Photosensitive composition, method for producing optical filter and method for producing solid state image sensor

Abstract

To provide a photosensitive composition capable of forming pixels with fine line width, and excellent in lithography property, a method for producing an optical filter and a method for producing a solid state image sensor.SOLUTION: A photosensitive composition includes a coloring agent A, a photopolymerization initiator B, a polymerizable monomer C containing an ethylenically unsaturated group, and a polymerizable resin D containing an ethylenically unsaturated bond-containing group, where a content of coloring agent A in the total solid content of the photosensitive composition exceeds 50 mass%, the content of polymerizable monomer C in the total solid content of the photosensitive composition is 4 mass% or more, and the composition contains 5 to 200 pts.mass of polymerizable monomer C per 100 pts.mass of polymerizable resin D, suitable for exposure with light at a wavelength of 300 nm or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive composition containing a coloring material. More specifically, the present invention relates to a photosensitive composition used for forming an optical filter for a solid-state imaging device. The present invention also relates to a method for producing an optical filter and a method for producing a solid-state imaging device. [Background technology]

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

[0003] The color filter is produced using a photosensitive composition that contains, for example, a color material, a photopolymerization initiator, and a polymerizable monomer.

[0004] Patent Document 1 describes the production of a color filter using a photosensitive composition that contains a color material, a photoradical polymerization initiator, and a radical polymerizable compound, in which the content of the radical polymerizable compound having a weight average molecular weight of 3000 or more in the total mass of the radical polymerizable compound is 70 mass% or more. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2019 / 172006 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, progress has been made in miniaturizing and increasing the resolution of solid-state imaging devices equipped with optical filters such as color filters, and therefore miniaturization of pixels in optical filters such as color filters has been considered.

[0007] In addition, in recent years, there has been a strong demand for smaller and thinner solid-state imaging devices. For this reason, it has been desired that films containing color materials, such as color filters, used in solid-state imaging devices be made thinner in recent years. In order to achieve a thinner film while maintaining the desired spectral performance, it is necessary to increase the concentration of the color material in the photosensitive composition used for film formation.

[0008] However, as the colorant concentration in the total solid content of the photosensitive composition increases, the proportion of components other than the colorant decreases relatively, so that the curing property tends to be insufficient. Therefore, when forming pixels by photolithography using the photosensitive composition, the degree of curing of the film when exposed through a mask tends to be insufficient, and the adhesion of the obtained pixels to the support tends to be insufficient. In particular, as the size of the opening of the mask becomes narrower, the amount of exposure light irradiated to the photosensitive composition in the exposed part decreases, so that the film cannot be cured sufficiently to the bottom (support side), and the adhesion of the obtained pixels to the support tends to be insufficient.

[0009] When forming pixels by photolithography, the film can be sufficiently cured during exposure by increasing the exposure dose, but the curing also proceeds in the non-exposed areas around the mask opening, which tends to increase the line width of the formed pixels and cause residues to form between the pixels. In addition, when the dimensions of the mask opening are less than 1.0 μm square, the effects of standing waves tend to cause the non-exposed areas around the mask opening to be cured more easily, and the line width of the pixels tends to be larger than the size of the mask opening. In particular, when the dimensions of the mask opening are 0.7 μm square or less, this problem is particularly likely to occur.

[0010] An object of the present invention is to provide a photosensitive composition having excellent photolithography properties and capable of forming pixels with fine line widths. Another object of the present invention is to provide a method for producing an optical filter and a method for producing a solid-state imaging device. [Means for solving the problem]

[0011] According to the inventor's investigations, it was found that the above object can be achieved by the following configuration, and the present invention was completed. <1> A photosensitive composition comprising a color material A, a photopolymerization initiator B, a polymerizable monomer C having an ethylenically unsaturated bond-containing group, and a polymerizable resin D having an ethylenically unsaturated bond-containing group, the content of the color material A in the total solid content of the photosensitive composition is more than 50 mass %, the content of the polymerizable monomer C in the total solid content of the photosensitive composition is 4 mass% or more, A photosensitive composition for exposure to light having a wavelength of 300 nm or less, comprising 5 to 200 parts by mass of the polymerizable monomer C per 100 parts by mass of the polymerizable resin D. <2> The color material A includes a chromatic color material. <1> The photosensitive composition according to claim 1. <3> The polymerizable monomer C includes a difunctional to octafunctional polymerizable monomer having 2 to 8 ethylenically unsaturated bond-containing groups. <1> or <2> The photosensitive composition according to claim 1. <4> the ethylenically unsaturated bond-containing group value derived from the polymerizable monomer C is 0.01 to 8 mmol / g in the total solid content of the photosensitive composition; <1> ~ <3> 13. The photosensitive composition according to claim 12 . <5> the ethylenically unsaturated bond-containing group value derived from the polymerizable resin D in the total solid content of the photosensitive composition is 0.001 to 5 mmol / g; <1> ~ <4> 13. The photosensitive composition according to claim 12 . <6> The polymerizable monomer C is contained in an amount of 10 to 100 parts by mass relative to 100 parts by mass of the polymerizable resin D. <1> ~ <5> 13. The photosensitive composition according to claim 12 . <7> the total amount of the polymerizable monomer C and the polymerizable resin D is 5 to 45 mass % of the total solid content of the photosensitive composition; <1> ~ <6> 13. The photosensitive composition according to claim 12 . <8> the content of the photopolymerization initiator B in the total solid content of the photosensitive composition is 1 to 10 mass %; <1> ~ <7> 13. The photosensitive composition according to claim 12 . <9> For forming red or green pixels of a color filter; <1> ~ <8> 13. The photosensitive composition according to claim 12 . <10> For solid-state imaging devices. <1> ~ <9> 13. The photosensitive composition according to claim 12 . <11> <1> ~ <10> forming a photosensitive composition layer on a support using the photosensitive composition according to any one of the above items; a step of exposing the photosensitive composition layer to light having a wavelength of 300 nm or less in a pattern; a step of developing and removing the photosensitive composition layer in the unexposed areas to form pixels; A method for producing an optical filter comprising the steps of: <12> The light having a wavelength of 300 nm or less that is irradiated onto the photosensitive composition layer is light having a wavelength of 248 nm. <11> A method for producing the optical filter according to claim 1. <13> <11> or <12> A method for manufacturing a solid-state imaging device, comprising the method for manufacturing the optical filter according to claim 1. Effect of the Invention

[0012] According to the present invention, it is possible to provide a photosensitive composition having excellent photolithography properties and capable of forming pixels with fine line widths, and a method for producing an optical filter and a method for producing a solid-state imaging device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In the description of groups (atomic groups) in this specification, when there is no indication of substitution or non-substitution, the notation includes both groups (atomic groups) that have no substituents and groups (atomic groups) that have a substituent. For example, an "alkyl group" includes not only an alkyl group that has no substituents (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group). In this specification, "(meth)acrylate" refers to both or either of acrylate and methacrylate, "(meth)acryl" refers to both or either of acryl and methacryl, and "(meth)acryloyl" refers to both or either of acryloyl and methacryloyl. In this specification, Me in the structural formulae represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the weight average molecular weight and number average molecular weight are values ​​calculated as polystyrene standards measured by GPC (gel permeation chromatography). In this specification, the total solids content refers to the total mass of all components of the composition excluding the solvent. In this specification, the pigment means a coloring material that is difficult to dissolve in a solvent. For example, the solubility of the pigment in 100 g of water at 23° C. and 100 g of propylene glycol monomethyl ether acetate at 23° C. is preferably 0.1 g or less, more preferably 0.01 g or less. In this specification, symbols (e.g., A, B, C, and D) added before or after a name are terms used to distinguish components, and do not limit the type, number, or superiority of the components. In this specification, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved.

[0014] <Photosensitive composition> The photosensitive composition of the present invention is a photosensitive composition comprising a color material A, a photopolymerization initiator B, a polymerizable monomer C having an ethylenically unsaturated bond-containing group, and a polymerizable resin D having an ethylenically unsaturated bond-containing group, The content of color material A in the total solid content of the photosensitive composition is more than 50 mass %, The content of the polymerizable monomer C in the total solid content of the photosensitive composition is 4 mass% or more, The photosensitive composition contains 5 to 200 parts by mass of polymerizable monomer C relative to 100 parts by mass of polymerizable resin D, and is intended for exposure to light having a wavelength of 300 nm or less.

[0015] According to the photosensitive composition of the present invention, although the content of the coloring material in the total solid content exceeds 50 mass %, it has excellent photolithography properties and can form pixels with fine line widths (for example, line widths less than 1.0 μm, preferably line widths 0.7 μm or less, more preferably line widths 0.6 μm or less). The detailed reason why such effects are obtained is unclear, but it is presumed to be due to the following.

[0016] The photosensitive composition of the present invention is a photosensitive composition for exposure to light having a wavelength of 300 nm or less. Since light having a wavelength of 300 nm or less has a high energy density, by irradiating the photosensitive composition of the present invention with light having a wavelength of 300 nm or less, active species such as radicals can be instantaneously generated in large quantities from the photopolymerization initiator in the exposed area. By instantaneously generating a large amount of active species such as radicals in the exposed area, deactivation by oxygen can be suppressed, and polymerizable monomers and polymerizable resins can be efficiently cured. The photosensitive composition of the present invention has a content of polymerizable monomer C in the total solid content of the photosensitive composition of 4 mass% or more, and contains 5 to 200 mass parts of polymerizable monomer C relative to 100 mass parts of polymerizable resin D. Although the detailed reason is unclear, it is presumed that the curing of the non-exposed part around the mask during exposure can be suppressed, and pixels with a fine line width can be formed.

[0017] The photosensitive composition of the present invention is a photosensitive composition for exposure to light having a wavelength of 300 nm or less. The light used for exposure is preferably light having a wavelength of 180 to 300 nm. Specifically, light having a wavelength of 248 nm (KrF radiation) and light having a wavelength of 193 nm (ArF radiation) can be mentioned, and light having a wavelength of 248 nm (KrF radiation) is preferable.

[0018] The ethylenically unsaturated bond-containing group value (hereinafter also referred to as C=C value) derived from the polymerizable monomer C in the total solid content of the photosensitive composition of the present invention is preferably 0.01 to 8 mmol / g. The lower limit is preferably 0.05 mmol / g or more, more preferably 0.1 mmol / g or more. The upper limit is preferably 4 mmol / g or less, more preferably 2.5 mmol / g or less. If the C=C value derived from the polymerizable monomer C in the total solid content of the photosensitive composition is within the above range, a high-density three-dimensional crosslink can be formed by exposure, which is effective for fine patterning. The C=C value derived from the polymerizable monomer C in the total solid content of the photosensitive composition is the total value of the product of the content of each polymerizable monomer and the C=C value of each polymerizable monomer in the total solid content of the photosensitive composition divided by the total solid content of the photosensitive composition. The C═C value of a polymerizable monomer is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.

[0019] The C=C value derived from the polymerizable resin D in the total solid content of the photosensitive composition of the present invention is preferably 0.001 to 5 mmol / g. The lower limit is preferably 0.005 mmol / g or more, more preferably 0.01 mmol / g or more. The upper limit is preferably 3 mmol / g or less, more preferably 1 mmol / g or less. If the C=C value derived from the polymerizable resin D in the total solid content of the photosensitive composition is within the above range, a polymer having a high molecular weight can be formed by exposure, and pixels having a fine line width and excellent adhesion to the support can be formed. The C=C value derived from the polymerizable resin D in the total solid content of the photosensitive composition is the total value of the product of the content of each polymerizable resin in the total solid content of the photosensitive composition and the C=C value of each polymerizable resin divided by the total solid content of the photosensitive composition. The C=C value of the polymerizable resin is a numerical value representing the molar amount of C=C groups per gram of solid content of the polymerizable resin. The C=C value of a polymerizable resin can be calculated from the following formula by extracting the low molecular weight component (a) at the C=C group site from the polymerizable resin by alkali treatment, measuring the content of the low molecular weight component (a) at the C=C group site relative to the polymerizable resin by high performance liquid chromatography (HPLC), and then calculating the C=C value from the following formula: In addition, when the C=C group site cannot be extracted from the polymerizable resin by alkali treatment, a value measured by NMR (nuclear magnetic resonance) is used. C of polymerizable resin = C value [mmol / g] = (content of low molecular weight component (a) [ppm] / molecular weight of low molecular weight component (a) [g / mol]) × 10 3

[0020] The C=C value of the solid content of the photosensitive composition of the present invention is preferably 0.01 to 10 mmol / g. The lower limit is preferably 0.05 mmol / g or more, more preferably 0.1 mmol / g or more. The upper limit is preferably 5 mmol / g or less, more preferably 3 mmol / g or less. If the C=C value of the solid content of the photosensitive composition is within the above range, the composition has excellent curability by exposure, the difference in alkali developability between the exposed part and the unexposed part is effectively widened, and it is effective for fine patterning. The C=C value of the solid content of the photosensitive composition is a numerical value representing the molar amount of C=C groups per 1 g of the solid content of the photosensitive composition. The C=C value of the solid content of the photosensitive composition can be calculated from the following formula by extracting the low molecular weight component (a) at the C=C group site from the solid content of the photosensitive composition by alkali treatment, measuring the content of the low molecular weight component (a) at the C=C group site relative to the solid content of the photosensitive composition by high performance liquid chromatography (HPLC). When the C=C group site cannot be extracted from the solid content of the photosensitive composition by alkali treatment, the value measured by NMR (nuclear magnetic resonance) is used. C of the solid content of the photosensitive composition = C value [mmol / g] = (content of low molecular weight component (a) [ppm] / molecular weight of low molecular weight component (a) [g / mol]) × 10 3

[0021] The photosensitive composition of the present invention is preferably used as a photosensitive composition for an optical filter. Examples of the optical filter include a color filter, a near-infrared cut filter, and a near-infrared transmission filter, and the color filter is preferable.

