evaluation of spectral characteristics of cyan)

[0498] The photosensitive resin composition was applied on a glass substrate by spin coating, and then heated at 100° C. for 120 seconds using a hot plate (pre-baking), and then irradiated with i-rays at 1000 mJ / cm 2The film was exposed to an exposure dose of 100 nm and then heated at 200°C for 5 minutes to produce a cured film with a thickness of 0.6 μm. The transmittance (transmittance) of the obtained cured film in the range of 400 to 700 nm was measured using MCPD-3000 manufactured by OTSUKA ELECTRONICS Co., LTD. The average value of the transmittance in the range of 400 to 530 nm was set as T1, the average value of the transmittance in the range of 610 to 700 nm was set as T2, and when the 50% transmittance was set as λ50, the spectral characteristics as cyan were judged according to the following criteria. The case where all three of the following items are satisfied is set as A, the case where only two of the items are satisfied is set as B, the case where only one of the items is satisfied is set as C, and the case where none of the items are satisfied is set as D.

[0499] T1 is 70% or more.

[0500] T2 is 30% or less.

[0501] ·λ50 is in the range of 540~590nm.

[0502] (Evaluation of light resistance)

[0503] The photosensitive resin composition was applied on a glass substrate by spin coating, and then heated at 100° C. for 120 seconds using a hot plate (pre-baking), and then irradiated with i-rays at 1000 mJ / cm 2 The film was exposed to an exposure dose of 100,000 lux, and then heated at 200°C for 5 minutes to produce a cured film with a thickness of 0.6 μm. The light transmittance (transmittance) of the obtained cured film within the wavelength range of 400 to 700 nm was measured using MCPD-3000 manufactured by OTSUKA ELECTRONICS Co., LTD. Next, the cured film produced above was irradiated with 100,000 lux of light for 1,000 hours (total irradiation amount of 100 million lux·hr) using a light resistance tester (Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments Co., Ltd.). The transmittance of the cured film after light irradiation was measured, and the light resistance was evaluated according to the following criteria.

[0504] A: The integrated value of the transmittance of the cured film after light irradiation at a wavelength of 400 to 700 nm is 97% or more of the integrated value of the transmittance of the cured film before light irradiation at a wavelength of 400 to 700 nm.

[0505] B: The integrated value of the transmittance of the cured film after light irradiation at a wavelength of 400 to 700 nm is 95% or more and less than 97% of the integrated value of the transmittance of the cured film before light irradiation at a wavelength of 400 to 700 nm.

[0506] C: The integrated value of the transmittance of the cured film after light irradiation at a wavelength of 400 to 700 nm is less than 95% of the integrated value of the transmittance of the cured film before light irradiation at a wavelength of 400 to 700 nm.

[0507] (Evaluation of rectangularity)

[0508] An 8-inch (1 inch = 25.4 mm) diameter silicon wafer was heat-treated in an oven at 200°C for 30 minutes. A primer photoresist (CT-4000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was then applied to the silicon wafer to a dry film thickness of 0.1 μm. The film was then dried in an oven at 220°C for 1 hour to form a primer layer, thereby obtaining a silicon wafer substrate with a primer layer.

[0509] The photosensitive resin composition was applied to the primer layer of the silicon wafer substrate with the primer layer prepared above. Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100°C. Then, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at a wavelength of 365nm through a patterned mask at a rate of 500mJ / cm 2 The exposure was performed with an exposure dose of 1.4 μm×1.4 μm. A mask having an island pattern was used.

[0510] Next, the substrate with the irradiated coating film was placed on the horizontal turntable of a spin / spray developer (DW-30, manufactured by Chemitronics Co., Ltd.) and subjected to spin immersion development for 60 seconds at room temperature using an alkaline developer (CD-2060, manufactured by Fujifilm Electronic Materials Co., Ltd.). The substrate, after spin immersion development, was then secured to the horizontal turntable using a vacuum chuck. While the silicon wafer was rotated at 50 rpm using a rotating device, pure water was sprayed from a nozzle above the center of rotation to perform a rinse treatment (23 seconds x 2 times). This was followed by spin drying and a heat treatment (post-baking) at 200°C for 300 seconds using a hot plate, thereby forming a cured film pattern (pixels).

[0511] The obtained cured film pattern was cut, and the cross section of the cured film pattern was observed at a magnification of 20,000 times using a scanning electron microscope (SEM), and rectangularity was evaluated according to the following criteria.

[0512] A: The width of the surface on the substrate side (the side in contact with the substrate) of the pattern of the cured film is 90% or more and 130% or less of the width of the surface on the side opposite to the substrate.

