Photosensitive composition, film, optical filter, solid-state imaging element, and image display device

Abstract

Provided is a photosensitive composition containing a colorant, a polymerizable compound, and a photopolymerization initiator, the content of the colorant in the total solid content of the photosensitive composition being 40 mass% or more, the polymerizable compound containing a polymerizable compound B1 having a weight-average molecular weight of 3000 or more, and the photopolymerization initiator containing a polymerizable compound B2 having a weight-average molecular weight of 3000 or more. The content of the polymerizable compound B1 in the total mass of the polymerizable compounds is 50 mass% or more, and the photopolymerization initiator contains a compound represented by formula (1). The invention also provides a film using the photosensitive composition, an optical filter, a solid-state imaging element, and an image display device. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a photosensitive composition containing a coloring material and also to a film, an optical filter, a solid-state imaging element, and an image display device using the photosensitive composition. Background Art

[0002] As described in Patent Document 1, there is a technique for producing an optical filter such as a color filter using a photosensitive composition containing a color material, a photopolymerization initiator, and a polymerizable compound.

[0003] Previous technical literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2012-189997 Summary of the invention

[0006] Technical issues to be solved by the invention

[0007] In recent years, there is a strong demand for miniaturization or thin filming in solid-state imaging elements. Therefore, for films containing color materials such as color filters used in solid-state imaging elements, further thin filming is also desired in recent years. In order to maintain the desired spectral performance and achieve thin filming, it is necessary to increase the color material concentration of the photosensitive composition used for film formation.

[0008] However, as the color material concentration of the photosensitive composition increases, the proportion of components other than the color material decreases relatively, so there is a tendency for insufficient curability. Therefore, when using the photosensitive composition and forming pixels by photolithography, as the color material concentration of the photosensitive composition increases, there is a tendency for the obtained pixels to have insufficient adhesion to the support.

[0009] Therefore, an object of the present invention is to provide a photosensitive composition capable of forming a film having excellent adhesion to a support. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging element, and an image display device.

[0010] Means for solving technical problems

[0011] According to the research of the present inventors, it was found that the above-mentioned object can be achieved by the photosensitive composition described below, and the present invention was completed. Therefore, the present invention provides the following.

[0012] <1> A photosensitive composition comprising a color material, a polymerizable compound and a photopolymerization initiator.

[0013] The content of the color material in the total solid content of the photosensitive composition is 40% by mass or more,

[0014] The polymerizable compound contains a polymerizable compound B1 having a weight average molecular weight of 3000 or more, and the content of the polymerizable compound B1 in the total mass of the polymerizable compound is 50 mass % or more,

[0015] The photopolymerization initiator contains a compound represented by formula (1),

[0016] [Chemical formula 1]

[0017]

[0018] In formula (1), X 1 represents a divalent linking group containing at least one selected from the group consisting of an aromatic ring and a heterocyclic ring,

[0019] R 1 represents a hydrogen atom or an acyl group,

[0020] R 2 represents an alkyl group or an aryl group,

[0021] R 3 and R 4 each independently represents a hydrogen atom or an alkyl group,

[0022] Alk 1 Alk 2 Each independently represents an alkyl group,

[0023] R 3 With R 4 can bond to form a ring,

[0024] Alk 1 With Alk 2 can bond to form a ring,

[0025] n represents 0 or 1.

[0026] <2> according to <1> The photosensitive composition, wherein

[0027] X in formula (1) 1 is a group represented by any of the formulae (X-1) to (X-13),

[0028] [Chemical formula 2]

[0029]

[0030] In the formula, R X1 ~R X9 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

[0031] <3> according to <2> The photosensitive composition, wherein

[0032] X in formula (1) 1 It is a group represented by the above-mentioned formula (X-2) or formula (X-6).

[0033] <4> according to <1> or <2> The photosensitive composition, wherein

[0034] The polymerizable compound B1 contains a repeating unit having a graft chain.

[0035] <5> according to <1> to <4> The photosensitive composition according to any one of the preceding claims, wherein

[0036] The polymerizable compound B1 contains a repeating unit having an ethylenically unsaturated bond-containing group in a side chain and a repeating unit having a graft chain.

[0037] <6> according to <4> or <5> The photosensitive composition, wherein

[0038] The graft chain contains a repeating unit of at least one structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylic acid structure.

[0039] <7> according to <1> to <6> The photosensitive composition according to any one of the preceding claims, wherein

[0040] The content of the color material in the total solid content of the photosensitive composition is 50% by mass or more.

[0041] <8> according to <1> to <7> The photosensitive composition according to any one of the preceding claims, wherein

[0042] The color material contains color index pigment red 272.

[0043] <9> according to <1> to <8> The photosensitive composition described in any one of the above aspects further contains a polymerization inhibitor.

[0044] <10> according to <1> to <9> The photosensitive composition described in any one of the above aspects further contains a silicone-based surfactant.

[0045] <11> A membrane, which is used <1> to <10> Obtained from any one of the photosensitive compositions described above.

[0046] <12> A filter having <11> The membrane.

[0047] <13> An image display device having <11> The membrane.

[0048] <14> A solid-state imaging element having <11> The membrane.

[0049] Effects of the Invention

[0050] According to the present invention, a photosensitive composition capable of forming a film having excellent adhesion to a support can be provided. In addition, according to the present invention, a film, an optical filter, a solid-state imaging element, and an image display device formed using the photosensitive composition can be provided. DETAILED DESCRIPTION

[0051] Hereinafter, the contents of the present invention will be described in detail.

[0052] In this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0053] In the marking of groups (atomic groups) in this specification, the marking not indicating substitution and unsubstituted includes not only groups (atomic groups) without substitution but also groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0054] The term "exposure" in this specification includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, electron beams, and other activating rays or radiation.

[0055] In the present specification, “(meth)acrylate” means both or either acrylate and methacrylate, “(meth)acrylic acid” means both or either acrylic acid and methacrylic acid, and “(meth)acryloyl” means both or either acryloyl and methacryloyl.

[0056] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0057] In this specification, the weight average molecular weight and the number average molecular weight are polystyrene conversion values ​​measured by GPC (gel permeation chromatography) method.

[0058] In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition.

[0059] In this specification, a pigment refers to a color material that is not easily dissolved in a solvent.

[0060] In this specification, the term "step" refers not only to an independent step but also to a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0061] <Photosensitive Composition>

[0062] The photosensitive composition of the present invention is characterized by comprising:

[0063] A color material, a polymerizable compound and a photopolymerization initiator, wherein:

[0064] The content of the coloring material in the total solid content of the photosensitive composition is 40% by mass or more,

[0065] The polymerizable compound contains a polymerizable compound B1 having a weight average molecular weight of 3000 or more, and the content of the polymerizable compound B1 in the total mass of the polymerizable compound is 50 mass % or more,

[0066] The photopolymerization initiator contains a compound represented by formula (1).

[0067] For photosensitive compositions with a large content of color materials, when cured by exposure, there is a tendency that the exposure light is not easy to reach the deep part of the film (support side). Therefore, in particular, in the deep part of the film, there is a tendency that the curing reaction during exposure is low. If the curing reaction in the deep part of the film is insufficient, the adhesion between the support and the obtained film is easily insufficient. However, although the content of the color material in the total solid content of the photosensitive composition is more than 40% by mass, the photosensitive composition of the present invention can also form a film with excellent adhesion to the support. The reason is not clear, but it is speculated that due to the increase in the amount of free radicals generated, the curing reaction can be fully carried out even in the deep part of the film. Moreover, it is speculated that the photosensitive composition of the present invention uses a composition containing a polymerizable compound B1 with a weight average molecular weight of more than 3000 as a polymerizable compound, and the content of the polymerizable compound B1 in the total mass of the polymerizable compound is more than 50% by mass, therefore, the molecular weight of the polymerizable compound caused by the free radical reaction during exposure increases greatly, which can suppress the permeability of the developer, thereby achieving good adhesion. Therefore, it is estimated that according to the photosensitive composition of the present invention, a film having excellent adhesion to a support can be formed.

[0068] Furthermore, the film obtained by using the photosensitive composition of the present invention is also excellent in moisture resistance. This is presumably because the molecular weight of the polymerizable compound increases significantly due to the radical reaction during exposure.

[0069] The photosensitive composition of the present invention also has excellent exposure sensitivity. In addition, the photosensitive composition of the present invention also has excellent developability, and when forming a pattern by photolithography to form pixels, pixels with excellent linearity can be formed, and the generation of residues between pixels can also be suppressed.

[0070] The photosensitive composition of the present invention can be preferably used as a photosensitive composition for an optical filter. As the optical filter, a color filter, a near-infrared transmission filter or a near-infrared cutoff filter, etc. can be cited, preferably a color filter. In addition, the photosensitive composition of the present invention can be preferably used as a solid-state imaging element. In more detail, it can be preferably used as a photosensitive composition for an optical filter used in a solid-state imaging element, and can be more preferably used as a photosensitive composition for forming colored pixels of a color filter used in a solid-state imaging element.

[0071] As a color filter, a filter having colored pixels that transmit light of a specific wavelength can be cited. As colored pixels, red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. can be cited. The colored pixels of the color filter can be formed using a photosensitive composition containing a color material.

[0072] The maximum absorption wavelength of the near infrared cut filter is preferably present in the range of wavelengths of 700 to 1800 nm, more preferably in the range of wavelengths of 700 to 1300 nm, and further preferably in the range of wavelengths of 700 to 1000 nm. In addition, the transmittance of the near infrared cut filter in the entire range of wavelengths of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. In addition, it is preferred that the transmittance of at least one point in the range of wavelengths of 700 to 1800 nm is 20% or less. In addition, 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, further preferably 70 to 450, and particularly preferably 100 to 400. The near infrared cut filter can be formed using a photosensitive composition containing a near infrared absorbing color material.

[0073] The near infrared transmission filter is a filter that transmits at least a portion of the near infrared rays. The near infrared transmission filter is preferably a filter that blocks at least a portion of the visible light and transmits at least a portion of the near infrared rays. As the near infrared transmission filter, preferably, there can be cited a filter that satisfies the spectral characteristics that the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the minimum transmittance in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). The near infrared transmission filter is preferably a filter that satisfies any one of the spectral characteristics of the following (1) to (5).