[0022] The color filter may be a filter having colored pixels, such as red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

[0023] The near-infrared cut filter may be a filter that blocks at least a part of light having a wavelength in the near-infrared region. The maximum absorption wavelength of the near-infrared cut filter is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. The transmittance of the near-infrared cut filter in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. The ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm (absorbance Amax / absorbance A550) is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400.

[0024] The near-infrared transmission filter may be a filter that blocks at least a part of visible light and transmits at least a part of near-infrared light. Specific examples of near-infrared transmission filters include filters that satisfy the spectral characteristics of a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm. The near-infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (IR1) to (IR5). (IR1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1500 nm. (IR2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm. (IR3): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. (IR4): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. (IR5): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm.

[0025] The photosensitive composition of the present invention is preferably a photosensitive composition for forming color pixels of a color filter. Examples of the color pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels, and are preferably red pixels or green pixels. The photosensitive composition of the present invention is also preferably used as a photosensitive composition for a solid-state imaging device. More specifically, it is preferably used as a photosensitive composition for an optical filter used in a solid-state imaging device, more preferably used as a photosensitive composition for forming color pixels of a color filter used in a solid-state imaging device, and particularly preferably used as a photosensitive composition for forming red pixels or green pixels of a color filter used in a solid-state imaging device. The color pixels of a color filter can be formed using a photosensitive composition containing a chromatic colorant.

[0026] The solid content of the photosensitive composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0027] Each component used in the photosensitive composition of the present invention will now be described.

[0028] <<Coloring materials>> The photosensitive composition of the present invention contains a color material A (hereinafter, referred to as color material). The color material may be a pigment or a dye. A pigment and a dye may be used in combination. The pigment may be either an inorganic pigment or an organic pigment. As the pigment, a material in which an inorganic pigment or an organic-inorganic pigment is partially substituted with an organic chromophore may also be used. Substituting an inorganic pigment or an organic-inorganic pigment with an organic chromophore makes it easier to design the hue.

[0029] The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. If the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the photosensitive composition is good. In the present invention, the primary particle diameter of the pigment can be obtained by observing the primary particles of the pigment with a transmission electron microscope and obtaining an image photograph. Specifically, the projected area of ​​the primary particles of the pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment. In the present invention, the average primary particle diameter is the arithmetic mean value of the primary particle diameters of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles without aggregation.

[0030] The coloring material preferably contains a pigment. The content of the pigment in the coloring material is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0031] The types of coloring materials include chromatic coloring materials, black coloring materials, white coloring materials, and near-infrared absorbing coloring materials, and chromatic coloring materials are preferred. The chromatic coloring materials are preferably pigments (chromatic pigments). The photosensitive composition containing the chromatic coloring materials can be preferably used as a photosensitive composition for forming colored pixels of a color filter.

[0032] (Chromatic color materials) Examples of chromatic colorants include colorants having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples include yellow colorants, orange colorants, red colorants, green colorants, purple colorants, and blue colorants. Specific examples of chromatic colorants include the following:

[0033] Color Index (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, Yellow pigments such as 138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,215,228,231,232 (methine type), 233 (quinoline type), 234 (amino ketone type), 235 (amino ketone type), and 236 (amino ketone type). Orange pigments such as 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. CIPigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,5 3:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150, Red pigments such as 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294 (xanthene type, Organo Ultramarine, Bluish Red), 295 (monoazo type), 296 (diazo type), and 297 (aminoketone type). Green pigments such as CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine type), 65 (phthalocyanine type), and 66 (phthalocyanine type). Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane type), and 61 (xanthene type). Blue pigments such as CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo type), and 88 (methine type).

[0034] In addition, as a green colorant, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used. Specific examples include compounds described in International Publication No. 2015 / 118720. In addition, as a green colorant, a compound described in Chinese Patent Application No. 106909027, a phthalocyanine compound having a phosphoric ester as a ligand described in International Publication No. 2012 / 102395, a phthalocyanine compound described in JP-A-2019-008014, a phthalocyanine compound described in JP-A-2018-180023, a compound described in JP-A-2019-038958, a core-shell type dye described in JP-A-2020-076995, and the like can also be used.

[0035] In addition, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue colorant. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.

[0036] Furthermore, as the yellow coloring material, an azobarbituric acid nickel complex having the following structure can also be used. [ka]

[0037] As red coloring materials, diketopyrrolopyrrole compounds having at least one bromine atom substituted in the structure described in JP 2017-201384 A, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 A, diketopyrrolopyrrole compounds described in WO 2012 / 102399 A, diketopyrrolopyrrole compounds described in WO 2012 / 117965 A, naphthol azo compounds described in JP 2012-229344 A, The red colorant described in JP 6516119 A, the red colorant described in JP 6525101 A, the brominated diketopyrrolopyrrole compound described in paragraph number 0229 of JP 2020-090632 A, the anthraquinone compound described in Korean Patent Publication No. 10-2019-0140741 A, the anthraquinone compound described in Korean Patent Publication No. 10-2019-0140744 A, the perylene compound described in JP 2020-079396 A, etc. can also be used. In addition, as the red colorant, a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is introduced and bonded to a diketopyrrolopyrrole skeleton can also be used.

[0038] In addition, as yellow coloring materials, compounds described in JP-A-2017-201003, compounds described in JP-A-2017-197719, compounds described in paragraphs 0011 to 0062 and 0137 to 0276 of JP-A-2017-171912, compounds described in paragraphs 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913, compounds described in paragraphs 0011 to 0062 and 0139 to 0190 of JP-A-2017-171914, compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915, compounds, quinophthalone compounds described in paragraphs 0011 to 0034 of JP 2013-054339 A, quinophthalone compounds described in paragraphs 0013 to 0058 of JP 2014-026228 A, isoindoline compounds described in JP 2018-062644 A, quinophthalone compounds described in JP 218-203798 A, quinophthalone compounds described in JP 2018-062578 A, quinophthalone compounds described in JP 6432077 A, quinophthalone compounds described in JP 6432076 A, JP 2018-155881 A Quinophthalone compounds described in JP 2018-111757 A, quinophthalone compounds described in JP 2018-040835 A, quinophthalone compounds described in JP 2017-197640 A, quinophthalone compounds described in JP 2016-145282 A, quinophthalone compounds described in JP 2014-085565 A, quinophthalone compounds described in JP 2014-021139 A, quinophthalone compounds described in JP 2013-209614 A, quinophthalone compounds described in JP 2013-209435 A quinophthalone compounds, quinophthalone compounds described in JP-A-2013-181015, quinophthalone compounds described in JP-A-2013-061622, quinophthalone compounds described in JP-A-2013-054339, quinophthalone compounds described in JP-A-2013-032486, quinophthalone compounds described in JP-A-2012-226110, quinophthalone compounds described in JP-A-2008-074987, quinophthalone compounds described in JP-A-2008-081565, quinophthalone compounds described in JP-A-2008-074986,Quinophthalone compounds described in JP 2008-074985 A, JP 2008-050420 A, JP 2008-031281 A, JP 48-032765 A, JP 2019-008014 A, compounds described in Korean Patent Publication No. 10-2014-0034963, compounds described in JP 2017-095706 A, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Japanese Patent No. 6607427 can also be used. In addition, oligomers of these compounds are also preferably used from the viewpoint of improving color value. In addition, compounds represented by the formula (QP1) and compounds represented by the formula (QP2) can also be used as yellow colorants. , [ka]

[0039] In formula (QP1), X 1 ~X 16 each independently represents a hydrogen atom or a halogen atom; Z 1 represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by formula (QP1) include the compounds described in paragraph 0016 of Japanese Patent No. 6443711. [ka]

[0040] 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 more. Specific examples of the compound represented by formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.

[0041] In addition, diarylmethane compounds described in JP-A-2020-504758 can also be used as colorants.

[0042] For the diffraction angles that various pigments preferably have, reference can be made to the descriptions in Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, and Japanese Patent Laid-Open No. 2020-026503, the contents of which are incorporated herein by reference.

[0043] In addition, dyes can be used as chromatic colorants. There is no particular limitation on the dye, and known dyes can be used. For example, pyrazole azo compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, xanthene compounds, phthalocyanine compounds, benzopyran compounds, indigo compounds, and pyrromethene compounds can be mentioned. In addition, dye multimers can be used as dyes. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. There is no particular limitation on the upper limit, but it can be 100 or less. The multiple dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30000 or less, and even more preferably 20000 or less. As the dye multimer, compounds described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A, JP2016-102191A, WO2016 / 031442, etc. can also be used.

[0044] Two or more chromatic colorants may be used in combination. For example, when the photosensitive composition of the present invention is used for forming green pixels of a color filter, it is preferable to use a green colorant and a yellow colorant in combination. The ratio of the green colorant to the yellow colorant is preferably 15 to 100 parts by mass, more preferably 20 to 70 parts by mass, and even more preferably 25 to 60 parts by mass, per 100 parts by mass of the green colorant. The green colorant is preferably CI Pigment Green 7, 36, 58, 59, or 63, and more preferably CI Pigment Green 36 or 58. The yellow colorant is preferably CI Pigment Yellow 129, 138, 139, 150, 185, 215, 231, or 233, and more preferably CI Pigment Yellow 129, 139, 185, or 215.

[0045] In addition, when the photosensitive composition of the present invention is used for forming red pixels of a color filter, it is preferable to use a red colorant and a yellow colorant in combination. In addition, the ratio of the red colorant to the yellow colorant is preferably 20 to 70 parts by mass, more preferably 25 to 60 parts by mass, and even more preferably 30 to 50 parts by mass, relative to 100 parts by mass of the red colorant. The red colorant is preferably CI Pigment Red 177, 254, 264, 269, 272, 291, 296, 297, and more preferably CI Pigment Red 177, 254, 264, 269, 272. The yellow colorant is preferably CI Pigment Yellow 129, 138, 139, 150, 185, 215, 231, 233, and more preferably CI Pigment Yellow 139, 185, 215, and even more preferably CI Pigment Yellow 139.

[0046] In addition, when two or more chromatic coloring materials are used in combination, the two or more chromatic coloring materials may be combined to form a black color. Examples of such combinations include the following embodiments (Bk1) to (Bk7). When the photosensitive composition contains two or more chromatic coloring materials and exhibits a black color by combining two or more chromatic coloring materials, such a photosensitive composition can be preferably used as a photosensitive composition for forming a near-infrared transmission filter. (Bk1) An embodiment containing a red coloring material and a blue coloring material. (Bk2) An embodiment containing a red coloring material, a blue coloring material, and a yellow coloring material. (Bk3) An embodiment containing a red color material, a blue color material, a yellow color material, and a purple color material. (Bk4) An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, a purple coloring material, and a green coloring material. (Bk5) An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, and a green coloring material. (Bk6) An embodiment containing a red coloring material, a blue coloring material, and a green coloring material. (Bk7) An embodiment containing a yellow coloring material and a purple coloring material.

[0047] (white color material) Examples of the white coloring material include inorganic pigments (white pigments) such as titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. The white pigment is preferably a particle having a titanium atom, and more preferably titanium oxide. In addition, the white pigment is preferably a particle having a refractive index of 2.10 or more with respect to light having a wavelength of 589 nm. The aforementioned refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75. In addition, the titanium oxide described in "Titanium Oxide: Physical Properties and Application Technology, by Kiyono Manabu, pages 13 to 45, published on June 25, 1991, published by Gihodo Publishing" can also be used as the white pigment.

[0048] The white pigment may be not only a single inorganic substance, but also a particle composited with other materials. For example, it is preferable to use a particle having a void or other material inside, a particle having a large number of inorganic particles attached to a core particle, or a core-shell composite particle composed of a polymer particle and a shell layer composed of inorganic nanoparticles. For the core-shell composite particle composed of a polymer particle and a shell layer composed of inorganic nanoparticles, the description in paragraphs 0012 to 0042 of JP 2015-047520 A can be referred to, and the contents of this specification are incorporated herein.

[0049] The white pigment can also be hollow inorganic particles. The hollow inorganic particles are inorganic particles with a structure having a cavity inside, and refer to inorganic particles with a cavity surrounded by an outer shell. Examples of the hollow inorganic particles include the hollow inorganic particles described in JP2011-075786A, WO2013 / 061621A, JP2015-164881A, etc., the contents of which are incorporated herein by reference.