[0513] B: The width of the surface on the substrate side (the side in contact with the substrate) of the cured film pattern is 80% or more and less than 90% or more than 130% and less than 160% of the width of the surface opposite to the substrate.

[0514] C: The width of the cured film pattern on the substrate side (the side in contact with the substrate) is less than 80% or 160% or greater of the width of the surface opposite to the substrate. Alternatively, the cured film pattern cannot be formed due to peeling caused by development.

[0515] (Evaluation of defects)

[0516] An 8-inch (1 inch = 25.4 mm) diameter silicon wafer was heat-treated in an oven at 200°C for 30 minutes. A primer photoresist (CT-4000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was then applied to the silicon wafer to a dry film thickness of 0.1 μm. The film was then dried in an oven at 220°C for 1 hour to form a primer layer, thereby obtaining a silicon wafer substrate with a primer layer.

[0517] The photosensitive resin composition was applied to the primer layer of the silicon wafer substrate with the primer layer prepared above. Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100°C. Then, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at a wavelength of 365nm through a patterned mask at a rate of 500mJ / cm 2 The entire wafer was exposed with an exposure dose of 1.4 μm × 1.4 μm. A mask capable of forming an island pattern of 1.4 μm × 1.4 μm at a period of 2.8 μm × 2.8 μm was used, and an 11 mm × 11 mm lens was used to expose the entire wafer except for the outer 3 mm area.

[0518] Next, the substrate with the irradiated coating film was placed on the horizontal turntable of a rotary spray developer (DW-30 model, manufactured by CHEMITRONICS CO., Ltd.), and an alkaline developer (CD-2060, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used to perform spin immersion development for 60 seconds at room temperature. Next, the substrate after spin immersion development was fixed on a horizontal turntable using a vacuum chuck, and the silicon wafer was rotated at a speed of 50 rpm by a rotating device while being rinsed with pure water from a nozzle above its rotation center in a spray state (23 seconds × 2 times), followed by spin drying, and then a heating treatment (post-baking) was performed at 200°C for 300 seconds using a hot plate, thereby forming a pattern (pixel) of the cured film. The number of defects in the pattern of the obtained cured film was checked using a wafer defect evaluation device (ComPLUS3, manufactured by AMAT). The defects were evaluated according to the following criteria.

[0519] A: The total number of defects in an 8-inch wafer is ≤30

[0520] B: 30<Total number of defects in 8-inch wafer ≤ 100

[0521] C: 100<total number of defects in 8-inch wafer

[0522] (Evaluation of mixed colors)

[0523] The photosensitive resin composition was applied to a silicon wafer having a diameter of 8 inches (1 inch = 25.4 mm). A heat treatment (pre-baking) was then performed using a hot plate at 100°C for 120 seconds. An i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was then used at a wavelength of 365 nm and a light intensity of 500 mJ / cm 2 The exposure was performed with an exposure amount of 2 cm × 2 cm. The mask used was a mask with an island pattern of 2 cm × 2 cm. Next, the substrate on which the irradiated coating film was formed was placed on a horizontal turntable of a rotary spray developer (DW-30 model, manufactured by CHEMITRONICS CO., Ltd.), and an alkaline developer (CD-2060, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used to perform spin immersion development for 60 seconds at room temperature. Next, the substrate after spin immersion development was fixed on a horizontal turntable by a vacuum suction cup, and the silicon wafer was rotated at a rotation speed of 50 rpm by a rotating device while pure water was supplied from a nozzle in a spray state from above its rotation center for rinsing (23 seconds × 2 times), followed by spin drying, and then a heating treatment (post-baking) was performed at 200°C for 300 seconds using a hot plate to form a cured film pattern.

[0524] The light transmittance (transmittance) of the obtained cured film pattern in the wavelength range of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.

[0525] Next, a photosensitive resin composition for color mixing evaluation was spin-coated onto the pattern of the cured film produced above and heated (prebaked) for 120 seconds using a 100°C hot plate to form a coating film with a thickness of 0.6 μm. The aforementioned Yellow composition and Magenta composition were used as the photosensitive resin compositions for color mixing evaluation.