[0074] (1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1500 nm.

[0075] (2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm.

[0076] (3): A filter having a maximum transmittance of less than 20% (preferably less than 15%, more preferably less than 10%) in the wavelength range of 400 to 830 nm and a minimum transmittance of more than 70% (preferably more than 75%, more preferably more than 80%) in the wavelength range of 1000 to 1500 nm.

[0077] (4): A filter having a maximum transmittance of less than 20% (preferably less than 15%, more preferably less than 10%) in the wavelength range of 400 to 950 nm and a minimum transmittance of more than 70% (preferably more than 75%, more preferably more than 80%) in the wavelength range of 1100 to 1500 nm.

[0078] (5): A filter having a maximum transmittance of less than 20% (preferably less than 15%, more preferably less than 10%) in the wavelength range of 400 to 1050 nm and a minimum transmittance of more than 70% (preferably more than 75%, more preferably more than 80%) in the wavelength range of 1200 to 1500 nm.

[0079] The solid content concentration of the photosensitive composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

[0080] Hereinafter, each component used in the photosensitive composition of the present invention will be described.

[0081] <<Color material>>

[0082] The photosensitive composition of the present invention contains a colorant. Examples of the colorant include white colorants, black colorants, chromatic colorants, and near-infrared absorbing colorants. In addition, in this specification, the white colorant includes not only pure white, but also light gray colorants (e.g., off-white, light gray, etc.) that are close to white.

[0083] The color material preferably includes at least one selected from the group consisting of chromatic color materials, black color materials, and near-infrared absorption color materials, and more preferably includes a chromatic color material.

[0084] When the photosensitive composition of the present invention is used as a color filter, it is preferred that the color material is substantially only a chromatic color material. In addition, in this specification, when the color material is substantially only a chromatic color material, it means that the content of the chromatic color material in the color material is 99% by mass or more, preferably 99.9% by mass or more, and more preferably the color material is only a chromatic color material.

[0085] The coloring material may be any of a pigment and a dye, but preferably contains a pigment.

[0086] The pigment may be any of an inorganic pigment and an organic pigment, but is preferably an organic pigment from the viewpoints of the amount of color variation, ease of dispersion, safety, etc. Furthermore, the pigment preferably includes at least one selected from a color pigment and a near infrared absorbing pigment, and more preferably includes a color pigment.

[0087] The average primary particle size 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 further preferably 100 nm or less. If the average primary particle size of the pigment is within the above range, the dispersion stability of the pigment in the photosensitive composition is good. In addition, in the present invention, the primary particle size of the pigment can be obtained by observing the primary particles of the pigment under a transmission electron microscope and based on the obtained photographs. Specifically, the projected area of ​​the primary particles of the pigment is obtained, and the equivalent circle diameter corresponding thereto is calculated as the primary particle size of the pigment. In addition, the average primary particle size in the present invention is set to the arithmetic mean of the primary particle sizes of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles that are not agglomerated.

[0088] The crystallite size determined from the half width of the peak derived from any crystal plane in the X-ray diffraction spectrum when the CuKα line of the pigment is used as the X-ray source is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, further preferably 1 to 30 nm, and particularly preferably 5 to 25 nm.

[0089] The specific surface area of ​​the pigment is preferably 1 to 300 m 2 / g. The lower limit is preferably 10m 2 / g or more, more preferably 30m 2 The upper limit is preferably 250 m 2 / g or less, more preferably 200m 2The value of the specific surface area can be measured according to the BET (Brunauer, Emmett and Teller) method in accordance with DIN 66131: determination of the specific surface area of ​​solids by gas adsorption.

[0090] As a preferred embodiment, the color material is preferably a color material containing color index pigment red 272.

[0091] (color material)

[0092] As the color material, there can be mentioned a color material having a maximum absorption wavelength in the range of 400 to 700 nm. For example, yellow color material, orange color material, red color material, green color material, purple color material, blue color material, etc. can be mentioned. From the viewpoint of heat resistance, the color material is preferably a pigment (color pigment), more preferably a red pigment, a yellow pigment and a blue pigment, and further preferably a red pigment and a blue pigment. As specific examples of color pigments, for example, the following pigments can be mentioned.

[0093] Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds, preferably diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds, and more preferably diketopyrrolopyrrole compounds. In addition, the red colorant is preferably a pigment.

[0094] Specific examples of red color materials include CI (color index) pigment red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 1 46, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297 and other red pigments. Furthermore, as a red color material, the compound described in paragraph 0034 of International Publication No. 2022 / 085485 and the brominated diketopyrrolopyrrole compound described in Japanese Patent Application Laid-Open No. 2020-085947 can also be used.

[0095] As the red color material, CI Pigment Red 122, 177, 254, 255, 264, 269, and 272 are preferred, CI Pigment Red 254, 264, and 272 are more preferred, CI Pigment Red 254 and 272 are further preferred, and CI Pigment Red 272 is particularly preferred.

[0096] Examples of green colorants include phthalocyanine compounds and squarylium compounds, preferably phthalocyanine compounds, and more preferably phthalocyanine pigments. The green colorant is preferably a pigment.

[0097] As specific examples of green color materials, green pigments such as CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66 can be cited. In addition, as a green color material, a zinc phthalocyanine halogenated 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. As a specific example, the compounds described in International Publication No. 2015 / 118720 can be cited. In addition, as a green color material, the compounds described in paragraph 0029 of International Publication No. 2022 / 085485, the aluminum phthalocyanine compounds described in Japanese Patent Publication No. 2020-070426, and the like can also be used.

[0098] As the green color material, CI Pigment Green 7, 36, 58, 62, and 63 are preferred, and CI Pigment Green 36 and 58 are more preferred.

[0099] Specific examples of the orange color material include 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, and 73.

[0100] Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. Specific examples of yellow color materials include 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 0, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 and other yellow pigments.

[0101] As a yellow colorant, an azobarbituric acid nickel complex having the following structure can also be used.

[0102] [Chemical formula 3]

[0103]

[0104] As a yellow colorant, the compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485, the methine dyes described in Japanese Patent Publication No. 2019-073695, the methine dyes described in Japanese Patent Publication No. 2019-073696, the methine dyes described in Japanese Patent Publication No. 2019-073697, the methine dyes described in Japanese Patent Publication No. 2019-073698, and the azo compounds described in Japanese Patent Publication No. 2020-093994 can be used.

[0105] Specific examples of the violet color material include violet pigments such as CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0106] Specific examples of blue color materials include 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, 88 and the like. In addition, aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue color materials. Specific examples include compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Application Publication No. 2011-157478.

[0107] As a green color material or a blue color material, a diarylmethane compound described in JP-A-2020-504758 can also be used.

[0108] Regarding the diffraction angles that various pigments preferably have, reference can be made to the records in Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Patent Publication No. 2020-026503, and Japanese Patent Publication No. 2020-033526, which are incorporated into this specification. In addition, as a pyrrolopyrrole pigment, it is also preferred to use a crystallite size of 0.040 mm in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the 8 planes in the lattice plane (±1±1±1). The following pigments. In addition, the physical properties of the pyrrolopyrrole pigment are preferably set as described in paragraphs 0028 to 0073 of JP-A-2020-097744.

[0109] As a pigment, from the viewpoint of improving spectral characteristics, it is also preferred to use a zinc phthalocyanine halogenide pigment having a Raman spectrum as described in Japanese Patent No. 6744002. Also, as a pigment, from the viewpoint of viscosity adjustment, it is also preferred to use a dioxazine pigment having a controlled contact angle as described in International Publication No. 2019 / 107166.

[0110] Color color materials can also use dyes. There are no particular restrictions on the dyes, and known dyes can be used. For example, dyes such as pyrazole azo series, anilino azo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, phthalocyanine series, benzopyran series, indigo series, and pyrromethene series can be cited.

[0111] Color pigments can also use pigment polymers. The pigment polymer is preferably a dye used by dissolving in a solvent. In addition, the pigment polymer can form particles. When the pigment polymer is a particle, it is usually used in a state dispersed in a solvent. The pigment polymer in a particle state can be obtained, for example, by emulsion polymerization. As a specific example, the compound and the production method described in Japanese Patent Publication No. 2015-214682 can be cited. The pigment polymer has two or more pigment structures in one molecule, preferably three or more pigment structures. The upper limit is not particularly limited, but can also be set to 100 or less. The multiple color pigment structures in one molecule can be the same pigment structure or different pigment structures. The weight average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and more preferably 6000 or more. The upper limit is more preferably 30000 or less, and more preferably 20000 or less. As the pigment multimer, compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, International Publication No. 2016 / 031442, and the like can also be used.

[0112] As the color material, a triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, a xanthene compound described in Japanese Patent Publication No. 2020-117638, a phthalocyanine compound described in International Publication No. 2020 / 174991, an isoindoline compound described in Japanese Patent Publication No. 2020-160279 or a salt thereof, a compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069442, a compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, a compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069 The compound represented by formula 1 described in the publication No. 070, the compound represented by formula 1 described in the publication No. 10-2020-0069067, the compound represented by formula 1 described in the publication No. 10-2020-0069062, the zinc phthalocyanine pigment described in Japanese Patent No. 6809649, the isoindoline compound described in Japanese Patent Publication No. 2020-180176, the phenothiazine compound described in Japanese Patent Publication No. 2021-187913, the zinc phthalocyanine halides described in International Publication No. 2022 / 004261, and the zinc phthalocyanine halides described in International Publication No. 2021 / 250883. The color material can be a rotaxane, and the pigment skeleton can be used for the cyclic structure of the rotaxane, can also be used for the rod-shaped structure, or can be used for both structures. As a color colorant, a quinophthalone compound represented by Formula 1 in Korean Patent Publication No. 10-2020-0030759, a polymer dye described in Korean Patent Publication No. 10-2020-0061793, a colorant described in Japanese Patent Publication No. 2022-029701, an isoindoline compound described in International Publication No. 2022 / 014635, and an aluminum phthalocyanine compound described in International Publication No. 2022 / 024926 can be used.