[0050] (Black color material) The black coloring material is not particularly limited, and known materials can be used. For example, examples of inorganic black coloring materials include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is a black particle containing titanium atoms, and low-order titanium oxide or titanium oxynitride is preferred. Titanium black can be surface-modified as necessary for the purpose of improving dispersibility, suppressing aggregation, etc. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. In addition, treatment with a water-repellent material such as that shown in JP-A-2007-302836 can also be performed. Examples of black coloring materials include Color Index (CI) Pigment Black 1,7, etc. It is preferable that both the primary particle size and the average primary particle size of the individual particles of titanium black are small. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, and the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50, can be mentioned. For the above dispersion, the description in paragraphs 0020 to 0105 of JP 2012-169556 A can be referred to, and the contents thereof are incorporated herein. Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, and 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.), and the like. Examples of organic black coloring materials include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferred. Examples of the bisbenzofuranone compound include compounds described in JP-T-2010-534726, JP-T-2012-515233, JP-T-2012-515234, WO 2014 / 208348, and JP-T-2015-525260, and are available as, for example, "Irgaphor Black" manufactured by BASF.Examples of perylene compounds include CI Pigment Black 31 and 32. Examples of azomethine compounds include compounds described in JP-A-01-170601 and JP-A-02-034664, and are available as "Chromofine Black A1103" manufactured by Dainichi Seika Chemicals Co., Ltd. In addition, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016 to 0020 of JP-A-2017-226821 may be used as an organic black coloring material.

[0051] (Near infrared absorbing colorant) The near-infrared absorbing colorant is preferably a pigment, more preferably an organic pigment. The near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1400 nm. The maximum absorption wavelength of the near-infrared absorbing colorant is preferably 1200 nm or less, more preferably 1000 nm or less, and even more preferably 950 nm or less. The near-infrared absorbing colorant has an absorbance A at a wavelength of 550 nm. 550 and absorbance A at the maximum absorption wavelength max A is the ratio of 550 / A max is preferably 0.1 or less, more preferably 0.05 or less, even more preferably 0.03 or less, and particularly preferably 0.02 or less. The lower limit is not particularly limited, but can be, for example, 0.0001 or more, or can be 0.0005 or more. If the above-mentioned absorbance ratio is within the above range, the near-infrared absorbing colorant can be excellent in visible transparency and near-infrared shielding properties. The maximum absorption wavelength and the absorbance value at each wavelength of the near-infrared absorbing colorant are values ​​obtained from the absorption spectrum of a film formed using a photosensitive composition containing the near-infrared absorbing colorant.

[0052] The near infrared absorbing colorant is not particularly limited, but includes pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, etc. Examples of pyrrolopyrrole compounds include the compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, the compounds described in paragraphs 0037 to 0052 of JP 2011-068731 A, and the compounds described in paragraphs 0010 to 0033 of WO 2015 / 166873 A. Examples of squarylium compounds include the compounds described in paragraphs 0044 to 0049 of JP 2011-208101 A, the compounds described in paragraphs 0060 to 0061 of JP 6065169 A, the compounds described in paragraph 0040 of WO 2016 / 181987 A, the compounds described in JP 2015-176046 A, and the compounds described in paragraph 0072 of WO 2016 / 190162 A. Compounds described in JP 2016-074649 A, paragraphs 0196 to 0228, compounds described in JP 2017-067963 A, paragraph 0124, compounds described in WO 2017 / 135359, compounds described in JP 2017-114956 A, compounds described in Japanese Patent No. 6197940, compounds described in WO 2016 / 120166, and the like. Examples of the cyanine compound include the compounds described in paragraphs 0044-0045 of JP 2009-108267 A, the compounds described in paragraphs 0026-0030 of JP 2002-194040 A, the compounds described in JP 2015-172004 A, the compounds described in JP 2015-172102 A, the compounds described in JP 2008-088426 A, the compounds described in paragraph 0090 of WO 2016 / 190162 A, the compounds described in JP 2017-031394 A, etc. Examples of the croconium compound include the compounds described in JP 2017-082029 A.Examples of the iminium compound include the compounds described in JP-T-2008-528706, JP-A-2012-012399, JP-A-2007-092060, and WO-2018 / 043564, paragraphs 0048 to 0063. Examples of the phthalocyanine compound include the compounds described in JP-A-2012-077153, paragraph 0093, oxytitanium phthalocyanine described in JP-A-2006-343631, and the compounds described in JP-A-2013-195480, paragraphs 0013 to 0029, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, and compounds described in WO-2020 / 071470. Examples of the naphthalocyanine compound include the compounds described in JP2012-077153A, paragraph 0093. Examples of the dithiolene metal complex include the compounds described in Japanese Patent No. 5733804.

[0053] Examples of near-infrared absorbing colorants include squarylium compounds described in JP 2017-197437 A, squarylium compounds described in JP 2017-025311 A, squarylium compounds described in WO 2016 / 154782 A, squarylium compounds described in Japanese Patent No. 5884953 A, squarylium compounds described in Japanese Patent No. 6036689 A, squarylium compounds described in Japanese Patent No. 5810604 A, squarylium compounds described in Japanese Patent No. 6036689 B, squarylium compounds described in Japanese Patent No. 6036689 C, squarylium compounds described in Japanese Patent No. 6036689 D, squarylium compounds described in Japanese Patent No. 6036689 E, squarylium compounds described in Japanese Patent No. 6036689 F, squarylium compounds described in Japanese Patent No. 6036689 H ... the squarylium compounds described in paragraphs 0090 to 0107 of WO 2017 / 213047; the pyrrole ring-containing compounds described in paragraphs 0019 to 0075 of JP 2018-054760 A; the pyrrole ring-containing compounds described in paragraphs 0078 to 0082 of JP 2018-040955 A; Pyrrole ring-containing compounds described in JP-A-2018-041047, squarylium compounds having an aromatic ring at the amide α-position described in paragraphs 0024 to 0086 of JP-A-2018-041047, amide-linked squarylium compounds described in JP-A-2017-179131, compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole bis-type squarylium compounds described in JP-A-2017-082029, asymmetric compounds described in paragraphs 0027 to 0114 of JP-A-2017-068120, pyrrole ring-containing compounds (carbazole type) described in JP-A-2017-067963, phthalocyanine compounds described in JP-A-6251530, and the like can also be used.

[0054] The content of the coloring material in the total solid content of the photosensitive composition is more than 50% by mass, preferably 51% by mass or more, more preferably 53% by mass or more, and even more preferably 55% 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.

[0055] The content of the coloring material is preferably 200 to 2000 parts by mass relative to 100 parts by mass of the polymerizable monomer. The lower limit is preferably 250 parts by mass or more, more preferably 300 parts by mass or more, and even more preferably 350 parts by mass or more. The upper limit is preferably 1500 parts by mass or less, more preferably 1200 parts by mass or less, even more preferably 800 parts by mass or less, and particularly preferably 600 parts by mass or less.

[0056] The content of the coloring material is preferably 100 to 1500 parts by mass relative to 100 parts by mass of the polymerizable resin. The lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 1200 parts by mass or less, more preferably 1000 parts by mass or less, and even more preferably 500 parts by mass or less.

[0057] <<Photopolymerization initiator>> The photosensitive composition of the present invention contains a photopolymerization initiator B (hereinafter referred to as a photopolymerization initiator). The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet to visible regions is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0058] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a 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 preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and Japanese Patent No. 6301489 A, MATERIAL STAGE Examples of the photopolymerization initiator include the peroxide-based photopolymerization initiator described in 37 to 60p, vol. 19, No. 3, 2019, the photopolymerization initiator described in WO 2018 / 221177, the photopolymerization initiator described in WO 2018 / 110179, the photopolymerization initiator described in JP 2019-043864 A, the photopolymerization initiator described in JP 2019-044030 A, the peroxide-based initiator described in JP 2019-167313 A, the aminoacetophenone-based initiator having an oxazolidine group described in JP 2020-055992 A, and the oxime-based photopolymerization initiator described in JP 2013-190459 A, the contents of which are incorporated herein by reference.

[0059] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (manufactured by BASF), etc. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by BASF), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819, Irgacure TPO (both manufactured by BASF), and the like.

[0060] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP 2000-066385 A, compounds described in JP-T-2004-534797 A, compounds described in JP-A-2017-019766 A, compounds described in Japanese Patent No. 6065596 A, compounds described in WO 2015 / 152153 A, compounds described in WO 2017 / 051680 A, compounds described in JP 2017-198865 A, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127 A, compounds described in WO 2013 / 167515 A, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. 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 Strong Electronic New Materials Co., Ltd.), and Adeka Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP 2012-014052 A). In addition, it is also preferable to use a compound that is not colorable or a compound that is highly transparent and does not easily discolor as the oxime compound. Examples of commercially available products include Adeka Arcles NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

[0061] As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used.Specific examples of the oxime compound having a fluorene ring include the compounds described in JP 2014-137466 A, the compounds described in JP 6636081 A, and the compounds described in KP 10-2016-0109444 A.

[0062] As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in WO 2013 / 083505.

[0063] 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.

[0064] As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 A, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

[0065] As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in WO 2015 / 036910.

[0066] As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in WO 2019 / 088055.

[0067] As a photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring is used. OX1 It is also possible to use an oxime compound having the aromatic ring group Ar OX1 Examples of the electron-withdrawing group of include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, and an acyl group is more preferred because it is easy to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and even more preferably an alkoxy group, an alkylsulfanyl group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group.

[0068] The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and is more preferably the compound represented by the formula (OX2). [ka] In the formula, R X1represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group, R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group, R X3 ~R X14 each independently represents a hydrogen atom or a substituent; However, R X10 ~R X14 At least one of the groups is an electron-withdrawing group.

[0069] Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Of these, an acyl group and a nitro group are preferred, and an acyl group is more preferred because a film having excellent light resistance is easily formed, and a benzoyl group is even more preferred.

[0070] In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 is preferably a hydrogen atom.

[0071] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.

[0072] Specific examples of oxime compounds that can be preferably used in the present invention are shown below, but the present invention is not limited to these.

[0073] [ka] [ka]

[0074] The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. In addition, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, even more preferably 2000 to 300000, and particularly preferably 5000 to 200000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using a spectrophotometer (Varian Cary-5 spectrophotometer) using ethyl acetate as a solvent at a concentration of 0.01 g / L.

[0075] As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in a solvent is improved, so that precipitation is less likely to occur over time, and the stability over time of the photosensitive composition can be improved. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015 / 004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in WO-T-2013-522445; Examples of the photoinitiator include Cmpd1 to 7 described in JP 2016 / 034963 A, the oxime ester photoinitiator described in paragraph 0007 of JP 2017-523465 A, the photoinitiator described in paragraphs 0020 to 0033 of JP 2017-167399 A, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP 2017-151342 A, and the oxime ester photoinitiator described in Japanese Patent No. 6,469,669 A.

[0076] The content of the photopolymerization initiator in the total solid content of the photosensitive composition is preferably 1 to 10% by mass. The lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less. The photopolymerization initiator may be used alone or in combination of two or more kinds. When two or more kinds are used in combination, the total amount thereof is preferably within the above range.

[0077] <<Polymerizable monomer>> The photosensitive composition of the present invention contains a polymerizable monomer C (hereinafter referred to as a polymerizable monomer) having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group that the polymerizable monomer has include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. The polymerizable monomer used in the present invention is preferably a radical polymerizable monomer.

[0078] The molecular weight of the polymerizable monomer is preferably 100 or more and less than 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more. It is also preferable that the polymerizable monomer is a compound having no molecular weight distribution.

[0079] The polymerizable monomer preferably contains a mono- to deca-functional polymerizable monomer having 1 to 10 ethylenically unsaturated bond-containing groups, more preferably a di- to octa-functional polymerizable monomer having 2 to 8 ethylenically unsaturated bond-containing groups, and even more preferably a di- to hexa-functional polymerizable monomer having 2 to 6 ethylenically unsaturated bond-containing groups. The polymerizable monomer preferably contains a mono- to deca-functional (meth)acrylate compound, more preferably a di- to octa-functional (meth)acrylate compound, and even more preferably a di- to hexa-functional (meth)acrylate compound. Specific examples of polymerizable monomers include those described in paragraphs 0095 to 0108 of JP 2009-288705 A, paragraph 0227 of JP 2013-029760 A, paragraphs 0254 to 0257 of JP 2008-292970 A, paragraphs 0034 to 0038 of JP 2013-253224 A, paragraph 0477 of JP 2012-208494 A, JP 2017-048367 A, Japanese Patent No. 6057891 A, and Japanese Patent No. 6031807 A, the contents of which are incorporated herein by reference.

[0080] The ethylenically unsaturated bond-containing group value (hereinafter also referred to as C=C value) of the polymerizable monomer is preferably 1.0 to 15.0 mmol / g. The lower limit is preferably 1.5 mmol / g or more, more preferably 2.0 mmol / g or more. The upper limit is preferably 14.0 mmol / g or less, more preferably 12.0 mmol / g or less.

[0081] As the polymerizable monomer, dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and 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 (e.g., SR454, SR499, commercially available from Sartomer Co., Ltd.) are preferred. As the polymerizable monomer, diglycerol EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (KAYARAD; manufactured by Nippon Kayaku Co., Ltd.) HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like can also be used.

[0082] In addition, the polymerizable monomer may be a trifunctional (meth)acrylate compound such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy-modified tri(meth)acrylate, trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, isocyanuric acid ethyleneoxy-modified tri(meth)acrylate, or pentaerythritol tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0083] In addition, a compound having an acid group can be used as the polymerizable monomer. By using a polymerizable monomer having an acid group, the polymerizable monomer in the unexposed area is easily removed during development, and the generation of development residues can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group, and the like, with a carboxyl group being preferred. Examples of the polymerizable monomer having an acid group include succinic acid-modified dipentaerythritol penta(meth)acrylate. Examples of commercially available polymerizable monomers having an acid group include ARONIX M-510, M-520, and ARONIX TO-2349 (manufactured by Toagosei Co., Ltd.). The preferred acid value of the polymerizable monomer 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 monomer is 0.1 mgKOH / g or more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous in terms of production and handling.