[0526] Next, the substrate with the coating film of the photosensitive resin composition for color mixing evaluation formed thereon was placed on the horizontal turntable of a spin / spray developer (Model DW-30, manufactured by Chemitronics Co., Ltd.) and subjected to spin immersion development at room temperature for 60 seconds using an alkaline developer (CD-2060, manufactured by Fujifilm Electronic Materials Co., Ltd.) to remove the coating film of the photosensitive resin composition for color mixing evaluation. The substrate, after spin immersion development, was then secured to the horizontal turntable using a vacuum chuck system. While the silicon wafer was rotated at 50 rpm using a rotating device, pure water was sprayed from a nozzle above the center of rotation to perform a rinse treatment (23 seconds x 2 times). The substrate was then spin-dried, and a color mixing evaluation test was performed.

[0527] The cured film pattern after the color mixing evaluation test was measured for light transmittance (transmittance) within a wavelength range of 400 to 700 nm using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the change in the integrated transmittance was determined. Color mixing was evaluated according to the following criteria.

[0528] A: The cumulative change in transmittance is less than 1%

[0529] B: The change in the cumulative value of transmittance is 1% or more and less than 1.5%

[0530] C: The change in the cumulative value of transmittance is 1.5% or more

[0531] [Table 3]

[0532]

[0533] [Table 4]

[0534]

[0535] [Table 5]

[0536]

[0537] As shown in the above table, in Examples, the spectral characteristics, light resistance, and color mixing evaluations for cyan were excellent.

[0538] (Example 100)

[0539] The Cyan composition was applied to a silicon wafer by spin coating so that the film thickness after film formation was 1.0 μm. Then, it was heated at 100°C for 2 minutes using a hot plate. Then, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at a rate of 1000 mJ / cm 2 The exposure was performed with an exposure dose of 2 μm and through a mask having a dot pattern of 2 μm square. Next, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform spin immersion development at 23°C for 60 seconds. Thereafter, the film was rinsed by spin spraying and further washed with pure water. Next, the Cyan composition was patterned by heating at 200°C for 5 minutes using a hot plate. Similarly, the Yellow composition and the Magenta composition were patterned in sequence to form cyan, yellow and magenta coloring patterns (Bayer patterns) to manufacture a color filter.

[0540] As the Cyan composition, the photosensitive resin composition of Example 2 was used.

[0541] As the Yellow composition and the Magenta composition, the above-mentioned Yellow composition and Magenta composition were used, respectively.

[0542] The obtained color filter is embedded in a solid-state imaging element according to a known method. The solid-state imaging element has a suitable image recognition capability.

Claims

1. A photosensitive resin composition comprising a colorant, a resin, a polymerizable compound, a photopolymerization initiator, an ultraviolet absorber and a solvent, The colorant is at least one phthalocyanine pigment selected from the group consisting of color index pigment blue 15:3 and color index pigment blue 15:

4. The ultraviolet absorber is contained in an amount of 0.1% to 10% by mass in the total solid content of the photosensitive resin composition. The photopolymerization initiator is at least one selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound; the ultraviolet absorber is at least one selected from a conjugated diene compound, a benzotriazole compound, and a triazine compound; and the photosensitive resin composition contains 1 to 200 parts by mass of the ultraviolet absorber relative to 100 parts by mass of the photopolymerization initiator.

2. The photosensitive resin composition according to claim 1, wherein The average secondary particle size of the phthalocyanine pigment is 50nm to 100nm.

3. The photosensitive resin composition according to claim 1 or 2, wherein The colorant is contained in an amount of 10% by mass or more in the total solid content of the photosensitive resin composition.

4. The photosensitive resin composition according to claim 1 or 2, wherein The resin contains a resin having an amine value of 25 mgKOH / g to 60 mgKOH / g.

5. The photosensitive resin composition according to claim 4, wherein The resin having an amine value of 25 mgKOH / g to 60 mgKOH / g is a (meth)acrylic resin.

6. The photosensitive resin composition according to claim 1 or 2, wherein The resin includes an alkali-soluble resin.

7. The photosensitive resin composition according to claim 1 or 2, wherein The ultraviolet absorber is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the polymerizable compound. The photosensitive resin composition according to claim 1 or 2, which is used for forming pixels of a color filter. 9 . The photosensitive resin composition according to claim 8 , which is used to form cyan pixels. 10 . The photosensitive resin composition according to claim 1 , which is used for a solid-state imaging device. 11 . A cured film obtained from the photosensitive resin composition according to claim 1 . 12 . A color filter comprising the cured film according to claim 11 . 13 . A solid-state imaging element comprising the cured film according to claim 11 .

14. The solid-state imaging element according to claim 13, wherein The cured film is a cyan pixel, and the solid-state imaging element further has a yellow pixel and a magenta pixel. 15 . An image display device comprising the cured film according to claim 11 .

Images