[0113] Two or more chromatic colorants may be used in combination. Furthermore, when two or more chromatic colorants are used in combination, black may be formed by the combination of two or more chromatic colorants. As such a combination, for example, the following modes (1) to (7) may be cited. When the photosensitive composition contains two or more chromatic colorants and black is presented by the combination of two or more chromatic colorants, the photosensitive composition of the present invention can be preferably used as a photosensitive composition for forming a near-infrared transmission filter.

[0114] (1) A method containing red colorant and blue colorant.

[0115] (2) A method containing red, blue and yellow colorants.

[0116] (3) A method containing red color material, blue color material, yellow color material and purple color material.

[0117] (4) A method containing a red color material, a blue color material, a yellow color material, a purple color material, and a green color material.

[0118] (5) A method containing a red color material, a blue color material, a yellow color material, and a green color material.

[0119] (6) A method containing a red colorant, a blue colorant, and a green colorant.

[0120] (7) A method containing a yellow colorant and a purple colorant.

[0121] (White color material)

[0122] As white color materials, inorganic pigments (white pigments) such as titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide can be cited. The white pigment is preferably a particle having a titanium atom, more preferably titanium oxide. In addition, the white pigment is preferably a particle having a refractive index of 2.10 or more relative to light of a wavelength of 589 nm. The refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.

[0123] The titanium oxide described in "Physical Properties and Applications of Titanium Oxide, written by Manabu Seino, pages 13-45, published on June 25, 1991, published by GIHIDO SHUPPAN CO., Ltd." can also be used as the white pigment.

[0124] White pigment can not only be made of single inorganic substance, but also can use the particle formed by compounding with other materials.For example, preferably use the particle with pore or other materials inside, the particle of multiple inorganic particles attached on core particle, the core particle that comprises the core particle that comprises polymer particles and the core and shell composite particle of the shell that comprises inorganic nanoparticle.As the above-mentioned core particle that comprises the core particle that comprises polymer particles and the core and shell composite particle of the shell that comprises inorganic nanoparticle, for example, can refer to the record of 0012~0042 paragraphs of Japanese Patent Publication No. 2015-047520, this content is incorporated in this specification.

[0125] White pigment can also use hollow inorganic particles.Hollow inorganic particles refer to the inorganic particles with the structure of the cavity inside, and have the inorganic particles of the cavity surrounded by the shell.As hollow inorganic particles, the hollow inorganic particles described in Japanese Unexamined Patent Publication No. 2011-075786, International Publication No. 2013 / 061621, Japanese Unexamined Patent Publication No. 2015-164881 etc. can be enumerated, and these contents are incorporated in this description.

[0126] (Black color material)

[0127] The black color material is not particularly limited, and known materials can be used. For example, inorganic black color materials include inorganic pigments (black pigments) such as carbon black, titanium black, and graphite, preferably carbon black and titanium black, and more preferably titanium black. Titanium black refers to black particles containing titanium atoms, preferably low-grade titanium oxide or titanium oxynitride. The surface of titanium black can be modified as needed for the purpose of improving dispersibility, inhibiting agglomeration, 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, it can also be treated with a waterproof substance as shown in Japanese Patent Gazette No. 2007-302836. As black pigments, CI Pigment Black 1, 7, etc. can be mentioned. It is preferred that the primary particle size and average primary particle size of each particle 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 dispersed material. For example, a dispersion containing titanium black particles and silicon dioxide particles and wherein the ratio of Si atoms to Ti atoms in the dispersion is adjusted within the range of 0.20 to 0.50 can be cited. For the above-mentioned dispersion, reference can also be made to the records of paragraphs 0020 to 0105 of Japanese Patent Publication No. 2012-169556, which are incorporated into this specification. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.), etc.

[0128] As organic black color materials, bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, etc. can be cited. As bisbenzofuranone compounds, compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, etc. can be cited, for example, "Irgaphor Black" manufactured by BASF can be obtained. As perylene compounds, compounds described in paragraphs 0016 to 0020 of Japanese Patent Publication No. 2017-226821, CI Pigment Black 31, 32, etc. can be cited. As the azomethine compound, there can be mentioned compounds described in Japanese Patent Publication No. 01-170601, Japanese Patent Publication No. 02-034664, etc., for example, it can be obtained as "Chromo Fine Black A1103" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. And as a black color material, black organic pigments described in Japanese Patent Publication No. 6985715, Lumogen Black FK4280, Paliogen Black S0084 (manufactured by BASF) can be used.

[0129] The color material used in the photosensitive composition of the present invention may be only the above-mentioned black color material, or may also contain a color color material. According to this mode, a photosensitive composition that can form a film with excellent light-shielding properties in the visible region is easily obtained. When a black color material and a color color material are used as a color material, the mass ratio of the two is preferably black color material: color color material = 100:10 to 300, and more preferably 100:20 to 200.

[0130] Preferred combinations of black color materials and chromatic color materials include the following, for example.

[0131] (A-1) A form containing an organic black color material and a blue color material.

[0132] (A-2) An embodiment containing an organic black color material, a blue color material, and a yellow color material.

[0133] (A-3) An embodiment in which an organic black color material, a blue color material, a yellow color material, and a red color material are contained.

[0134] (A-4) An embodiment in which an organic black color material, a blue color material, a yellow color material, and a violet color material are contained.

[0135] In the embodiment (A-1) above, the mass ratio of the organic black color material to the blue color material is preferably organic black color material:blue color material=100:1-70, more preferably 100:5-60, and even more preferably 100:10-50.

[0136] In the above embodiment (A-2), the mass ratio of the organic black color material, the blue color material and the yellow color material is preferably organic black color material: blue color material: yellow color material = 100:10-90:10-90, more preferably 100:15-85:15-80, and further preferably 100:20-80:20-70.

[0137] In the above-mentioned method (A-3), the mass ratio of organic black colorant, blue colorant, yellow colorant and red colorant is preferably organic black colorant: blue colorant: yellow colorant: red colorant = 100:20~150:1~60:10~100, more preferably 100:30~130:5~50:20~90, and further preferably 100:40~120:10~40:30~80.

[0138] In the above-mentioned method (A-4), the mass ratio of organic black colorant, blue colorant, yellow colorant and purple colorant is preferably organic black colorant: blue colorant: yellow colorant: purple colorant = 100:20~150:1~60:10~100, more preferably 100:30~130:5~50:20~90, and further preferably 100:40~120:10~40:30~80.

[0139] (Near infrared absorbing color material)

[0140] The near-infrared absorbing color material is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700nm. The near-infrared absorbing color material is preferably a compound having a maximum absorption wavelength in the range of more than 700nm and less than 1800nm, more preferably a compound having a maximum absorption wavelength in the range of more than 700nm and less than 1400nm, further preferably a compound having a maximum absorption wavelength in the range of more than 700nm and less than 1200nm, and particularly preferably a compound having a maximum absorption wavelength in the range of more than 700nm and less than 1000nm. In addition, the absorbance A of the near-infrared absorbing color material at a wavelength of 500nm is 1 and the absorbance A at the maximum absorption wavelength 2 Ratio A 1 / A 2 It is preferably 0.08 or less, and more preferably 0.04 or less. Furthermore, the near infrared absorbing color material is preferably a pigment, and more preferably an organic pigment.

[0141] As near-infrared absorbing color materials, pyrrolopyrrole compounds, cyanine compounds, squaric acid compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, crotonium compounds, oxocyanine compounds, imine compounds, dithiol compounds, triarylmethane compounds, pyrrole methylene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiol metal complexes, metal oxides, metal borides, etc. As specific examples of these, the compounds described in paragraph 0114 of International Publication No. 2022 / 065215 can be cited. In addition, as near-infrared absorbing color materials, the compounds described in paragraph 0121 of International Publication No. 2022 / 065215, the square acid compounds described in Japanese Patent Gazette No. 2020-075959, the copper complexes described in Korean Patent Gazette No. 10-2019-0135217, the croton acid compounds described in Japanese Patent Gazette No. 2021-195515, and the near-infrared absorbing pigments described in Japanese Patent Gazette No. 2022-022070 can also be used.

[0142] The content of the colorant in the total solid content of the photosensitive composition is 40% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more, and the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less.

[0143] The content of the pigment in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and further preferably 75% by mass or less.

[0144] The content of the pigment in the color material is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.

[0145] <<Polymerizable Compound>>

[0146] The photosensitive composition of the present invention contains a polymerizable compound. As the polymerizable compound, a compound having a group containing an ethylenically unsaturated bond can be cited. As the group containing an ethylenically unsaturated bond, vinyl, (meth)allyl, (meth)acryloyl, (meth)acryloyloxy, etc. can be cited. The polymerizable compound is preferably a free radical polymerizable compound.

[0147] (Polymerizable compound B1)

[0148] In the photosensitive composition of the present invention, the polymerizable compound uses a compound containing a polymerizable compound B1 having a weight average molecular weight of 3000 or more. The content of the polymerizable compound B1 in the total mass of the polymerizable compound contained in the photosensitive composition is 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more. The upper limit can be set to 100% by mass or less, and can also be set to 95% by mass or less, and can also be set to 90% by mass or less.

[0149] The weight average molecular weight of the polymerizable compound B1 is 3000 or more, preferably 3000 to 300000. The upper limit is preferably 200000 or less, more preferably 100000 or less. The lower limit is preferably 5000 or more, more preferably 10000 or more.