[0084] In addition, a polymerizable monomer having an alkyleneoxy group can also be used as the polymerizable monomer. The polymerizable monomer having an alkyleneoxy group is preferably a polymerizable monomer having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable monomer having an ethyleneoxy group, and even more preferably a trifunctional to hexafunctional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Examples of commercially available polymerizable monomers having an alkyleneoxy group include SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups, manufactured by Sartomer, and KAYARAD TPA-330, a trifunctional (meth)acrylate having three isobutyleneoxy groups.

[0085] It is also preferable to use a polymerizable monomer having a fluorene skeleton as the polymerizable monomer. By using a polymerizable monomer having a fluorene skeleton, it is possible to increase the degree of curing by exposure to adsorb to an organic pigment, and the effect of the present invention can be more significantly obtained. It is preferable that the polymerizable monomer having a fluorene skeleton is a bifunctional polymerizable monomer.

[0086] Examples of the polymerizable monomer having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr). [ka]

[0087] In the formula, the wavy line represents a bond, and R f1 and R f2 each independently represents a substituent, and m and n each independently represent an integer of 0 to 5. When m is 2 or more, m R f1 may be the same or different, and m R f1 Two of the R f1 may be bonded to each other to form a ring. When n is 2 or more, n R f2 may be the same or different, and n R f2 Two of the R f2 They may be bonded together to form a ring.f1 and R f2 The substituent represented by is a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR f11 , -COR f12 , -COOR f13 , -OCOR f14 , -NR f15 R f16 , -NHCOR f17 , -CONR f18 R f19 , -NHCONR f20 R f21 , -NHCOOR f22 , -SR f23 , -SO2R f24 , -SO2OR f25 , -NHSO2R f26 or -SO2NR f27 R f28 Examples include: R f11 ~R f28 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

[0088] Specific examples of polymerizable monomers having a fluorene skeleton include compounds having the following structures: Commercially available polymerizable monomers having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton). [ka]

[0089] As the polymerizable monomer, compounds represented by the following formulae (MO-1) to (MO-6) can also be used. In the formulae, when T is an oxyalkylene group, the end on the carbon atom side is bonded to R.

[0090] [ka]

[0091] In the above formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R's and T's present in one molecule may be the same or different. In each of the compounds represented by the above formulas (MO-1) to (MO-6), at least one of the multiple R's represents -OC(=O)CH=CH2, -OC(=O)C(CH3)=CH2, -NHC(=O)CH=CH2, or -NHC(=O)C(CH3)=CH2. Specific examples of the polymerizable compounds represented by the above formulas (MO-1) to (MO-6) include the compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-269779.

[0092] It is also preferable to use a compound having a caprolactone structure as the polymerizable monomer. The compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).

[0093] [ka]

[0094] In formula (Z-1), all of the six R's are groups represented by formula (Z-2), or 1 to 5 of the six R's are groups represented by formula (Z-2), and the remainder are groups represented by formula (Z-3), acid groups, or hydroxy groups.

[0095] [ka] In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents the number 1 or 2, and "*" represents a bond.

[0096] [ka] In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bond.

[0097] Commercially available polymerizable monomers having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.).

[0098] As the polymerizable monomer, a compound represented by formula (Z-4) or (Z-5) can also be used.

[0099] [ka]

[0100] In formulas (Z-4) and (Z-5), each E is independently -((CH2) y CH2O)- or -((CH2) y CH(CH3)O)-, each y independently represents an integer of 0 to 10, and each X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

[0101] In formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The sum of the m's is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8. In formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The sum of the n's is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12. In addition, -((CH2) y CH2O)- or -((CH2) y In the case of CH(CH3)O)-, the terminal on the oxygen atom side is preferably bonded to X.

[0102] The content of the polymerizable monomer in the total solid content of the photosensitive composition is 4% by mass or more, and preferably 4 to 20% by mass. The upper limit is preferably 17% by mass or less, and more preferably 15% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 68% by mass or more, even more preferably 10% by mass or more, and even more preferably 12% by mass or more.

[0103] The content of the polymerizable monomer is 5 to 200 parts by mass, preferably 10 to 100 parts by mass, more preferably 15 to 90 parts by mass, even more preferably 20 to 80 parts by mass, and particularly preferably 25 to 75 parts by mass, relative to 100 parts by mass of the polymerizable resin.

[0104] The content of the polymerizable monomer is preferably 100 to 1000 parts by mass, more preferably 200 to 800 parts by mass, and further preferably 300 to 600 parts by mass, relative to 100 parts by mass of the photopolymerization initiator.

[0105] The photosensitive composition of the present invention may contain two or more polymerizable monomers. When the photosensitive composition of the present invention contains two or more polymerizable monomers, the total amount thereof is within the above range.

[0106] When the photosensitive composition of the present invention contains two or more kinds of polymerizable monomers, it is preferable to use polymerizable monomers having different numbers of ethylenically unsaturated bond-containing groups in combination. In this case, it is preferable to use a monofunctional to trifunctional polymerizable monomer C1 having 1 to 3 ethylenically unsaturated bond-containing groups in combination with a tetrafunctional to decafunctional polymerizable monomer C2 having 4 to 10 ethylenically unsaturated bond-containing groups in combination. According to this embodiment, crosslinking can be performed at a higher density. In addition, it is preferable that the polymerizable monomer C1 is a bifunctional polymerizable monomer. In addition, it is preferable that the polymerizable monomer C1 is a polymerizable monomer having a fluorene skeleton. In addition, it is preferable that the polymerizable monomer C2 is a tetrafunctional to octafunctional polymerizable monomer, and more preferably a hexafunctional to octafunctional polymerizable monomer. When the polymerizable monomer C1 and the polymerizable monomer C2 are used in combination, the ratio of the two is preferably 10 to 5,000 parts by mass of the polymerizable monomer C1 to 100 parts by mass of the polymerizable monomer C2. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more. The upper limit is preferably 3000 parts by mass or less, more preferably 2000 parts by mass or less, even more preferably 1000 parts by mass or less, even more preferably 500 parts by mass or less, and particularly preferably 200 parts by mass or less.

[0107] <<Polymerizable resin>> The photosensitive composition of the present invention contains a polymerizable resin D (hereinafter referred to as a polymerizable resin) having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group contained in the polymerizable resin include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.

[0108] The weight average molecular weight of the polymerizable resin is preferably 3,000 or more, more preferably 3,000 to 50,000, further preferably 5,000 to 50,000, and particularly preferably 5,000 to 40,000.

[0109] The C=C value of the polymerizable resin is preferably 0.04 to 2.0 mmol / g. The upper limit is preferably 1.5 mmol / g or less, more preferably 1.0 mmol / g or less. The lower limit is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more.

[0110] The polymerizable resin is preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in a side chain, and more preferably a resin containing a repeating unit represented by the following formula (A-1-1): In the polymerizable resin, the content of the repeating unit having an ethylenically unsaturated bond-containing group is preferably 10 mol % or more, more preferably 10 to 80 mol %, and even more preferably 20 to 70 mol %, of all the repeating units of the polymerizable resin. [ka]

[0111] In formula (A-1-1), X 1 represents a trivalent linking group, L 1 represents a single bond or a divalent linking group; Y 1 represents an ethylenically unsaturated bond-containing group.

[0112] X in formula (A-1-1) 1 Examples of the trivalent linking group represented by the formula (I) include a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, a polystyrene linking group, and the like. Of these, a poly(meth)acrylic linking group, a polyalkyleneimine linking group, and a polyester linking group are preferred, and a poly(meth)acrylic linking group is more preferred.

[0113] L in formula (A-1-1) 1Examples of the divalent linking group represented by include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, and a group formed by combining two or more of these. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and are preferably linear or branched. In addition, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group, with a hydroxy group being preferred from the viewpoint of manufacturability.

[0114] Y in formula (A-1-1) 1 Examples of the ethylenically unsaturated bond-containing group represented by the formula (I) include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a styrene group, of which a (meth)acryloyl group and a styrene group are preferred, a (meth)acryloyl group is more preferred, and an acryloyl group is particularly preferred.

[0115] Specific examples of the repeating unit represented by formula (A-1-1) include a repeating unit represented by the following formula (A-1-1a) and a repeating unit represented by the following formula (A-1-1b). [ka]

[0116] In formula (A-1-1a), R a1 ~R a3 each independently represents a hydrogen atom or an alkyl group; Q 1a represents -CO-, -COO-, -OCO-, -CONH- or a phenylene group; L 1 represents a single bond or a divalent linking group; Y1 R represents an ethylenically unsaturated bond-containing group. a1 ~R a3 The number of carbon atoms in the alkyl group represented by Q is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1. 1a is preferably -COO- or -CONH-, and more preferably -COO-.

[0117] In formula (A-1-1b), R a10 and R a11 each independently represents a hydrogen atom or an alkyl group; m1 represents an integer of 1 to 5; L 1 represents a single bond or a divalent linking group; Y 1 R represents an ethylenically unsaturated bond-containing group. a10 and R a11 The alkyl group represented by the formula (I) preferably has 1 to 10 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0118] The polymerizable resin is also preferably a resin having a graft chain. An example of the resin having a graft chain is a resin containing a repeating unit having a graft chain. The polymerizable resin having a graft chain can be preferably used as a dispersant. When a polymerizable resin having a graft chain is used, the polymerizable resin is polymerized in the vicinity of the colorant during exposure, and the colorant can be firmly held in the film, and the thermal diffusion of these compounds due to heating can be effectively suppressed. The graft chain means a molecular chain branched from the main chain. The main chain means a molecular chain with the most branch points.

[0119] The weight average molecular weight of the graft chain is preferably from 500 to 30,000, more preferably from 1,000 to 20,000, and further preferably from 2,000 to 10,000.

[0120] The graft chain preferably contains a repeating unit of at least one structure selected from a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure, more preferably contains a repeating unit of at least one structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure, and further preferably contains a repeating unit of a polyester structure. Examples of the repeating unit of the polyester structure include a repeating unit of a structure represented by the following formula (G-1), formula (G-4), or formula (G-5). Examples of the repeating unit of the polyether structure include a repeating unit of a structure represented by the following formula (G-2). Examples of the repeating unit of the poly(meth)acrylic structure include a repeating unit of a structure represented by the following formula (G-3). [ka]

[0121] In the above formula, R G1 and R G2 Each of R represents an alkylene group. G1 and R G2 The alkylene group represented by the formula (I) is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and even more preferably a linear or branched alkylene group having 3 to 12 carbon atoms. In the above formula, R G3 represents a hydrogen atom or a methyl group. In the above formula, Q G1 represents -O- or -NH-. In the above formula, L G1represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and a group formed by combining two or more of these. R G4 represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an ethylenically unsaturated bond-containing group, a cyclic ether group, and a blocked isocyanate group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group.

[0122] The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group. Among them, from the viewpoint of improving the dispersibility of the pigment, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 30 carbon atoms is preferable. The alkyl group and the alkoxy group may be any of a straight chain, a branched group, and a cyclic group, and a straight chain or a branched group is preferable.

[0123] The polymerizable resin is preferably a resin containing a repeating unit represented by the following formula (A-1-2). [ka]

[0124] In formula (A-1-2), X 2 represents a trivalent linking group, L 2 represents a single bond or a divalent linking group, W 1 represents a graft chain.

[0125] X in formula (A-1-2) 2 The trivalent linking group represented by X in formula (A-1-1) is 1 The preferred ranges of L in formula (A-1-2) are also the same. 2 Examples of the divalent linking group represented by include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and a group formed by combining two or more of these. 1 The graft chain represented by the formula (I) includes the graft chains described above.

[0126] Specific examples of the repeating unit represented by formula (A-1-2) include a repeating unit represented by the following formula (A-1-2a) and a repeating unit represented by the following formula (A-1-2b). [ka]

[0127] In formula (A-1-2a), R b1 ~R b3 each independently represents a hydrogen atom or an alkyl group; Q b1 represents -CO-, -COO-, -OCO-, -CONH- or a phenylene group; L 2 represents a single bond or a divalent linking group; W 1 represents a graft chain. R b1 ~R b3 The number of carbon atoms in the alkyl group represented by Q is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1. b1 is preferably -COO- or -CONH-, and more preferably -COO-.

[0128] In formula (A-1-2b), R b10 and R b11 each independently represents a hydrogen atom or an alkyl group; m2 represents an integer of 1 to 5; L 2 represents a single bond or a divalent linking group; W 1 represents a graft chain. R b10 and R b11 The alkyl group represented by the formula (I) preferably has 1 to 10 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0129] When the polymerizable resin contains a repeating unit having a graft chain, the weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and even more preferably 1000 to 7500. In the present invention, the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used in the polymerization of the repeating unit. For example, the repeating unit having a graft chain can be formed by polymerizing a macromonomer. Here, the macromonomer means a polymeric compound having a polymerizable group introduced at the polymer end. When the repeating unit having a graft chain is formed using a macromonomer, the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.

[0130] When the polymerizable resin contains a repeating unit represented by formula (A-1-2), the content of the repeating unit represented by formula (A-1-2) is preferably 1.0 to 60 mol %, and more preferably 1.5 to 50 mol %, of all repeating units in the polymerizable resin.

[0131] It is also preferable that the polymerizable resin further contains a repeating unit having an acid group. By containing a repeating unit having an acid group, the dispersibility of pigments and the like can be further improved. Furthermore, the developability can be improved. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group.