[0150] The group value containing ethylenically unsaturated bonds of the polymerizable compound B1 (hereinafter also referred to as C=C value) is preferably 0.1 to 5.0 mmol / g. The upper limit is preferably 4.0 mmol / g or less, and more preferably 3.0 mmol / g or less. The lower limit is preferably 0.2 mmol / g or more, and more preferably 0.2 mmol / g or more. The C=C value of the polymerizable compound B1 is a numerical value representing the molar amount of the group value containing ethylenically unsaturated bonds per 1 g of the solid content of the polymerizable compound B1. When it can be calculated from the structural formula of the polymerizable compound B1, the value calculated from the structural formula is used. Furthermore, when it can be calculated from the structural formula and can be calculated from the raw materials used in the synthesis of the polymerizable compound B1, the value calculated from the added raw materials is used. Furthermore, with respect to the group value containing ethylenically unsaturated bonds of the polymerizable compound B1, when it cannot be calculated from the raw materials used in the synthesis of the polymerizable compound B1, the value measured by the hydrolysis method is used. Specifically, component (a) containing an ethylenically unsaturated bond group is extracted from polymerizable compound B1 by alkali treatment, and the content is measured by high performance liquid chromatography (HPLC) and calculated by the following formula. When component (a) cannot be extracted from polymerizable compound B1 by alkali treatment, the value measured by NMR (nuclear magnetic resonance) is used.

[0151] Ethylenically unsaturated bond-containing group value of polymerizable compound B1 [mmol / g] = (content of component (a) [ppm] / molecular weight of component (a) [g / mol]) / (weight value of polymerizable compound B1 [g] × (solid content concentration of polymerizable compound B1 [mass %] / 100) × 10)

[0152] The polymerizable compound B1 is also preferably a compound containing an acid group. Examples of the acid group include a carboxyl group, a sulfonic group, and a phosphoric acid group, preferably a carboxyl group. The acid value of the polymerizable compound B1 is preferably 20 to 200 mgKOH / g. The upper limit is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less. The lower limit is preferably 30 mgKOH / g or more, more preferably 35 mgKOH / g or more.

[0153] The polymerizable compound B1 is preferably a compound containing a repeating unit having an ethylenically unsaturated bond-containing group in a side chain. Examples of the repeating unit having an ethylenically unsaturated bond-containing group in a side chain include repeating units represented by formula (b1-1).

[0154] [Chemical formula 4]

[0155]

[0156] In the formula, A b11 represents a trivalent linking group, L b11 represents a single bond or an n+1 valent connecting group, Y b11 represents a group containing an ethylenically unsaturated bond, and n represents 1 or 2.

[0157] As A b11 The trivalent linking group represented may include a poly(meth)acrylic acid-based linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, a polyurea-based linking group, a polyamide-based linking group, a polyether-based linking group, a polystyrene-based linking group, etc., preferably a poly(meth)acrylic acid-based linking group or a polyalkyleneimine-based linking group, and more preferably a poly(meth)acrylic acid-based linking group.

[0158] As L b11 The n+1-valent connecting group represented may include aliphatic hydrocarbon groups (preferably aliphatic hydrocarbon groups having 1 to 12 carbon atoms), aromatic hydrocarbon groups (preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these groups.

[0159] As Y b11 Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group, and a (meth)acryloyloxy group is preferred.

[0160] In the polymerizable compound B1, the content of the repeating unit having an ethylenically unsaturated bond in the side chain is preferably 1 mol% or more, more preferably 1 to 80 mol% of the total repeating units of the polymerizable compound B1. The upper limit is preferably 70 mol% or less, more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 5 mol% or more.

[0161] The polymerizable compound B1 preferably contains a repeating unit having a graft chain in addition to a repeating unit having an ethylenically unsaturated bond-containing group on a side chain. That is, the polymerizable compound B1 is preferably a compound containing a repeating unit having an ethylenically unsaturated bond-containing group on a side chain and a repeating unit having a graft chain.

[0162] In this specification, a graft chain refers to a polymer chain branched from the main chain of a repeating unit. The number of atoms in the graft chain excluding hydrogen atoms is preferably 40 to 10,000, more preferably 50 to 2,000, and even more preferably 60 to 500.

[0163] The graft chain preferably contains repeating units of at least one structure selected from the group consisting of 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 repeating units of at least one structure selected from the group consisting of a polyester structure, a polyether structure, a poly(meth)acrylic structure and a polystyrene structure, further preferably contains repeating units of at least one structure selected from the group consisting of a polyester structure, a polyether structure and a poly(meth)acrylic structure, further preferably contains repeating units of a polyester structure or a polyether structure, and particularly preferably contains repeating units of a polyester structure.

[0164] As repeating units of polyester structure, repeating units of structures represented by the following formula (G-1), formula (G-4) or formula (G-5) can be cited. As repeating units of polyether structure, repeating units of structures represented by the following formula (G-2) can be cited. As repeating units of poly(meth)acrylic acid structure, repeating units of structures represented by the following formula (G-3) can be cited. As repeating units of polystyrene structure, repeating units of structures represented by the following formula (G-6) can be cited.

[0165] [Chemical formula 5]

[0166]

[0167] In the above formula, R G1 and R G2 Each independently represents an alkylene group. G1 and R G2The alkylene group represented is not particularly limited, but 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 still more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.

[0168] In the above formula, R G3 represents a hydrogen atom or a methyl group, Q G1 Indicates -O- or -NH-, L G1 represents a single bond or a divalent linking group, R G4 represents a hydrogen atom or a substituent.

[0169] As L G1 Examples of the divalent linking group represented include alkylene (preferably an alkylene group having 1 to 12 carbon atoms), alkyleneoxy (preferably an alkyleneoxy group having 1 to 12 carbon atoms), oxyalkylenecarbonyl (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), arylene (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 them.

[0170] As R G4 Examples of the substituents represented by the group include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl thioether group, an aryl thioether group, and a heterocyclic thioether group.

[0171] R G5 represents a hydrogen atom or a methyl group, R G6 R represents an aryl group. G6 The number of carbon atoms of the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. G6 The aryl group represented may have a substituent, and examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl thioether group, an aryl thioether group, and a heterocyclic thioether group.

[0172] The terminal structure of the graft chain is not particularly limited. It can be a hydrogen atom or a substituent. As the substituent, hydroxyl, carboxyl, alkyl, aryl, heterocyclic, alkoxy, aryloxy, heterocyclic oxy, alkyl thioether, aryl thioether, heterocyclic thioether, etc. can be mentioned. Among them, a group having a steric repulsion effect is preferred, preferably an alkyl or alkoxy group having 5 to 24 carbon atoms. The alkyl and alkoxy groups can be any of straight chain, branched and cyclic, preferably straight chain or branched.

[0173] The graft chain is preferably a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a), formula (G-5a) or formula (G-6a), and more preferably a structure represented by formula (G-1a), formula (G-4a) or formula (G-5a).

[0174] [Chemical formula 6]

[0175]

[0176] In the above formula, R G1 and R G2 represent alkylene, R G3 represents a hydrogen atom or a methyl group, Q G1 Indicates -O- or -NH-, L G1 represents a single bond or a divalent linking group, R G4 represents a hydrogen atom or a substituent, R G5 represents a hydrogen atom or a methyl group, R G6 represents an aryl group, W 100 represents a hydrogen atom or a substituent, and n1 to n6 each independently represent an integer greater than 2. G1 ~R G6 , Q G1 , L G1 , and R described in formulas (G-1) to (G-6) G1 ~R G6 , Q G1 , L G1 The meanings are the same, and the preferred ranges are also the same.

[0177] In formulas (G-1a) to (G-6a), W 100 Preferably, it is a substituent. As the substituent, hydroxyl, carboxyl, alkyl, aryl, heterocyclic, alkoxy, aryloxy, heterocyclic oxy, alkyl thioether, aryl thioether, heterocyclic thioether, etc. can be mentioned. Among them, a group having a steric repulsion effect is preferred, preferably an alkyl or alkoxy group having 5 to 24 carbon atoms. The alkyl and alkoxy groups may be any of linear, branched and cyclic, preferably linear or branched.

[0178] In formulae (G-1a) to (G-6a), n1 to n6 are each preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and still more preferably an integer of 8 to 60.

[0179] In the formula (G-1a), when n1 is 2 or more, R in each repeating unit is G1 They can be the same or different. And, when R G1When containing two or more different repeating units, the arrangement of each repeating unit is not particularly limited, and may be any of random, alternating, and block. The same is true for formula (G-2a) to formula (G-6a). In addition, the graft chain is a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a), and R is also preferably G1 It is a structure containing two or more different repeating units.

[0180] Examples of the repeating unit having a graft chain include repeating units represented by formula (b1-2).

[0181] [Chemical formula 7]

[0182]

[0183] In the formula, A b12 represents a trivalent linking group, L b12 represents a single bond or a divalent linking group, Y b12 Represents a grafted chain.

[0184] As A b12 The trivalent linking group represented may include a poly(meth)acrylic acid-based linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, a polyurea-based linking group, a polyamide-based linking group, a polyether-based linking group, a polystyrene-based linking group, etc., preferably a poly(meth)acrylic acid-based linking group or a polyalkyleneimine-based linking group, and more preferably a poly(meth)acrylic acid-based linking group.

[0185] As L b12 Examples of the divalent linking group represented include alkylene groups (preferably alkylene groups having 1 to 12 carbon atoms), arylene groups (preferably arylene groups having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these groups.

[0186] As Y b12 Examples of the grafted chains represented include the above-mentioned grafted chains.

[0187] In the polymerizable compound B1, the weight average molecular weight of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and further preferably 1000 to 7500. In addition, in the present specification, the weight average molecular weight of the repeating unit having a graft chain is a value calculated based on the weight average molecular weight of the raw 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, a macromonomer refers to a polymer compound having a polymerizable group introduced at the end of the polymer. In the case of using a macromonomer to form a repeating unit having a graft chain, the weight average molecular weight of the macromonomer is equivalent to the repeating unit having a graft chain.

[0188] When the polymerizable compound B1 contains a repeating unit having a graft chain, the content of the repeating unit having a graft chain is preferably 1 to 60 mol% of the total repeating units of the polymerizable compound B1. The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 5 mol% or more.

[0189] It is also preferred that the polymerizable compound B1 contains a repeating unit having an acid group in addition to the repeating unit having an ethylenically unsaturated bond-containing group in the side chain. Examples of the acid group include a carboxyl group, a sulfone group, and a phosphoric acid group.

[0190] Examples of the repeating unit having an acid group include repeating units represented by formula (b1-3).