[0132] When the polymerizable resin contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 80 mol % or less, more preferably 10 to 80 mol %, of all repeating units of the polymerizable resin. When the polymerizable resin contains a repeating unit having an acid group, the acid value of the polymerizable resin is preferably 20 to 150 mgKOH / g. The upper limit is more preferably 100 mgKOH / g or less. The lower limit is preferably 30 mgKOH / g or more, more preferably 35 mgKOH / g or more. When the acid value of the polymerizable resin is in the above range, particularly excellent dispersibility is easily obtained. Furthermore, excellent developability is easily obtained.

[0133] The polymerizable resin is also preferably a resin containing a repeating unit represented by formula (Ac-1). [ka] In formula (Ac-1), Ar 10 represents a group containing an aromatic carboxyl group, L 11 represents -COO- or -CONH-, and L 12 represents a trivalent linking group, P 10 represents a polymer chain having an ethylenically unsaturated bond-containing group.

[0134] In formula (Ac-1), Ar 10 Examples of the aromatic carboxyl group-containing group represented by the formula (1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, etc. Examples of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures. [ka]

[0135] In the above formula, Q 1 represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2). [ka] [ka]

[0136] In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2. In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 2. In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, and are 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 more. In formula (Ar-13), Q 1 represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the above formula (Q-1) or a group represented by the above formula (Q-2). In formulas (Ar-11) to (Ar-13), *1 represents L 11 represents the bonding position with

[0137] L in formula (Ac-1) 11 represents -COO- or -CONH-, and preferably represents -COO-.

[0138] L in formula (Ac-1) 12Examples of the trivalent linking group represented by include a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and a group combining two or more of these. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. L 12 The trivalent linking group represented by formula (L12-1) is preferable, and a group represented by formula (L12-2) is more preferable. [ka]

[0139] In formula (L12-1), L 12b represents a trivalent linking group, X 1 represents S, and *1 represents L in formula (Ac-1). 11 *2 represents the bond position of P in formula (Ac-1). 10 It represents the bond position with L 12b Examples of the trivalent linking group represented by include a hydrocarbon group; a group in which a hydrocarbon group is combined with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-; and the like. A hydrocarbon group or a group in which a hydrocarbon group is combined with -O- is preferred.

[0140] In formula (L12-2), L 12c represents a trivalent linking group, X 1 represents S, and *1 represents L in formula (Ac-1). 11 *2 represents the bond position of P in formula (Ac-1). 10 It represents the bond position with L 12c Examples of the trivalent linking group represented by include a hydrocarbon group; a group formed by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and a hydrocarbon group is preferred.

[0141] P in formula (Ac-1) 10 represents a polymer chain having an ethylenically unsaturated bond-containing group. 10 The polymer chain represented by the formula (G-1), (G-4) or (G-5) may preferably include a repeating unit of at least one structure selected from polyester structure, polyether structure, poly(meth)acrylic structure, polystyrene structure, polyurethane structure, polyurea structure and polyamide structure, more preferably include a repeating unit of at least one structure selected from polyester structure, polyether structure and poly(meth)acrylic structure, and further preferably include a repeating unit of polyester structure. The repeating unit of polyester structure may include a repeating unit of the structure represented by the formula (G-1), (G-4) or (G-5) described above. The repeating unit of polyether structure may include a repeating unit of the structure represented by the formula (G-2) described above. The repeating unit of poly(meth)acrylic structure may include a repeating unit of the structure represented by the formula (G-3) described above.

[0142] Also, P 10 For the polymer chain represented by P 10 The proportion of repeating units containing an ethylenically unsaturated bond-containing group in a side chain in all repeating units constituting the polymer is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. The upper limit can be set to 100% by mass, and is preferably 90% by mass or less, and even more preferably 60% by mass or less.

[0143] Also, P 10 It is also preferable that the polymer chain represented by has a repeating unit containing an acid group. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group. According to this embodiment, the dispersibility of the pigment in the composition can be further improved. Furthermore, the developability can also be further improved. The proportion of the repeating unit containing an acid group is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 10% by mass.

[0144] P 10 The weight average molecular weight of the polymer chain represented by is preferably 500 to 20,000. The lower limit is preferably 600 or more, more preferably 1,000 or more. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. 10 If the weight average molecular weight is within the above range, the dispersibility of the pigment in the composition is good. This resin is preferably used as a dispersant.

[0145] The weight average molecular weight of the resin containing the repeating unit represented by formula (Ac-1) is preferably 3000 to 35000. The upper limit is preferably 25000 or less, more preferably 20000 or less, and even more preferably 15000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more, and even more preferably 6000 or more.

[0146] The acid value of the resin containing the repeating unit represented by formula (Ac-1) is preferably 5 to 200 mgKOH / g. The upper limit is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less. The lower limit is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and even more preferably 20 mgKOH / g or more.

[0147] The content of the polymerizable resin in the total solid content of the photosensitive composition is preferably 1 to 40% by mass. The upper limit is preferably 35% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 18% by mass or more. The total amount of the polymerizable monomer and the polymerizable resin in the total solid content of the photosensitive composition is preferably 5 to 45% by mass. The upper limit is preferably 40% by mass or less, and more preferably 38% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.

[0148] The photosensitive composition of the present invention may contain two or more polymerizable resins. When the photosensitive composition of the present invention contains two or more polymerizable resins, the total amount thereof is within the above range.

[0149] <<Other resins>> The photosensitive composition of the present invention may contain a resin other than the above-mentioned polymerizable resin (hereinafter, also referred to as other resin). The other resin is blended, for example, for dispersing a pigment in the photosensitive composition or for use as a binder. Note that a resin used mainly for dispersing a pigment is also referred to as a dispersant. However, such uses of the resin are merely examples, and the resin may be used for purposes other than these uses.

[0150] The weight average molecular weight (Mw) of the other resin is preferably 3,000 to 2,000,000. The upper limit is more preferably 1,000,000 or less, and even more preferably 500,000 or less. The lower limit is more preferably 4,000 or more, and even more preferably 5,000 or more.

[0151] Examples of other resins include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, etc. One of these resins may be used alone, or two or more of them may be used in combination. In addition, resins described in paragraphs 0041 to 0060 of JP 2017-206689 A, resins described in paragraphs 0022 to 0071 of JP 2018-010856 A, resins described in JP 2017-057265 A, resins described in JP 2017-032685 A, resins described in JP 2017-075248 A, and resins described in JP 2017-066240 A can also be used.

[0152] As the other resin, it is preferable to use a resin having an acid group. According to this embodiment, the developability of the pixel-forming composition can be improved. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxyl group, and the carboxyl group is preferable. The resin having an acid group can be used, for example, as an alkali-soluble resin. The resin having an acid group is preferably a resin containing a repeating unit having an acid group in a side chain, and more preferably a resin containing 5 to 70 mol % of the repeating unit having an acid group in a side chain in the total repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in a side chain is more preferably 50 mol % or less, and particularly preferably 30 mol % or less. The lower limit of the content of the repeating unit having an acid group in a side chain is more preferably 10 mol % or more, and particularly preferably 20 mol % or more. For the resin having an acid group, the description in paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding to paragraphs 0685 to 0700 of U.S. Patent Application Publication No. 2012 / 0235099 A) and the description in paragraphs 0076 to 0099 of JP 2012-198408 A can be referred to, the contents of which are incorporated herein by reference. In addition, a commercially available product can be used as the resin having an acid group.

[0153] The other resins may be resins used as dispersants. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the acid groups and the basic groups is 100 mol%, and more preferably a resin substantially composed of only acid groups. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g. The basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin having a basic group amount exceeding 50 mol % when the total amount of the acid group amount and the basic group amount is 100 mol %. The basic group of the basic dispersant is preferably an amino group. The resin used as the dispersant is also preferably a graft resin. Examples of the graft resin include the resins described in paragraphs 0025 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein by reference. The resin used as the dispersant is also preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant is preferably a resin having a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having an atomic number of 40 to 10,000, and having a basic nitrogen atom in at least one of the main chain and the side chain. There is no particular limitation on the basic nitrogen atom as long as it is a nitrogen atom that exhibits basicity. Examples of polyimine-based dispersants include resins described in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference. In addition, it is also preferable that the resin used as the dispersant is a resin having a structure in which a plurality of polymer chains are bonded to a core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP 2013-043962 A.In addition, as the dispersant, polyethyleneimine having a polyester side chain described in WO 2016 / 104803, a block copolymer described in WO 2019 / 125940, a block polymer having an acrylamide structural unit described in JP 2020-066687 A, a block polymer having an acrylamide structural unit described in JP 2020-066688 A, and the like can also be used. In addition, the dispersant is also available as a commercially available product, and specific examples thereof include the DISPERBYK series (e.g., DISPERBYK-111, 161, etc.) manufactured by BYK Chemie, and the Solsperse series (e.g., Solsperse 76500, etc.) manufactured by Nippon Lubrizol Co., Ltd. In addition, the pigment dispersant described in paragraphs 0041 to 0130 of JP 2014-130338 A can also be used, and the contents of this specification are incorporated herein. In addition, the resin described as the dispersant above can also be used for purposes other than dispersants. For example, it can be used as a binder.

[0154] The content of other resins in the total solid content of the photosensitive composition is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The total content of the polymerizable resin and other resins in the total solid content of the photosensitive composition is preferably 1 to 40% by mass. The upper limit is preferably 35% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 18% by mass or more. The other resin may be one kind or two or more kinds. When two or more kinds are contained, the total amount thereof is preferably within the above range.

[0155] <<Pigment derivatives>> The photosensitive composition of the present invention may contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton. Examples of the pigment skeleton constituting the pigment derivative include a quinoline pigment skeleton, a benzimidazolone pigment skeleton, a benzisoindole pigment skeleton, a benzothiazole pigment skeleton, an inimium pigment skeleton, a squarylium pigment skeleton, a croconium pigment skeleton, an oxonol pigment skeleton, a pyrrolopyrrole pigment skeleton, a diketopyrrolopyrrole pigment skeleton, an azo pigment skeleton, an azomethine pigment skeleton, a phthalocyanine pigment skeleton, a naphthalocyanine pigment skeleton, an anthraquinone pigment skeleton, a quinacridone pigment skeleton, a dioxazine pigment skeleton, a perinone pigment skeleton, a perylene pigment skeleton, a thioindigo pigment skeleton, an isoindoline pigment skeleton, an isoindolinone pigment skeleton, a quinophthalone pigment skeleton, an iminium pigment skeleton, a dithiol pigment skeleton, a triarylmethane pigment skeleton, and a pyrromethene pigment skeleton. Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric acid group, and salts thereof. The atoms or atomic groups that make up the salt are alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ Examples of the basic group include an amino group, a pyridinyl group and its salt, an ammonium group salt, and a phthalimidomethyl group. Examples of the atom or atomic group constituting the salt include a hydroxide ion, a halogen ion, a carboxylate ion, a sulfonate ion, and a phenoxide ion.

[0156] Pigment derivatives with excellent visible transparency (hereinafter also referred to as transparent pigment derivatives) can also be used. The maximum molar absorption coefficient (εmax) of transparent pigment derivatives in the wavelength range of 400 to 700 nm is 3000 L·mol -1 ·cm -1 It is preferable that the concentration is less than 1000 L·mol -1 ·cm -1 It is more preferable that it is less than 100 L·mol -1·cm -1 The lower limit of εmax is, for example, 1 L mol -1 ·cm -1 is greater than or equal to 10 L mol -1 ·cm -1 More than that is fine.

[0157] Specific examples of the pigment derivative include the compounds described in the examples described later, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, JP-A-03-153780, JP-A-03-045662, JP-A-04-285669, JP-A-06-145546, JP-A-06-212088, JP-A-06-240158, JP-A-10-030063, JP-A-10-195326, and paragraphs of International Publication No. 2011 / 024896. Nos. 0086 to 0098, paragraphs 0063 to 0094 of International Publication No. 2012 / 102399, paragraph 0082 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 compounds described in JP-A-2008-081565 are included.

[0158] The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the coloring material. Only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0159] <<Polyalkyleneimine>> The photosensitive composition of the present invention may also contain a polyalkyleneimine. The polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine, and has a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group. The number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0160] The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. In addition, when the value of the molecular weight of the polyalkyleneimine can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. In addition, when the molecular weight cannot be measured by the boiling point elevation method or is difficult to measure, the value of the number average molecular weight measured by the viscosity method is used. In addition, when the molecular weight cannot be measured by the viscosity method or is difficult to measure by the viscosity method, the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.

[0161] The amine value of the polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.

[0162] Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, and are preferably ethyleneimine or propyleneimine, and more preferably ethyleneimine. The polyalkyleneimine is particularly preferably polyethyleneimine. Moreover, the polyethyleneimine preferably contains 10 mol% or more of primary amino groups, more preferably 20 mol% or more, and even more preferably 30 mol% or more of primary amino groups, based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. Commercially available polyethyleneimine products include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).