[0191] [Chemical formula 8]

[0192]

[0193] In the formula, A b13 represents a trivalent linking group, L b13 represents a single bond or an n+1 valent connecting group, Y b13 represents an acid group, and n represents 1 or 2.

[0194] As A b13 The trivalent linking group represented may include a poly(meth)acrylic acid-based linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, a polyurea-based linking group, a polyamide-based linking group, a polyether-based linking group, a polystyrene-based linking group, etc., preferably a poly(meth)acrylic acid-based linking group or a polyalkyleneimine-based linking group, and more preferably a poly(meth)acrylic acid-based linking group.

[0195] As L b13The n+1-valent connecting group represented may include aliphatic hydrocarbon groups (preferably aliphatic hydrocarbon groups having 1 to 12 carbon atoms), aromatic hydrocarbon groups (preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these groups.

[0196] As Y b13 Examples of the acid group represented include a carboxyl group, a sulfo group, and a phosphoric acid group.

[0197] When polymerizable compound B1 contains repeating units having an acid group, the content of repeating units having an acid group is preferably 1 to 80 mol %, more preferably 5 to 80 mol %, and further preferably 10 to 80 mol % in the total repeating units of polymerizable compound B1.

[0198] The polymerizable compound B1 may contain a repeating unit derived from a monomer component including a compound represented by the formula (ED1) and / or a compound represented by the formula (ED2) (hereinafter, these compounds may also be referred to as “ether dimers”).

[0199] [Chemical formula 9]

[0200]

[0201] In formula (ED1), R 1 and R 2 Each independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

[0202] [Chemical formula 10]

[0203]

[0204] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), reference can be made to the description of Japanese Unexamined Patent Publication No. 2010-168539, the contents of which are incorporated herein.

[0205] For specific examples of the ether dimer, reference can be made to the description in paragraph 0317 of JP-A-2013-029760, for example, and the contents are incorporated into the present specification.

[0206] The polymerizable compound B1 may contain a repeating unit derived from a compound represented by the formula (X).

[0207] [Chemical formula 11]

[0208]

[0209] In the formula, R1 represents a hydrogen atom or a methyl group, R 21 and R 22 Each independently represents an alkylene group, and n represents an integer of 0 to 15. 21 and R 22 The number of carbon atoms of the alkylene group represented is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, particularly preferably 2 or 3. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, further preferably an integer of 0 to 3.

[0210] It is also preferred that the polymerizable compound B1 is a resin containing a repeating unit represented by the formula (Ac-2).

[0211] [Chemical formula 12]

[0212]

[0213] In formula (Ac-2), Ar 10 represents a group containing an aromatic carboxyl group, L 11 Indicates -COO- or -CONH-, L 12 represents a trivalent linking group, P 10 It refers to a polymer chain containing a repeating unit (having an ethylenically unsaturated bond-containing group on a side chain).

[0214] As Ar of formula (Ac-2) 10 Examples of the aromatic carboxyl group-containing group include structures derived from aromatic tricarboxylic anhydrides, structures derived from aromatic tetracarboxylic anhydrides, etc. Examples of the aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds of the following structures.

[0215] [Chemical formula 13]

[0216]

[0217] In the above formula, Q 1 It represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

[0218] [Chemical formula 14]

[0219]

[0220] Ar 10 The aromatic carboxyl group-containing group represented by may have an ethylenically unsaturated bond-containing group. 10Specific examples of the aromatic carboxyl group-containing group represented by include a group represented by the formula (Ar-11), a group represented by the formula (Ar-12), a group represented by the formula (Ar-13), and the like.

[0221] [Chemical formula 15]

[0222]

[0223] In the formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.

[0224] In the 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.

[0225] In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and further preferably 1. However, at least one of n3 and n4 is an integer of 1 or more.

[0226] In the formula (Ar-13), Q 1 It represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -S02-, -C(CF3)2-, a group represented by the above formula (Q-1) or a group represented by the above formula (Q-2).

[0227] In the formulas (Ar-11) to (Ar-13), *1 represents 10 bonding position.

[0228] L of formula (Ac-2) 11 It represents -COO- or -CONH-, and is preferably -COO-.

[0229] As L in formula (Ac-2) 12 The trivalent linking group represented by may include hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups formed by combining two or more of them. Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group and the like. L 12 The trivalent connecting group represented is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).

[0230] [Chemical formula 16]

[0231]

[0232] In formula (L12-1), L 12b represents a trivalent linking group, X 1 represents S, and *1 represents L in formula (Ac-2) 11 The bonding position of *2 indicates the bonding position with P of formula (Ac-2). 10 The bonding position of L 12b The trivalent linking group represented by the above-mentioned may include a hydrocarbon group; a group formed by combining a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-, etc., preferably a hydrocarbon group or a group formed by combining a hydrocarbon group and -O-.

[0233] In formula (L12-2), L 12c represents a trivalent linking group, X 1 represents S, and *1 represents L in formula (Ac-2) 11 The bonding position of *2 indicates the bonding position with P of formula (Ac-2). 10 The bonding position of L 12c Examples of the trivalent linking group represented by include a hydrocarbon group; and a group consisting of a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Preferably, the hydrocarbon group is used.

[0234] P10 in the formula (Ac-2) represents a polymer chain containing a repeating unit (having an ethylenically unsaturated bond-containing group in a side chain).

[0235] As the polymer chain represented by P10, there can be mentioned a polymer chain containing repeating units of at least one structure selected from the group consisting of a polyester structure, a polyether structure, a poly(meth)acrylic acid structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure. As the repeating unit of the polyester structure, there can be mentioned a repeating unit of the structure represented by the above formula (G-1), formula (G-4) or formula (G-5). As the repeating unit of the polyether structure, there can be mentioned a repeating unit of the structure represented by the above formula (G-2). As the repeating unit of the poly(meth)acrylic acid structure, there can be mentioned a repeating unit of the structure represented by the above formula (G-3). As the repeating unit of the polystyrene structure, there can be mentioned a repeating unit of the structure represented by the above formula (G-6).

[0236] As P 10 The repeating unit having an ethylenically unsaturated bond-containing group on the side chain of the polymer chain represented by exemplifies the repeating unit represented by the above-mentioned formula (b1-1). 10The ratio of repeating units having a group containing an ethylenically unsaturated bond on the side chain in the total repeating units is preferably 1 mol% or more, more preferably 1 to 80 mol%. The upper limit is preferably 70 mol% or less, more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 5 mol% or more.

[0237] P is also preferred 10 The polymer chain represented by has a repeating unit containing an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, etc. Examples of the repeating unit having an acid group include a repeating unit represented by the above formula (b1-3). 10 When the polymer chain represented by P contains repeating units having an acid group, 10 The ratio of the repeating unit having an acid group in the total repeating units is preferably 1 to 80 mol %, more preferably 5 to 80 mol %, further preferably 10 to 80 mol %.

[0238] P 10 The weight average molecular weight of the polymer chain represented is preferably 500 to 20000. The lower limit is preferably 1000 or more. The upper limit is preferably 10000 or less, more preferably 5000 or less, and further preferably 3000 or less.

[0239] (Polymerizable compound B2)

[0240] The photosensitive composition of the present invention may further contain a polymerizable compound B2 having a molecular weight of less than 3,000.

[0241] The polymerizable compound B2 may be in any chemical form such as a monomer, a prepolymer, or an oligomer, but preferably a monomer. The molecular weight of the polymerizable compound B2 is preferably 100 to 2500. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.

[0242] From the viewpoint of storage stability of the photosensitive composition, the group value (C=C value) containing an ethylenically unsaturated bond of the polymerizable compound B2 is preferably 2 to 14 mmol / g. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and further preferably 5 mmol / g or more. The upper limit is preferably 12 mmol / g or less, more preferably 10 mmol / g or less, and further preferably 8 mmol / g or less. The C=C value of the polymerizable compound B2 is a value calculated by dividing the number of groups containing an ethylenically unsaturated bond contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.

[0243] The polymerizable compound B2 is preferably a compound containing three or more groups containing ethylenically unsaturated bonds, and more preferably a compound containing four or more groups containing ethylenically unsaturated bonds. From the viewpoint of the storage stability of the photosensitive composition, the upper limit of the group containing ethylenically unsaturated bonds is preferably 15 or less, more preferably 10 or less, and further preferably 6 or less. Furthermore, the polymerizable compound B2 is preferably a (meth)acrylate compound having three or more functions, more preferably a (meth)acrylate compound having 3 to 15 functions, further preferably a (meth)acrylate compound having 3 to 10 functions, and particularly preferably a (meth)acrylate compound having 3 to 6 functions. Specific examples of the polymerizable compound B2 include compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraphs 0254 to 0257 of JP-A-2008-292970, paragraphs 0034 to 0038 of JP-A-2013-253224, paragraph 0477 of JP-A-2012-208494, JP-A-2017-048367, Japanese Patent No. 6057891, and Japanese Patent No. 6031807, and the contents thereof are incorporated into this specification.

[0244] Preferred polymerizable compound B2 include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ESTER A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and compounds having a structure in which these (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, compounds manufactured by SARTOMER Company, Inc., SR454, SR499). In addition, as the polymerizable compound, diglycerol EO (ethylene oxide) modified (meth) acrylate (commercially available as M-460; manufactured by TOAGOSEI CO., LTD.), pentaerythritol tetraacrylate (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., NK ESTER A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARADHDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), NK Oligo UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), 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 TaiseiFine Chemical Co., Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL Co., LTD.), etc.

[0245] As the polymerizable compound B2, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate can be used. Examples of commercially available trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and TMPT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0246] The polymerizable compound B2 may also use a compound having an acid group. Examples of the acid group include a carboxyl group, a sulfonic group, a phosphoric acid group, and the like, preferably a carboxyl group. Examples of commercially available polymerizable compounds having an acid group include ARONIX M-510, M-520, and ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.). The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.

[0247] The polymerizable compound B2 may also be a compound having a caprolactone structure. Examples of commercially available polymerizable compounds having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.).