[0163] The content of the alkyleneimine in the total solid content of the photosensitive composition is preferably 0.1 to 5 mass%. The lower limit is preferably 0.2 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more. The upper limit is preferably 4.5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less. The content of the alkyleneimine is preferably 0.5 to 10 mass parts relative to 100 mass parts of the pigment. The lower limit is preferably 0.6 mass parts or more, more preferably 1 mass% or more, and even more preferably 2 mass parts or more. The upper limit is preferably 8 mass parts or less, more preferably 7 mass% or less, and even more preferably 5 mass parts or less. Only one type of alkyleneimine may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0164] <<Compounds containing cyclic ether groups>> The photosensitive composition of the present invention may contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy groups contained in the epoxy compound may be, for example, 10 or less, or 5 or less. The lower limit of the epoxy groups contained in the epoxy compound is preferably 2 or more. As the epoxy compound, the compounds described in paragraphs 0034 to 0036 of JP 2013-011869 A, paragraphs 0147 to 0156 of JP 2014-043556 A, paragraphs 0085 to 0092 of JP 2014-089408 A, and the compounds described in JP 2017-179172 A can also be used. The contents of these are incorporated herein by reference.

[0165] The epoxy compound may be either a low molecular weight compound (e.g., a molecular weight less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (e.g., a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 3,000 or less.

[0166] As the epoxy compound, an epoxy resin can be preferably used. Examples of the epoxy resin include an epoxy resin which is a glycidyl ether of a phenolic compound, an epoxy resin which is a glycidyl ether of various novolac resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine epoxy resin, an epoxy resin obtained by glycidylating halogenated phenols, a condensate of a silicon compound having an epoxy group and another silicon compound, and a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and even more preferably 310 to 1000 g / eq.

[0167] Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).

[0168] The content of the compound having a cyclic ether group in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is, for example, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is, for example, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0169] <<Curing accelerator>> The photosensitive composition of the present invention may contain a curing accelerator, such as a thiol compound, a methylol compound, an amine compound, a phosphonium salt compound, an amidine salt compound, an amide compound, a base generator, an isocyanate compound, an alkoxysilane compound, or an onium salt compound. Specific examples of the curing accelerator include compounds described in paragraphs 0094 to 0097 of International Publication No. 2018 / 056189, compounds described in paragraphs 0246 to 0253 of JP-A-2015-034963, compounds described in paragraphs 0186 to 0251 of JP-A-2013-041165, ionic compounds described in JP-A-2014-055114, compounds described in paragraphs 0071 to 0080 of JP-A-2012-150180, alkoxysilane compounds described in JP-A-2011-253054, compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, and carboxyl group-containing epoxy curing agents described in JP-A-2017-036379. The content of the curing accelerator in the total solid content of the photosensitive composition is preferably from 0.3 to 8.9 mass %, more preferably from 0.8 to 6.4 mass %.

[0170] <<Surfactants>> The photosensitive composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants may be used. As the surfactant, the surfactants described in paragraphs 0238 to 0245 of WO 2015 / 166779 may be mentioned, the contents of which are incorporated herein by reference.

[0171] The surfactant is preferably a fluorosurfactant. By including a fluorosurfactant in the photosensitive composition, the liquid properties (particularly, fluidity) can be improved, and the liquid saving can be improved. In addition, a film with less unevenness in thickness can be formed.

[0172] The fluorine content in the fluorosurfactant is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and particularly preferably 7 to 25 mass%. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the coating film thickness and liquid saving, and also has good solubility in the photosensitive composition.

[0173] Examples of fluorine-based surfactants include those described in paragraphs 0060 to 0064 of JP 2014-041318 A (corresponding paragraphs 0060 to 0064 of WO 2014 / 017669 A), those described in paragraphs 0117 to 0132 of JP 2011-132503 A, and those described in JP 2020-008634 A, the contents of which are incorporated herein by reference. Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, and R-01. , R-40, R-40-LM, R-41, R-41-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Corporation), PolyFox Examples of such agents include PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Ftergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, FTX-218 (all manufactured by NEOS Co., Ltd.).

[0174] In addition, the fluorosurfactant may be an acrylic compound that has a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the functional group containing the fluorine atom is broken and the fluorine atom volatilizes. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016)), such as Megafac DS-21.

[0175] In addition, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant. Examples of such a fluorine-based surfactant include the fluorine-based surfactants described in JP 2016-216602 A, the contents of which are incorporated herein by reference.

[0176] The fluorosurfactant may be a block polymer. The fluorosurfactant may be a fluorine-containing polymer compound that contains a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups). In addition, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorosurfactant used in the present invention. [ka] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compound, % indicating the proportion of repeating units is mol %.

[0177] In addition, the fluorine-based surfactant may be a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in a side chain.Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, and Megafac RS-101, RS-102, RS-718K, and RS-72-K manufactured by DIC Corporation.In addition, the fluorine-based surfactant may be the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A.

[0178] In addition, it is also preferable from the viewpoint of environmental regulations to use the surfactants described in WO 2020 / 084854 as a substitute for surfactants having a perfluoroalkyl group having 6 or more carbon atoms.

[0179] It is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant. [ka] In formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, α represents 1 or 2, and X α+ is an α-valent metal ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion, or NH4 + Represents.

[0180] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid. Examples of such an agent include ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil Co., Ltd.), Olfin E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0181] Examples of silicone surfactants 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 Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, and TSF- 4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie), FZ-2122 (manufactured by Dow-Toray Co., Ltd.), and the like.

[0182] Furthermore, the silicone surfactant may also be a compound having the following structure: [ka]

[0183] The content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0184] <<Solvent>> The photosensitive composition of the present invention may contain a solvent. The type of solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. The solvent is preferably an organic solvent. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details of these, refer to paragraph 0223 of International Publication No. 2015 / 166779, the contents of which are incorporated herein by reference. In addition, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, and butyl ether. Examples of suitable organic solvents include ethyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, and diacetone alcohol. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be reduced for environmental reasons (for example, the amount of the organic solvent may be reduced to 50 ppm (parts per million) or less, 10 ppm or less, or 1 ppm or less).

[0185] In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent with a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).

[0186] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter used for filtration has a filter pore size of preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0187] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). In addition, the organic solvent may contain only one type of isomer or multiple types of isomers.

[0188] The organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

[0189] The content of the solvent in the photosensitive composition is preferably 10 to 95% by mass. The upper limit is preferably 92.5% by mass or less, and more preferably 90% by mass or less. From the viewpoint of coatability, the lower limit is preferably 20% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, still more preferably 75% by mass or more, and even more preferably 80% by mass or more.

[0190] In addition, from the viewpoint of environmental regulations, the photosensitive composition of the present invention preferably does not substantially contain environmentally regulated substances. In the present invention, "substantially does not contain environmentally regulated substances" means that the content of the environmentally regulated substances in the photosensitive composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm 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 the REACH (Registration Evaluation Authorization and Restriction of CHemicals) regulations, the PRTR (Pollutant Release and Transfer Register) Act, and the VOC (Volatile Organic Compounds) regulations, and their usage and handling methods are strictly regulated. These compounds may be used as solvents when producing each component used in the photosensitive composition, and may be mixed into the photosensitive composition as a residual solvent. From the viewpoint of human safety and environmental consideration, it is preferable to reduce these substances as much as possible. A method for reducing the environmentally regulated substances includes a method of heating or reducing the pressure in the system to a temperature equal to or higher than the boiling point of the environmentally regulated substances, and distilling off the environmentally regulated substances from the system. In addition, when a small amount of the environmentally regulated substances is distilled off, it is also useful to perform azeotropy with a solvent having a boiling point equivalent to that of the corresponding solvent in order to increase efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like may be added and distilled off under reduced pressure in order to suppress crosslinking between molecules caused by the progress of radical polymerization reaction during distillation under reduced pressure. These distillation methods are possible at any stage, such as the stage of the raw materials, the stage of the product obtained by reacting the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or the stage of the photosensitive composition prepared by mixing these compounds.

[0191] <<Silane coupling agents>> The photosensitive composition of the present invention may contain a silane coupling agent. In this specification, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group means a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, and an amino group, a (meth)acryloyl group, and an epoxy group are preferred. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxypropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-502), and 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-503). 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, the contents of which are incorporated herein by reference. The content of the silane coupling agent in the total solid content of the photosensitive composition is preferably 0.1 to 5% by mass. The upper limit is more preferably 3% by mass or less, and even more preferably 2% by mass or less. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.The silane coupling agent may be used alone or in combination with two or more kinds. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

[0192] <<Ultraviolet absorber>> The photosensitive composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Examples of such compounds include those described in paragraphs 0038-0052 of JP 2009-217221 A, paragraphs 0052-0072 of JP 2012-208374 A, paragraphs 0317-0334 of JP 2013-068814 A, and paragraphs 0061-0080 of JP 2016-162946 A, the contents of which are incorporated herein by reference. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.). In addition, examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016). In addition, the ultraviolet absorber may be a compound described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967. The content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10 mass%, more preferably 0.01 to 5 mass%. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0193] <<Antioxidants>> The photosensitive composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant may be used. Examples of preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to a phenolic hydroxy group is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, as the antioxidant, a compound having a phenolic group and a phosphite group in the same molecule is also preferred. In addition, as the antioxidant, a phosphorus-based antioxidant may also be suitably used. In addition, as the antioxidant, a compound described in Korean Patent Publication No. 10-2019-0059371 may also be used. The content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20 mass%, more preferably 0.3 to 15 mass%. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

[0194] <<Polymerization inhibitor>> The photosensitive composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.0001 to 5 mass %. The polymerization inhibitor may be one type or two or more types. When two or more types are used, the total amount is preferably within the above range.

[0195] <<Other ingredients>> In the present invention, the photosensitive composition may contain, as necessary, a sensitizer, a curing accelerator, a filler, a heat curing accelerator, a plasticizer, and other auxiliaries (for example, conductive particles, a filler, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension adjuster, a chain transfer agent, etc.). By appropriately incorporating these components, it is possible to adjust the properties such as film properties. For these components, for example, the description in paragraphs 0183 and after of JP-A-2012-003225 (corresponding to paragraph 0237 of US Patent Application Publication No. 2013 / 0034812) and the description in paragraphs 0101-0104, 0107-0109, etc. of JP-A-2008-250074 can be referred to, and the contents of these are incorporated herein. In addition, the photosensitive composition of the present invention may contain, as necessary, a latent antioxidant. Examples of the latent antioxidant include compounds in which the site functioning as an antioxidant is protected by a protecting group, and the protecting group is removed by heating at 100 to 250° C. or at 80 to 200° C. in the presence of an acid / base catalyst, thereby functioning as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and JP-A No. 2017-008219. Examples of commercially available latent antioxidants include ADEKA ARCLES GPA-5001 (manufactured by ADEKA Corporation).

[0196] The photosensitive composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, the compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of JP-A-2017-129774, the compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of JP-A-2017-129674, the compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of JP-A-2017-122803, the compounds described in paragraphs 0025 to 0039 of WO 2017 / 164127, and the compounds described in paragraphs 0025 to 0039 of JP-A-2017-186546. JP-A-2015-025116, JP-A-2012-145604, JP-A-2012-103475, JP-A-2012-103475, JP-A-2012-103475, JP-A-2011-257591, JP-A-2011-257591, JP-A-2011-191483, JP-A-2011-145668, JP-A-2011-145668, JP-A-2011-253174 ...7591, JP-A-2011-257591, JP-A-2011-253174, JP-A-2011-253174, JP-A-2011-253174, JP-A-2011-253174, JP-A-2011-253174,

[0197] In the photosensitive composition of the present invention, the content of free metals that are not bonded or coordinated to pigments, etc. is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 10 ppm or less, and particularly preferably substantially free. According to this embodiment, it is possible to expect effects such as stabilization of pigment dispersibility (prevention of aggregation), improvement of spectral characteristics due to improved dispersibility, stabilization of curable components, prevention of conductivity fluctuation due to elution of metal atoms and metal ions, and improvement of display characteristics. In addition, the effects described in JP 2012-153796 A, JP 2000-345085 A, JP 2005-200560 A, JP 08-043620 A, JP 2004-145078 A, JP 2014-119487 A, JP 2010-083997 A, JP 2017-090930 A, JP 2018-025612 A, JP 2018-025797 A, JP 2017-155228 A, JP 2018-036521 A, and the like can also be obtained. 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, Bi, etc. In addition, the content of free halogens not bonded or coordinated with pigments, etc. in the photosensitive composition of the present invention is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 10 ppm or less, and particularly preferably substantially free. Examples of halogens include F, Cl, Br, I, and anions thereof. Methods for reducing free metals and halogens in the photosensitive composition include washing with ion-exchanged water, filtration, ultrafiltration, purification with ion-exchange resin, etc.

[0198] It is also preferred that the photosensitive composition of the present invention is substantially free of terephthalic acid esters. Here, "substantially free" means that the content of terephthalic acid esters in the total amount of the photosensitive composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0199] From the viewpoint of environmental regulations, the use of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt may be restricted. In the photosensitive composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkylsulfonic acid (particularly perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt, and perfluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is preferably in the range of 0.01 ppb to 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, based on the total solid content of the photosensitive composition. The photosensitive composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt. For example, a photosensitive composition that is substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt may be selected by using a compound that can be a substitute for perfluoroalkylsulfonic acid and its salt, and a compound that can be a substitute for perfluoroalkylcarboxylic acid and its salt. Examples of compounds that can be a substitute for regulated compounds include compounds that are excluded from the scope of regulation due to the difference in the number of carbon atoms in the perfluoroalkyl group. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt. The photosensitive composition of the present invention may contain perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt within the maximum allowable range.

[0200] <<Containment Container>> The container for storing the photosensitive composition is not particularly limited, and a known container can be used. In addition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six-layer resin or a bottle with a seven-layer structure made of six types of resin as the container, in order to suppress the incorporation of impurities into the raw materials or the photosensitive composition. Examples of such containers include the container described in JP-A-2015-123351. In addition, it is also preferable that the inner wall of the container is made of glass or stainless steel in order to prevent metal elution from the inner wall of the container, increase the storage stability of the photosensitive composition, and suppress the deterioration of the components.

[0201] <Method of preparing photosensitive composition> The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photosensitive composition, all the components may be simultaneously dissolved and / or dispersed in a solvent to prepare the photosensitive composition, or, if necessary, each component may be appropriately prepared as two or more solutions or dispersions, which are mixed at the time of use (at the time of application) to prepare the photosensitive composition.

[0202] In addition, the photosensitive composition is preferably prepared by including a process for dispersing the pigment. In the process for dispersing the pigment, mechanical forces used for dispersing the pigment include compression, squeezing, impact, shear, and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand grinder, a flow jet mixer, high-pressure wet atomization, and ultrasonic dispersion. In addition, in the grinding of the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter, increase the bead packing rate, and perform the treatment under conditions that increase the grinding efficiency. In addition, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the grinding treatment. In addition, the process and dispersing machine for dispersing the pigment may be suitably used as described in "Dispersion Technology Encyclopedia, published by Joho Kika Co., Ltd., July 15, 2005" or "Dispersion Technology and Industrial Application Practices Focusing on Suspension (Solid / Liquid Dispersion System) Comprehensive Data Collection, published by Management Development Center Publishing Department, October 10, 1978" and in paragraph number 0022 of JP2015-157893A. In addition, in the process for dispersing the pigment, a salt milling process may be performed to refine the particles. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in, for example, JP2015-194521A and JP2012-046629A may be referred to.

[0203] In preparing the photosensitive composition, it is preferable to filter the photosensitive composition with a filter for the purpose of removing foreign matter and reducing defects. As the filter, any filter that has been used for filtering purposes can be used without any particular limitation. For example, there are filters using materials such as fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins (including high-density and ultra-high-molecular-weight polyolefin resins) such as polyethylene and polypropylene (PP). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0204] The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. The nominal value of the filter manufacturer can be referred to for the pore size value of the filter. Various filters provided by Nippon Pall Corporation (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Microfilter Co., Ltd., etc. can be used.

[0205] It is also preferable to use a fibrous filter medium as the filter. Examples of fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber, etc. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by ROKI TECHNO CO., LTD.

[0206] When using a filter, different filters (for example, a first filter and a second filter, etc.) may be combined. In this case, filtration with each filter may be performed only once or two or more times. Filters having different pore sizes within the above-mentioned range may be combined. Filtration with the first filter may be performed only on the dispersion liquid, and filtration with the second filter may be performed after mixing with other components.

[0207] <Method of manufacturing optical filters> Next, the method for producing the optical filter of the present invention will be described. Types of optical filters include color filters, near-infrared cut filters, and near-infrared transmission filters. The method for producing the optical filter of the present invention includes a step of forming a photosensitive composition layer on a support using the above-mentioned photosensitive composition of the present invention, a step of exposing the photosensitive composition layer by irradiating light having a wavelength of 300 nm or less in a pattern, and a step of developing and removing the photosensitive composition layer in the unexposed areas to form pixels. Each step will be described below.

[0208] In the step of forming a photosensitive composition layer, the photosensitive composition layer is formed on a support using the photosensitive composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. For example, a glass substrate, a silicon substrate, etc. can be mentioned, and a silicon substrate is preferable. A charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate. A partition wall for isolating each pixel may be formed on the silicon substrate. A base layer may be provided on the silicon substrate to improve adhesion with the upper layer, prevent diffusion of a substance, or flatten the substrate surface. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. The surface contact angle of the base layer is preferably 30 to 80° when measured with water. If the surface contact angle of the base layer is within the above range, the photosensitive composition has good wettability. The surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.

[0209] The photosensitive composition can be applied by any known method, including, for example, a dropping method (drop casting), a slit coating method, a spray method, a roll coating method, a rotary coating method (spin coating), a casting coating method, a slit and spin method, a pre-wetting method (e.g., a method described in JP-A-2009-145395), various printing methods such as ejection printing such as inkjet (e.g., on-demand method, piezo method, thermal method), nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing, a transfer method using a mold, and a nanoimprint method. The application method in inkjet is not particularly limited, and examples thereof include the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents -, published in February 2005, Sumibe Techno Research" (particularly pages 115 to 133), and the methods described in JP 2003-262716 A, JP 2003-185831 A, JP 2003-261827 A, JP 2012-126830 A, JP 2006-169325 A, etc. In addition, for the application method of the photosensitive composition, the descriptions in WO 2017 / 030174 and WO 2017 / 018419 can be referred to, and the contents of these are incorporated herein.

[0210] The photosensitive composition layer formed on the support may be dried (prebaked). When the film is produced by a low-temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower. The lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.

[0211] Next, the photosensitive composition layer formed on the support as described above is exposed to light having a wavelength of 300 nm or less in a pattern, whereby the exposed portions of the photosensitive composition layer can be cured.

[0212] The light used for exposure may have a wavelength of 300 nm or less, and preferably has a wavelength of 180 to 300 nm.Specific examples include light having a wavelength of 248 nm (KrF radiation) and light having a wavelength of 193 nm (ArF radiation), and the like, and light having a wavelength of 248 nm (KrF radiation) is preferred.

[0213] In addition, the exposure may be performed by irradiating the light continuously or by irradiating the light in pulses (pulse exposure). Pulse exposure is an exposure method in which light irradiation and pauses are repeated in a short cycle (for example, on the order of milliseconds or less).

[0214] The irradiation dose (exposure amount) is 0.03 to 2.5 J / cm 2 is preferable, and 0.05 to 1.0 J / cm 2 is more preferable. The oxygen concentration during exposure can be appropriately selected. In addition to being exposed in air, exposure may be performed in a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration of more than 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%). The exposure illuminance can be appropriately set, and is usually 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 may be appropriately combined. For example, the oxygen concentration is 10% by volume and the illuminance is 10,000 W / m 2 , oxygen concentration 35% by volume, illuminance 20000W / m 2 etc.

[0215] Next, the photosensitive composition layer in the unexposed portion of the photosensitive composition layer after the exposure step is developed and removed, whereby the photosensitive composition layer in the unexposed portion in the exposure step is dissolved into a developer, and only the photocured portion remains, forming pixels.

[0216] The temperature of the developer is preferably, for example, 20 to 30° C. The development time is preferably 20 to 180 seconds. In order to improve the removability of residues, the developer may be shaken off every 60 seconds and a process of supplying fresh developer may be repeated several times.

[0217] Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferred. Examples of the alkaline agent include organic alkaline compounds such as 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, and 1,8-diazabicyclo-[5.4.0]-7-undecene, and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, and sodium metasilicate. As the alkaline agent, compounds with a large molecular weight are preferred in terms of the environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. The developer may be prepared as a concentrated solution from the viewpoint of convenience of transportation and storage, and then diluted to a required concentration when used. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. It is also preferable to perform rinsing by supplying a rinsing liquid to the developed composition layer while rotating the support on which the developed composition layer is formed. It is also preferable to perform rinsing by moving the nozzle that ejects the rinsing liquid from the center of the support to the periphery of the support. In this case, when moving the nozzle from the center of the support to the periphery, the nozzle may be moved while gradually decreasing the moving speed. By performing rinsing in this manner, the in-plane variation of the rinse can be suppressed. The same effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.

[0218] After development and drying, it is preferable to perform additional exposure treatment or heating treatment (post-baking). Additional exposure treatment and post-baking are curing treatments after development to complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater to heat the developed film to the above conditions. When additional exposure treatment is performed, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure treatment may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

[0219] The thickness of the pixel to be formed can be adjusted appropriately depending on the purpose. The thickness of the pixel is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the thickness of the pixel is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0220] The line width of the formed pixel is preferably less than 1.0 μm, more preferably 0.9 μm or less, even more preferably 0.8 μm or less, even more preferably 0.7 μm or less, and particularly preferably 0.6 μm or less. There is no particular lower limit, but it can be 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, or 0.4 μm or more.

[0221] When a plurality of types of pixels are to be formed, the above-described steps can be repeated for each pixel to manufacture an optical filter having a plurality of pixels.

[0222] <Method of manufacturing a solid-state imaging device> The method for producing a solid-state imaging device of the present invention includes the method for producing the optical filter of the present invention described above. The configuration of the solid-state imaging device is not particularly limited as long as it has an optical filter and functions as a solid-state imaging device, and examples thereof include the following configurations.

[0223] The substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging device (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal oxide semiconductor) image sensor) and a transfer electrode formed of polysilicon or the like, a light shielding film with only the light receiving portion of the photodiodes open on the photodiodes and the transfer electrodes, a device protection film formed of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving portion of the photodiode, and an optical filter such as a color filter on the device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the optical filter (on the side closer to the substrate), or a light collecting means on the optical filter. The optical filter may have a structure in which each pixel is embedded in a space partitioned by partitions, for example, in a lattice shape. In this case, the partitions preferably have a low refractive index with respect to each pixel. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018 / 043654 A. In addition, as shown in JP 2019-211559 A, an ultraviolet absorbing layer may be provided in the structure of the solid-state imaging element to improve light resistance. The imaging device including the solid-state imaging element of the present invention can be used for digital cameras, electronic devices having imaging functions (such as mobile phones), as well as vehicle-mounted cameras and surveillance cameras.

[0224] <Manufacturing method for image display device> This specification discloses a method for manufacturing an image display device. This manufacturing method includes the above-mentioned method for manufacturing the optical filter of the present invention. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology" (edited by Uchida Tatsuo, published by Kogyo Chosakai Co., Ltd. in 1994). There are no particular limitations on the liquid crystal display device to which the present invention can be applied, and the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology." EXAMPLES

[0225] The present invention will be described in more detail below with reference to examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0226] <Conditions for measuring weight-average molecular weight and number-average molecular weight by gel permeation chromatography> Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 connected together Developing solvent: Tetrahydrofuran Column temperature: 40℃ Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1% by mass) Device name: Tosoh HLC-8220GPC Detector: RI (refractive index) detector Calibration curve base resin: polystyrene resin

[0227] <Production of Dispersion> The raw materials shown in the table were mixed to obtain a mixture. The mixture was subjected to a dispersion treatment using an Ultra Apex Mill manufactured by Kotobuki Industries Co., Ltd. as a circulation type dispersion device (bead mill) to produce a dispersion.

[0228] [Table 1]

[0229] Details of the abbreviations for the raw materials listed in the table above are as follows: [Pigment] PG58: CI Pigment Green58 (green pigment) PG36: CI Pigment Green36 (green pigment) PY185: CI Pigment Yellow 185 (yellow pigment) PY215: CI Pigment Yellow 215 (yellow pigment) PY129: CI Pigment Yellow 129 (yellow pigment) PY139: CI Pigment Yellow 139 (yellow pigment) PR254: CI Pigment Red 254 (red pigment) PR272: CI Pigment Red 272 (red pigment)

[0230] [Dispersion aid] A-1: Polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd., molecular weight 600, amine value 20 mmol / g)

[0231] [Pigment derivatives] D-1 to D-4: Compounds having the following structures [ka]

[0232] [Dispersant 1] B-1 to B-5: Resins having the following structures (polymerizable resins. x, y, and z attached to the main chain are molar ratios, and the numbers attached to the side chains are the numbers of repeating units. The values ​​of x, y, and z, the weight average molecular weight (Mw), and the ethylenically unsaturated bond-containing group value (C=C value) are as shown in the table below. [ka] [Table 2]

[0233] [Dispersant 2] E-1: Resin having the following structure (a resin having no ethylenically unsaturated bond-containing group. The number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 24,000) [ka] E-2: Resin having the following structure (a resin having no ethylenically unsaturated bond-containing group. The number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 21,000) [ka]

[0234] [solvent] S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Cyclohexanone S-3: Cyclopentanone S-4: Diacetone alcohol S-5: Anisole

[0235] <Production of Photosensitive Composition> The raw materials shown in the table below were mixed to prepare a photosensitive composition. [Table 3] [Table 4]

[0236] The content of the colorant in the total solid content of each photosensitive composition, the content of the polymerizable monomer in the total solid content of the photosensitive composition, the parts by mass of the polymerizable monomer per 100 parts by mass of the polymerizable resin, the ethylenically unsaturated bond-containing group value (C=C value 1) derived from the polymerizable monomer in the total solid content of the photosensitive composition, and the ethylenically unsaturated bond-containing group value (C=C value 2) derived from the polymerizable resin in the total solid content of the photosensitive composition are as follows: The C=C value 1 is a value calculated by dividing the total product of the content of each polymerizable monomer in the total solid content of the photosensitive composition and the C=C value of each polymerizable monomer by the total solid content of the photosensitive composition. The C=C value 2 is a value calculated by dividing the total product of the content of each polymerizable resin in the total solid content of the photosensitive composition and the C=C value of each polymerizable resin by the total solid content of the photosensitive composition. The sum of C=C value 1 and C=C value 2 corresponds to the ethylenically unsaturated bond-containing group value of the solid content of the photosensitive composition.