[0248] The polymerizable compound B2 can also use a polymerizable compound having an alkyleneoxy group. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and further preferably a 3-6 functional (meth) acrylate compound having 4 to 20 ethyleneoxy groups. As commercially available polymerizable compounds having an alkyleneoxy group, for example, SR-494, a 4-functional (meth) acrylate having 4 ethyleneoxy groups manufactured by Sartomer Company, Inc., KAYARAD TPA-330, a 3-functional (meth) acrylate having 3 isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd., and the like can be cited.

[0249] As the polymerizable compound B2, a polymerizable compound having a fluorene skeleton can also be used. The polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound. Examples of the polymerizable compound having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr).

[0250] [Chemical formula 17]

[0251]

[0252] In the formula, the wavy line represents the bond, 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 Can be the same or different, m R f1 The 2 R's f1 When n is 2 or more, n R f2 Can be the same or different, n R f2 The 2 R's f2 They may be bonded to each other to form a ring. f1 and R f2 The substituent represented by includes 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 . R f11 ~R f28 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.

[0253] Specific examples of polymerizable compounds having a fluorene skeleton include compounds having the following structures: Commercially available polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0254] [Chemical formula 18]

[0255]

[0256] As the polymerizable compound B2, it is also preferable to use a compound that does not substantially contain environmentally regulated substances such as toluene. Examples of commercially available products of such a compound include KAYARAD DPHA LT and KAYARAD DPEA-12LT (manufactured by Nippon Kayaku Co., Ltd.).

[0257] The content of the polymerizable compound in the total solid content of the photosensitive composition is preferably 5 to 50% by mass. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.

[0258] The content of the polymerizable compound B1 in the total solid content of the photosensitive composition is preferably 5 to 50% by mass, the upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.

[0259] Furthermore, the content of the polymerizable compound B1 is preferably 100 to 5000 parts by mass relative to 100 parts by mass of the specific oxime compound described below. The upper limit is preferably 3000 parts by mass or less, more preferably 2000 parts by mass or less. The lower limit is preferably 200 parts by mass or more, more preferably 300 parts by mass or more.

[0260] When the photosensitive composition of the present invention contains the above-mentioned polymerizable compound B2, the content of the above-mentioned polymerizable compound B2 in the total solid content of the photosensitive composition is preferably 1 to 30% by mass. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. The lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more.

[0261] Furthermore, the content of the polymerizable compound B2 is preferably 50 to 1000 parts by mass relative to 100 parts by mass of the specific oxime compound described later. The upper limit is preferably 700 parts by mass or less, more preferably 500 parts by mass or less. The lower limit is preferably 75 parts by mass or more, more preferably 100 parts by mass or more.

[0262] The photosensitive composition of the present invention may contain only one polymerizable compound or may contain two or more polymerizable compounds. When containing two or more polymerizable compounds, the total amount thereof is preferably within the above range.

[0263] <<Photopolymerization Initiator>>

[0264] The photosensitive composition of the present invention contains a photopolymerization initiator. The photosensitive composition of the present invention uses a compound represented by formula (1) as a photopolymerization initiator. Hereinafter, the compound represented by formula (1) is also referred to as a specific oxime compound.

[0265] [Chemical formula 19]

[0266]

[0267] In formula (1), X 1 represents a divalent linking group containing at least one selected from the group consisting of an aromatic ring and a heterocyclic ring,

[0268] R 1 represents a hydrogen atom or an acyl group,

[0269] R 2 represents an alkyl group or an aryl group,

[0270] R 3 and R 4 each independently represents a hydrogen atom or an alkyl group,

[0271] Alk 1 Alk 2 Each independently represents an alkyl group,

[0272] R 3 With R 4 can bond to form a ring,

[0273] Alk 1 With Alk 2 can bond to form a ring,

[0274] n represents 0 or 1.

[0275] X in formula (1) 1 It represents a divalent linking group containing at least one selected from the group consisting of an aromatic ring and a heterocyclic ring.

[0276] As X 1 Examples of the divalent aromatic ring group include a divalent heterocyclic group, a divalent group formed by bonding two or more aromatic rings via a single bond or a connecting group, a divalent group formed by bonding two or more heterocyclic rings via a single bond or a connecting group, and a divalent group formed by bonding an aromatic ring and a heterocyclic ring via a single bond or a connecting group. Examples of the above-mentioned connecting group include -CH2-, -O-, -CO-, -S-, -NR x - and groups formed by combining them, etc. x represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

[0277] X in formula (1) 1 Preferably, it is a group represented by any of the formulas (X-1) to (X-13). From the perspective of being able to form a film with better adhesion, it is more preferably a group represented by the formula (X-1), the formula (X-2), the formula (X-4), the formula (X-6) or the formula (X-8). Further preferably, it is a group represented by the formula (X-2) or the formula (X-6). Particularly preferably, it is a group represented by the formula (X-6).

[0278] [Chemical formula 20]

[0279]

[0280] In the formula, R X1 ~R X9 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

[0281] R X1 ~R X9 The number of carbon atoms of the alkyl group represented is preferably 1 to 15, more preferably 1 to 10. The alkyl group may be any of linear, branched, and cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.

[0282] R X1 ~R X9 The number of carbon atoms of the alkenyl group represented is preferably 2 to 15, more preferably 2 to 10. The alkenyl group may be any of linear, branched, and cyclic. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heterocyclic group, and the like.

[0283] R X1 ~RX9 The number of carbon atoms of the alkynyl group represented is preferably 2 to 15, more preferably 2 to 10. The alkynyl group may be any of linear, branched, and cyclic. The alkynyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heterocyclic group, and the like.

[0284] R X1 ~R X9 The number of carbon atoms of the aryl group represented is preferably 6 to 20, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group.

[0285] R X1 ~R X9 The heterocyclic group represented is preferably a 5-membered ring or a 6-membered ring. The heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom and a sulfur atom. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and the like.

[0286] R in formula (1) 1 represents a hydrogen atom or an acyl group, and is preferably an acyl group.

[0287] R 1 The acyl group represented by is preferably -C(O)-R 101 Represents a group. 101 represents an aryl group or a heterocyclic group, and is preferably an aryl group.

[0288] R 101 The number of carbon atoms of the aryl group represented is preferably 6 to 20, more preferably 6 to 12. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, and the like. 101 The aryl group represented is preferably phenyl, methylphenyl or naphthyl, more preferably methylphenyl or naphthyl.

[0289] R 101 The heterocyclic group represented is preferably a 5-membered ring or a 6-membered ring. The heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom and a sulfur atom. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and the like.

[0290] R in formula (1) 2 represents an alkyl group or an aryl group, and is preferably an alkyl group because of its high reactivity in generating radicals.

[0291] R 2The number of carbon atoms of the alkyl group represented is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, and further preferably 1 to 3. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. R 2 The alkyl group represented is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group.

[0292] R 2 The number of carbon atoms of the aryl group represented is preferably 6 to 20, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent, but is preferably an unsubstituted aryl group.

[0293] R in formula (1) 3 and R 4 Each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom.

[0294] R 3 and R 4 The number of carbon atoms of the alkylene group is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, and further preferably 1 to 3. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.

[0295] R 3 With R 4 The ring formed may be bonded to form a ring, and the formed ring is preferably a 5-membered or 6-membered ring, and more preferably a 5-membered or 6-membered aliphatic hydrocarbon ring.

[0296] Alk in formula (1) 1 Alk 2 Each independently represents an alkyl group.

[0297] R 3 and R 4 The number of carbon atoms of the alkylene group is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, and further preferably 1 to 3. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.

[0298] Alk 1 With Alk 2 They may be bonded to form a ring, and preferably form a ring. The formed ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring or a 6-membered aliphatic hydrocarbon ring, and more preferably a cyclopentane ring or a cyclohexane ring.

[0299] In formula (1), n ​​represents 0 or 1, and is preferably 0.

[0300] Specific examples of the specific oxime compound include compounds I-1 to I-21 described in Examples described below, compounds described in paragraphs 0092 to 0096 of JP-A-2012-113104, and compounds described in paragraph 0041 of JP-A-2012-189997.

[0301] The content of the specific oxime compound in the total mass of the photopolymerization initiator contained in the photosensitive composition is preferably 50 mass % or more, more preferably 60 mass % or more, and further preferably 70 mass % or more. The upper limit can be 100 mass % or less.

[0302] The photopolymerization initiator contained in the photosensitive composition of the present invention may be substantially only the above-mentioned specific oxime compound, or may further contain a photopolymerization initiator other than the above-mentioned specific oxime compound (hereinafter also referred to as other photopolymerization initiator).

[0303] When the photopolymerization initiator is substantially only a specific oxime compound, it is preferred from the viewpoint of high exposure sensitivity. In addition, in this specification, the photopolymerization initiator is substantially only a specific oxime compound, which means that the specific oxime compound in the photopolymerization initiator is 99% by mass or more, preferably 99.9% by mass or more, and more preferably only a specific oxime compound.

[0304] When the photopolymerization initiator contains other photopolymerization initiators in addition to the specific oxime compound, the exposure sensitivity can be adjusted. When the photopolymerization initiator contains other photopolymerization initiators in addition to the specific oxime compound, the content of the other photopolymerization initiators is preferably 5 to 50 parts by mass relative to 100 parts by mass of the specific oxime compound. The lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

[0305] As other photopolymerization initiators, there can be mentioned halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, 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 the group consisting of an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in JP-A-6301489, and MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, a peroxide-based photopolymerization initiator described in International Publication No. 2018 / 221177, a photopolymerization initiator described in International Publication No. 2018 / 110179, a photopolymerization initiator described in Japanese Patent Publication No. 2019-043864, a photopolymerization initiator described in Japanese Patent Publication No. 2019-044030, a peroxide-based initiator described in Japanese Patent Publication No. 2019-167313, an oxazolidinyl group described in Japanese Patent Publication No. 2020-055992 e) aminoacetophenone-based initiators, oxime-based photopolymerization initiators described in Japanese Patent Publication No. 2013-190459, polymers described in Japanese Patent Publication No. 2020-172619, compounds represented by formula 1 described in International Publication No. 2020 / 152120, compounds described in Japanese Patent Publication No. 2021-181406, photopolymerization initiators described in Japanese Patent Publication No. 2022-013379, compounds represented by formula (1) described in Japanese Patent Publication No. 2022-015747, fluorine-containing fluorene oxime ester-based photoinitiators described in Japanese Patent Publication No. 2021-507058, etc.