[0237] [Table 5]

[0238] Details of the abbreviations for the raw materials used in the preparation of each photosensitive composition are as follows:

[0239] [Polymerizable monomer] M-1: Compound having the following structure (C=C value: 9.94 mmol / g) [ka] M-2: A mixture of compounds with the following structures (compound with the structure on the left: compound with the structure on the right = 7:3 (mass ratio), C=C value: 10.12 mmol / g) [ka] M-3: Compound having the following structure (C=C value: 11.35 mmol / g) [ka] M-4: Compound with the following structure (C=C value: 2.12 mmol / g) [ka] M-5: Compound having the following structure (C=C value: 7.57 mmol / g) [ka]

[0240] [resin] C-1: Resin with the following structure (polymerizable resin. The numbers attached to the main chain are molar ratios. Weight average molecular weight: 11,000, C=C value: 1.44 mmol / g) [ka] C-2: Resin with the following structure (the numbers attached to the main chain are molar ratios. Weight average molecular weight: 14,000) [ka]

[0241] [Photopolymerization initiator] I-1: Irgacure OXE02 (BASF, oxime compound)

[0242] [Surfactants] W-1: Compound having the following structure (fluorosurfactant, weight average molecular weight 14,000, the percentage indicating the proportion of repeating units is mol%) [ka]

[0243] [Polymerization inhibitor] Q-1: p-Methoxyphenol

[0244] [solvent] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0245] <Evaluation of photolithography properties> Each of the photosensitive compositions obtained above was applied by spin coating using Act8 manufactured by Tokyo Electron onto an 8-inch (203.2 mm) silicon wafer with an undercoat layer so that the film thickness after application was 0.4 μm, and then the wafer was heated at 100° C. for 2 minutes using a hot plate to form a composition layer. Next, the obtained composition layer was exposed to light (KrF line) with a wavelength of 248 nm at 35,000 W / m through a mask having a pattern of 0.7 μm square or a mask having a pattern of 0.6 μm square using a KrF scanner exposure machine. 2 , 200mJ / cm 2 The composition layer was exposed to light at an exposure dose of 1000 nm. The composition layer after exposure was then shower-developed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. After that, the layer was rinsed with pure water by spin shower to form pixels. The obtained pixels were observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Technologies Corporation). Based on the observed images, the photolithographic properties were evaluated according to the following criteria. The photolithographic properties were tested three times for each sample, and the results were evaluated comprehensively. The evaluation results using a mask having a 0.7 μm square pattern are shown in the Photolithographic Properties 1 column, and the evaluation results using a mask having a 0.6 μm square pattern are shown in the Photolithographic Properties 2 column. (Evaluation Criteria) 5: The four sides of the pixel have good linearity and no residue between the pixels. 4: The four sides of the pixel have good linearity and there is little residue between the pixels. 3: The four sides of the pixel are slightly rounded and there is little residue between the pixels. 2: The four sides of the pixel are rounded and there is a lot of residue between the pixels. 1: Pixels cannot be formed.

[0246] [Table 6]

[0247] As shown in the above table, the photolithography properties of the examples were evaluated as good, and pixels could be formed even when a mask having a pattern of 0.6 μm square was used. In addition, there was little residue between pixels.

[0248] Similar effects were obtained when the surfactant W-1 in the photosensitive compositions of Examples 25 to 43 was changed to the surfactants W-2 to W-44 shown below.

[0249] W-2: FZ-2122 (Dow Toray Industries, Inc., silicone surfactant) W-3: BYK-322 (BYK-Chemie, silicone surfactant) W-4: BYK-323 (BYK-Chemie, silicone surfactant) W-5: BYK-330 (BYK-Chemie, silicone surfactant) W-6: BYK-3760 (BYK-Chemie, silicone surfactant) W-7: BYK-UV3510 (BYK-Chemie, silicone surfactant) W-8: KF-6001 (Shin-Etsu Chemical Co., Ltd., silicone surfactant) W-9: Megafac F-477 (DIC Corporation, fluorosurfactant) W-10: Megafac F-554 (DIC Corporation, fluorosurfactant) W-11: Megafac F-555-A (DIC Corporation, fluorosurfactant) W-12: Megafac F-556 (DIC Corporation, fluorosurfactant) W-13: Megafac F-557 (DIC Corporation, fluorosurfactant) W-14: Megafac F-558 (DIC Corporation, fluorosurfactant) W-15: Megafac F-559 (DIC Corporation, fluorosurfactant) W-16: Megafac F-560 (DIC Corporation, fluorosurfactant) W-17: Megafac F-561 (DIC Corporation, fluorosurfactant) W-18: Megafac F-563 (DIC Corporation, fluorosurfactant) W-19: Megafac F-565 (DIC Corporation, fluorosurfactant) W-20: Megafac F-568 (DIC Corporation, fluorosurfactant) W-21: Megafac F-575 (DIC Corporation, fluorosurfactant) W-22: Megafac R-01 (DIC Corporation, fluorosurfactant) W-23: Megafac R-40 (DIC Corporation, fluorosurfactant) W-24: Megafac R-40-LM (DIC Corporation, fluorosurfactant) W-25: Megafac R-41 (DIC Corporation, fluorosurfactant) W-26: Megafac R-41-LM (DIC Corporation, fluorosurfactant) W-27: Megafac R-94 (DIC Corporation, fluorosurfactant) W-28: Megafac DS-21 (DIC Corporation, fluorosurfactant) W-29: Megafac RS-43 (DIC Corporation, fluorosurfactant) W-30: Megafac RS-72-K (DIC Corporation, fluorosurfactant) W-31: Megafac RS-90 (DIC Corporation, fluorosurfactant) W-32: Megafac TF-1956 (DIC Corporation, fluorosurfactant) W-33: Futergent 208G (NEOS Co., Ltd., fluorosurfactant) W-34: Futergent 215M (NEOS Co., Ltd., fluorosurfactant) W-35: Futergent 245F (NEOS Co., Ltd., fluorosurfactant) W-36: Futergent 601AD (NEOS Co., Ltd., fluorosurfactant) W-37: Futergent 601ADH2 (NEOS Co., Ltd., fluorosurfactant) W-38: Futergent 602A (NEOS Co., Ltd., fluorosurfactant) W-39: Futergent 610FM (NEOS Co., Ltd., fluorosurfactant) W-40: Futergent 710FL (NEOS Co., Ltd., fluorosurfactant) W-41: Futergent 710FM (NEOS Co., Ltd., fluorosurfactant) W-42: Futergent 710FS (NEOS Co., Ltd., fluorosurfactant) W-43: Futergent FTX-218 (NEOS Co., Ltd., fluorosurfactant) W-44: PF-6320 (OMNOVA, fluorosurfactant)

[0250] (Example 1001) A green photosensitive composition was applied onto a silicon wafer by spin coating so that the film thickness after formation would be 0.4 μm. Then, the wafer was heated at 100° C. for 2 minutes using a hot plate. Next, a KrF scanner exposure machine was used to irradiate the wafer with 248 nm light (KrF line) at 200 mJ / cm through a mask having a Bayer pattern with a pixel (pattern) size of 0.7 μm square. 2The substrate was exposed to light with an exposure dose of 1000 nm. Then, paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). After that, the substrate was rinsed with a spin shower and further washed with pure water. Then, the substrate was heated at 200° C. for 5 minutes using a hot plate to form green pixels. The red photosensitive composition and the blue photosensitive composition were also patterned in the same process to sequentially form red and blue pixels, thereby forming a color filter having green, red and blue pixels. In this color filter, the green pixels are formed in a Bayer pattern, and in the adjacent area, the red and blue pixels are formed in an island pattern. The obtained color filter was incorporated into a solid-state imaging device according to a known method. This solid-state imaging device had suitable image recognition ability. The photosensitive composition of Example 31 was used as the green photosensitive composition. The photosensitive composition of Example 36 was used as the red photosensitive composition. The composition shown below was used as the blue photosensitive composition.

[0251] -Blue photosensitive composition- The following components were mixed and stirred, and then filtered through a nylon filter having a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a blue photosensitive composition. Blue pigment dispersion: 44.9 parts by weight Resin 101...2.1 parts by mass Polymerizable compound 101...1.5 parts by mass Polymerizable compound 102...0.7 part by mass Photopolymerization initiator 101: 0.8 parts by mass Surfactant 101: 4.2 parts by mass PGMEA: 45.8 parts by mass

[0252] The raw materials used in the blue-sensitive composition are as follows:

[0253] Blue pigment dispersion A mixture of 9.7 parts by mass of CI Pigment Blue 15:6, 2.4 parts by mass of CI Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm in diameter). Then, the mixture was mixed and dispersed at 2000 kg / cm using a high-pressure disperser NANO-3000-10 equipped with a pressure reducing mechanism (manufactured by Japan BEE Co., Ltd.). 3 The dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 1000 g / min. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion.

[0254] Resin 101: 40% by mass solution of a resin having the following structure (the number attached to the main chain is the molar ratio; weight average molecular weight 11,000) in PGMEA [ka] Polymerizable compound 101: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) Polymerizable compound 102: a compound having the following structure [ka] Photopolymerization initiator 101: Irgacure OXE02 (BASF) Surfactant 101: A 1% by mass solution of a compound having the following structure (weight average molecular weight 14,000, in the following formula, % indicating the proportion of repeating units is mol %) in PGMEA. [ka]

Claims

1. A photosensitive composition comprising a color material A, a photopolymerization initiator B, a polymerizable monomer C having an ethylenically unsaturated bond-containing group, and a polymerizable resin D having an ethylenically unsaturated bond-containing group, the content of the color material A in the total solid content of the photosensitive composition is more than 50 mass %, the content of the polymerizable monomer C in the total solid content of the photosensitive composition is 12 to 20 mass %, The polymerizable monomer C is contained in an amount of 5 to 200 parts by mass per 100 parts by mass of the polymerizable resin D, The polymerizable monomer C is contained in an amount of 300 to 600 parts by mass relative to 100 parts by mass of the photopolymerization initiator B, The photosensitive composition contains two or more types of the polymerizable resin D, and the polymerizable resin D contains a resin containing a repeating unit represented by formula (A-1-1) and a repeating unit represented by formula (A-1-2). A photosensitive composition for exposure to light having a wavelength of 300 nm or less. 【Chemistry 1】 (In formula (A-1-1), X １ represents a trivalent linking group; L １ represents a single bond or a divalent linking group; Y １ represents an ethylenically unsaturated bond-containing group. 【Chemistry 2】 (In the formula (A-1-2), X ２ represents a trivalent linking group; L ２ represents a single bond or a divalent linking group; W １ represents a graft chain.)

2. The photosensitive composition according to claim 1 , wherein the color material A includes a chromatic color material.

3. 3. The photosensitive composition according to claim 1, wherein the polymerizable monomer C comprises a di- to octa-functional polymerizable monomer having 2 to 8 ethylenically unsaturated bond-containing groups.

4. 3. The photosensitive composition according to claim 1, wherein the polymerizable monomer C is a di- to hexa-functional (meth)acrylate compound.

5. The photosensitive composition according to any one of claims 1 to 4, wherein an ethylenically unsaturated bond-containing group value derived from the polymerizable monomer C in a total solid content of the photosensitive composition is 0.01 to 8 mmol / g.

6. The photosensitive composition according to any one of claims 1 to 5, wherein an ethylenically unsaturated bond-containing group value derived from the polymerizable resin D in a total solid content of the photosensitive composition is 0.001 to 5 mmol / g.

7. 7. The photosensitive composition according to claim 1, comprising 10 to 100 parts by mass of the polymerizable monomer C relative to 100 parts by mass of the polymerizable resin D.

8. the content of the polymerizable resin D in the total solid content of the photosensitive composition is 18 to 30 mass %, The polymerizable monomer C is contained in an amount of 25 to 75 parts by mass relative to 100 parts by mass of the polymerizable resin D, the ethylenically unsaturated bond-containing group value derived from the polymerizable monomer C in the total solid content of the photosensitive composition is 0.1 to 2.5 mmol / g, the ethylenically unsaturated bond-containing group value derived from the polymerizable resin D in the total solid content of the photosensitive composition is 0.01 to 1 mmol / g; The photosensitive composition according to any one of claims 1 to 4.

9. 9. The photosensitive composition according to claim 1, wherein a total amount of the polymerizable monomer C and the polymerizable resin D is 5 to 45 mass % based on the total solid content of the photosensitive composition.

10. 10. The photosensitive composition according to claim 1, wherein the content of the photopolymerization initiator B is 1 to 10 mass % based on the total solid content of the photosensitive composition.

11. The photosensitive composition according to any one of claims 1 to 10, wherein the polymerizable monomer C includes a polymerizable monomer having a fluorene skeleton.

12. The photosensitive composition according to any one of claims 1 to 11, which is used for forming red or green pixels of a color filter.

13. The photosensitive composition according to any one of claims 1 to 12, which is for use in a solid-state imaging device.

14. A step of forming a photosensitive composition layer on a support using the photosensitive composition according to any one of claims 1 to 13; a step of exposing the photosensitive composition layer to light having a wavelength of 300 nm or less in a pattern; a step of developing and removing the photosensitive composition layer in the unexposed areas to form pixels; A method for producing an optical filter comprising the steps of:

15. The method for producing an optical filter according to claim 14, wherein the light having a wavelength of 300 nm or less that is irradiated onto the photosensitive composition layer is light having a wavelength of 248 nm.

16. A method for manufacturing a solid-state imaging device, comprising the method for manufacturing an optical filter according to claim 14 or 15.

Images