[0306] Specific examples of the hexaarylbiimidazole compound include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole and the like.

[0307] Examples of commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Examples of commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Examples of commercially available products of the acylphosphine compound include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819 and Irgacure TPO (both manufactured by BASF).

[0308] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science. and Technology (1995, pp. 202-232), compounds described in Japanese Unexamined Patent Publication No. 2000-066385, compounds described in Japanese Unexamined Patent Publication No. 2004-534797, compounds described in Japanese Unexamined Patent Publication No. 2006-342166, compounds described in Japanese Unexamined Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 0 The compounds described in JP-A-2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, the compounds described in International Publication No. 2013 / 167515, the compounds represented by the general formula (1) and the compounds described in paragraphs 0022 to 0024 of JP-A-2021-173858, the compounds represented by the general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP-A-2021-170089, etc. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(0-acetyloxime), and the like.As commercial products, Irgacure OXE01, Irgacure OXE02, Irgacure OXE03 (all manufactured by BASF), TR-PBG-301, TR-PBG-327 (manufactured by TRONLY), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). In addition, as oxime compounds, non-coloring compounds or compounds with high transparency and low color change are also preferably used. As commercial products, ADEKA ARKLS NCI-730, NCI-831, NCI-930 (all manufactured by ADEKA CORPORATION) and the like can be mentioned.

[0309] As other photopolymerization initiators, oxime compounds having a fluorene ring can also be used. As specific examples of oxime compounds having a fluorene ring, compounds described in Japanese Patent Publication No. 2014-137466, compounds described in Japanese Patent Publication No. 6636081, compounds described in Korean Patent Publication No. 10-2016-0109444, fluorenyl amino ketone photoinitiators described in Japanese Patent Publication No. 2020-507664, and oxime ester compounds described in International Publication No. 2021 / 023144 can be cited.

[0310] As other photopolymerization initiators, an oxime compound having a carbazole ring and a skeleton in which at least one benzene ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013 / 083505.

[0311] As other photopolymerization initiators, oxime compounds having fluorine atoms can also be used. Specific examples of oxime compounds having fluorine atoms include 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.

[0312] As other photopolymerization initiators, oxime compounds having a nitro group can be used. Oxime compounds having a nitro group are also preferably dimers. Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and paragraphs 0007 to 0025 of Japanese Patent Publication No. 4223071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

[0313] As other photopolymerization initiators, oxime compounds having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0314] As other photopolymerization initiators, oxime compounds formed by bonding a substituent having a hydroxyl group to a carbazole skeleton can also be used. As such photopolymerization initiators, compounds described in International Publication No. 2019 / 088055 can be cited.

[0315] As other photopolymerization initiators, an aromatic ring group Ar having an electron-withdrawing group introduced into the aromatic ring can also be used. 0X1 As the aromatic ring group Ar 0X1 The electron withdrawing group possessed may include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano, preferably acyl and nitro, more preferably acyl, and further preferably benzoyl. The benzoyl may have a substituent. As a substituent, preferably a halogen atom, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclic oxy, alkenyl, alkylsulfanyl (sulfanyl group), arylsulfanyl, acyl or amino, more preferably alkyl, alkoxy, aryl, aryloxy, heterocyclic oxy, alkylsulfanyl, arylsulfanyl or amino, further preferably alkoxy, alkylsulfanyl or amino.

[0316] Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.

[0317] As other photopolymerization initiators, bifunctional or trifunctional or higher photoradical polymerization initiators can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in solvents is improved, and it becomes difficult to precipitate over time, thereby improving the storage stability of the photosensitive composition. Specific examples of the bifunctional or trifunctional or higher photoradical polymerization initiator include dimers of oxime compounds described in JP-T 2010-527339, JP-T 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-T 2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and compounds described in JP-T 2013-522445 (E ) and compound (G), Cmpd1~7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, the photoinitiator described in paragraphs 0020~0033 of Japanese Patent Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017~0026 of Japanese Patent Publication No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc.

[0318] The content of the photopolymerization initiator in the total solid content of the photosensitive composition is preferably 0.5 to 20% by mass. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and further preferably 3.5% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less.

[0319] The content of the specific oxime compound in the total solid content of the photosensitive composition is preferably 0.5 to 20% by mass. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and further preferably 3.5% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less.

[0320] In the photosensitive composition of the present invention, only one photopolymerization initiator may be used, or two or more photopolymerization initiators may be used. When two or more photopolymerization initiators are used, the total amount thereof is preferably within the above range.

[0321] <<Pigment Derivatives>>

[0322] The photosensitive composition of the present invention may contain a pigment derivative. When the color material used in the photosensitive composition of the present invention contains a pigment, it is preferred that the photosensitive composition of the present invention further contains a pigment derivative. The pigment derivative can be used as a dispersing aid, for example. Examples of the pigment derivative include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure and an acid group or a base group.

[0323] Examples of the pigment structure include a quinoline pigment structure, a benzimidazolone pigment structure, a benzisoindole pigment structure, a benzothiazole pigment structure, an iminium pigment structure, a squaric acid pigment structure, a crotonium pigment structure, an oxonol pigment structure, a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, an azo pigment structure, an azomethine pigment structure, a phthalocyanine pigment structure, a naphthalocyanine pigment structure, anthraquinone pigment structure, a quinacridone pigment structure, a dioxazine pigment structure, a perindole pigment structure, a perylene pigment structure, a thiazine indigo pigment structure, a thioindigo pigment structure, an isoindoline pigment structure, an isoindolinone pigment structure, a quinophthalone pigment structure, a dithiol pigment structure, a triarylmethane pigment structure, and a pyrromethene pigment structure.

[0324] Examples of the acid group contained in the pigment derivative include a carboxyl group, a sulfone group, a phosphoric acid group, a phosphonic acid group, and a phenolic hydroxyl group.

[0325] Examples of the base group of the pigment derivative include amino, pyridyl and salts thereof, ammonium salts and phthalimidomethyl groups, and examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylate ion, sulfonate ion, phenoxide ion and the like.

[0326] The pigment derivative may have excellent visible transparency (hereinafter referred to as a transparent pigment derivative). The maximum value (εmax) of the molar absorption coefficient of the transparent pigment derivative in the wavelength range of 400 to 700 nm is preferably 3000 L·mol -1 cm -1 Below, more preferably 1000 L·mol -1 cm -1 Below, more preferably 100 L·mol -1 cm -1 The lower limit of εmax is, for example, 1 L·mol -1 cm -1 Above, it can be 10L·mol -1 cm -1 above.

[0327] Specific examples of pigment derivatives include compounds described in paragraph 0124 of International Publication No. 2022 / 085485, benzimidazolone compounds described in Japanese Patent Application Publication No. 2018-168244, or salts thereof. As pigment derivatives, compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282 can be used.

[0328] The content of the pigment derivative is preferably 1 to 30 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, more preferably 4 parts by mass or more. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less. The pigment derivative may be used alone or in combination of two or more. When two or more are used in combination, their total amount is preferably within the above range.

[0329] <<Polyalkyleneimine>>

[0330] The photosensitive composition of the present invention may also contain polyalkyleneimines. Polyalkyleneimines are used, for example, as dispersing aids for pigments. Polyalkyleneimines refer to polymers obtained by ring-opening polymerization of alkyleneimines, and are polymers having at least secondary amino groups. Polyalkyleneimines may contain primary amino groups or tertiary amino groups in addition to secondary amino groups. Polyalkyleneimines are preferably polymers having branched structures containing primary amino groups, secondary amino groups, and tertiary amino groups, respectively. The number of carbon atoms in the alkyleneimines is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2. Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-buteneimine, 2,3-buteneimine, etc., preferably ethyleneimine or propyleneimine, more preferably ethyleneimine.

[0331] 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, further preferably 10,000 or less, and particularly preferably 2,000 or less. In addition, regarding the value of the molecular weight of the polyalkyleneimine, when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, 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 rise method is used. Furthermore, when the boiling point rise method cannot be measured or is difficult to measure, the value of the number average molecular weight measured by the viscosity method is used. Furthermore, when the viscosity method cannot be measured or is difficult to measure by the viscosity method, the value of the number average molecular weight of the polystyrene conversion value measured by the GPC (gel permeation chromatography) method is used.

[0332] The amine value of the polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and further preferably 15 mmol / g or more.

[0333] The polyalkylene imine is particularly preferably polyethylene imine. The polyethylene imine preferably contains 10 mol% or more of primary amino groups, more preferably 20 mol% or more of primary amino groups, and further preferably 30 mol% or more of primary amino groups relative to the total of primary amino groups, secondary amino groups, and tertiary amino groups. Commercially available products of polyethylene imine include EPOMIN SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by NIPPON SHOKUBAI CO., LTD.).

[0334] The content of the polyalkylene imine 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 further preferably 1 mass % or more. The upper limit is preferably 4.5 mass % or less, more preferably 4 mass % or less, and further preferably 3 mass % or less. In addition, the content of the polyalkylene imine is preferably 0.5 to 20 mass parts relative to 100 mass parts of pigment. The lower limit is preferably 0.6 mass parts or more, more preferably 1 mass part or more, and further preferably 2 mass parts or more. The upper limit is preferably 10 mass parts or less, and more preferably 8 mass parts or less. Only one polyalkylene imine may be used, or two or more may be used. When two or more are used, it is preferred that their total amount is within the above range.

[0335] <<Resin>>

[0336] The photosensitive composition of the present invention may further contain a resin other than the above-mentioned polymerizable compound B1. For example, the resin is formulated for the purpose of dispersing pigments, etc. in the photosensitive composition, or for the purpose of a binder. In addition, a resin mainly used for dispersing pigments, etc. in a photosensitive composition is also referred to as a dispersant. However, this use of the resin is an example, and the resin may also be used for purposes other than this use.

[0337] As the resin, for example, there can be mentioned a (meth)acrylic resin, an epoxy resin, a (meth)acrylamide resin, an ene-thiol resin, a polycarbonate resin, a polyether resin, a polyarylate resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene resin, a polyarylene ether phosphine oxide resin, a polyimide resin, a polyamideimide resin, a polyolefin resin, a cyclic olefin resin, a polyester resin, a styrene resin, a siloxane resin, and the like. In addition, as the resin, the resin described in the embodiment of International Publication No. 2016 / 088645, the resin described in Japanese Patent Application Publication No. 2017-057265, the resin described in Japanese Patent Application Publication No. 2017-032685, the resin described in Japanese Patent Application Publication No. 2017-075248, the resin described in Japanese Patent Application Publication No. 2017-066240, the resin described in Japanese Patent Application Publication No. 2017-167513, the resin described in Japanese Patent Application Publication No. 2017-173787, the resin described in paragraphs 0041 to 0060 of Japanese Patent Application Publication No. 2017-206689, the resin described in paragraphs 0022 to 0071 of Japanese Patent Application Publication No. 2018-010856, the resin described in paragraphs 0022 to 0071 of Japanese Patent Application Publication No. 2016-222891, The blocked polyisocyanate resin described in the Japanese Patent Publication No. 2020-122052, the resin described in Japanese Patent Publication No. 2020-111656, the resin described in Japanese Patent Publication No. 2020-139021, the resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in Japanese Patent Publication No. 2017-138503, the resin described in paragraphs 0199 to 0233 of Japanese Patent Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Publication No. 2020-186325, the resin represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339, and the copolymer containing an epoxy group and an acid group described in International Publication No. 2022 / 030445.

[0338] The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4,000 or more, more preferably 5,000 or more.

[0339] As the resin, it is preferred to use a resin having an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. 1 When a compound containing a basic group is used as the specific compound described later, it is preferable to use a resin having an acid group as the resin. According to this embodiment, the storage stability of the photosensitive composition can be further improved.

[0340] The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 40 mgKOH / g or more, particularly preferably 50 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 300 mgKOH / g or less, particularly preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having an acid group is preferably 5000 to 100000, more preferably 5000 to 50000. Furthermore, the number average molecular weight (Mn) of the resin having an acid group is preferably 1000 to 20000.

[0341] The resin having an acid group preferably contains a repeating unit having an acid group on the side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group on the side chain in the total repeating units of the resin. The upper limit of the content of the repeating unit having an acid group on the side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group on the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.

[0342] Regarding the resin having an acid group, reference can be made to paragraphs 0558 to 0571 of Japanese Patent Publication No. 2012-208494 (paragraphs 0685 to 0700 of the corresponding U.S. Patent Application Publication No. 2012 / 0235099), and paragraphs 0076 to 0099 of Japanese Patent Publication No. 2012-198408, which are incorporated into this specification. In addition, commercially available products can also be used as resins having an acid group. In addition, the method for introducing an acid group into the resin is not particularly limited, but for example, the method described in Japanese Patent Publication No. 6349629 can be cited. In addition, as a method for introducing an acid group into the resin, a method for introducing an acid group by reacting the hydroxyl group generated in the ring-opening reaction of the epoxy group with an acid anhydride can also be cited.

[0343] As the resin, a resin having a basic group can also be used. 1 When a compound having an acid group is used as the specific compound described later, it is preferable to use a resin having a basic group as the resin. According to this embodiment, the storage stability of the photosensitive composition can be further improved.

[0344] The resin having a base is preferably a resin containing a repeating unit having a base on the side chain, more preferably a copolymer having a repeating unit having a base on the side chain and a repeating unit not containing a base, and further preferably a block copolymer having a repeating unit having a base on the side chain and a repeating unit not containing a base. The resin having a base can also be used as a dispersant. The amine value of the resin having a base is preferably 5 to 300 mgKOH / g. The lower limit is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more. The upper limit is preferably 200 mgKOH / g or less, more preferably 100 mgKOH / g or less.

[0345] Examples of commercially available products of the resin having a basic group include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by BYK-Chemie GmbH), SOLSPERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Japan Lubrizol Corporation), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), etc. Furthermore, the resin having a basic group can also use the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Publication No. 2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of Japanese Patent Publication No. 2018-156021, and the vinyl resin having a basic group described in paragraphs 0150 to 0153 of Japanese Patent Publication No. 2019-184763, and these contents are incorporated into the present description.

[0346] The resin preferably uses a resin having an acid group and a resin having a basic group. According to this mode, the storage stability of the photosensitive composition can be further improved. When a resin having an acid group and a resin having a basic group are used together, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass relative to 100 parts by mass of the resin having an acid group.

[0347] As the resin, it is also preferred to use a resin having an aromatic carboxyl group (hereinafter also referred to as resin Ac). In resin Ac, the aromatic carboxyl group may be contained in the main chain of the repeating unit or in the side chain of the repeating unit. The aromatic carboxyl group is preferably contained in the main chain of the repeating unit. In addition, in this specification, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In the aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.

[0348] As the resin, it is preferred to use at least one selected from the group consisting of a graft polymer, a star polymer, a block copolymer, and a resin in which at least one end of a polymer chain is capped with an acid group. Such a resin can be preferably used as a dispersant.

[0349] As graft polymers, resins containing repeating units having graft chains can be cited. As graft chains, graft chains containing at least one structure selected from polyester structure, polyether structure, polystyrene structure and poly(meth)acrylic acid structure can be cited. The terminal structure of the graft chain is not particularly limited. It can be a hydrogen atom or a substituent. As substituents, alkyl groups, alkoxy groups, alkyl thioether groups and the like can be cited. Among them, from the viewpoint of improving the dispersibility of the pigment, groups having a steric repulsion effect are preferred, preferably alkyl groups or alkoxy groups having 5 to 30 carbon atoms. Alkyl groups and alkoxy groups can be any of linear, branched and cyclic, preferably linear or branched.

[0350] Specific examples of the graft polymer include resins described in paragraphs 0025 to 0094 of JP-A-2012-255128, paragraphs 0022 to 0097 of JP-A-2009-203462, and paragraphs 0102 to 0166 of JP-A-2012-255128.

[0351] Examples of the star polymer include resins having a structure in which a plurality of polymer chains are bonded to a core portion. Specific examples of the star polymer include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

[0352] As a block copolymer, it is preferred that the block of a polymer having a repeating unit containing an acid group or a base (hereinafter, also referred to as block A) and the block of a polymer having a repeating unit without an acid group and a base (hereinafter, also referred to as block B) are block copolymers. Block copolymers can also use the block copolymers (B) described in paragraphs 0063 to 0112 of Japanese Patent Publication No. 2014-219665 and the block copolymers A1 described in paragraphs 0046 to 0076 of Japanese Patent Publication No. 2018-156021, and these contents are incorporated into this description.

[0353] As the resin in which at least one end of the polymer chain is blocked with an acid group, there can be mentioned a resin having a structure in which at least one end of the polymer chain is blocked with an acid group, which contains at least one structure selected from a polyester structure, a polyether structure and a poly(meth)acrylic acid structure. As the acid group blocking the end of the polymer chain, there can be mentioned a carboxyl group, a sulfonic group and a phosphoric acid group.

[0354] The resin can also be used as a dispersant. As the dispersant, an acidic dispersant (acidic resin) and an alkaline dispersant (alkaline resin) can be cited. Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of base groups. As an acidic dispersant (acidic resin), when the total amount of the amount of acid groups and the amount of base groups is set to 100 mol%, a resin in which the amount of acid groups is 70 mol% or more is preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. In addition, an alkaline dispersant (alkaline resin) refers to a resin in which the amount of base groups is greater than the amount of acid groups. As an alkaline dispersant (alkaline resin), when the total amount of the amount of acid groups and the amount of base groups is set to 100 mol%, a resin in which the amount of base groups exceeds 50 mol% is preferred. The base possessed by the alkaline dispersant is preferably an amino group.

[0355] The dispersant can also be obtained as a commercial product, and specific examples thereof include the Disperbyk series manufactured by BYK-Chemie GmbH (e.g., Disperbyk-111, 161, 2001, etc.), the SOLSPERSE series manufactured by Lubrizol Japan Ltd. (e.g., SOLSPERSE 20000, 76500, etc.), the Ajispar series manufactured by AJinomoto Fine-Techno Co., Inc., A208F (manufactured by DKS Co. Ltd.), H-3606 (manufactured by DKS Co. Ltd.), and SANDET ET (manufactured by SANYOKASEI CO., LTD.), etc. Furthermore, the products described in paragraph 0129 of Japanese Patent Application Laid-Open No. 2012-137564 and the products described in paragraph 0235 of Japanese Patent Application Laid-Open No. 2017-194662 can also be used as the dispersant.

[0356] The content of the resin in the total solid content of the photosensitive composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.

[0357] The photosensitive composition of the present invention may contain only one resin or two or more resins. When containing two or more resins, the total amount thereof is preferably within the above range.

[0358] <<Solvents>>

[0359] The photosensitive composition of the present invention preferably contains a solvent. As the solvent, an organic solvent can be mentioned. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coating property of the composition. As the organic solvent, ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, etc. can be mentioned. For details of these, reference can be made to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated into this specification. In addition, cyclic alkyl substituted ester solvents and cyclic alkyl substituted ketone solvents can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether ... alcohol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, cyclopentane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, 1,3-butanediol diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropanol, etc. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be preferably reduced for reasons such as environmental considerations (for example, it can be 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less relative to the total amount of the organic solvent).

[0360] In the present invention, it is preferred to use an organic solvent with a low metal content. The metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion: parts per billion) or less. Organic solvents of mass ppt (parts pertrillion: parts per trillion) level can be used as needed, such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

[0361] As a method for removing impurities such as metals from an organic solvent, for example, distillation (molecular distillation, thin film distillation, etc.) or filtering using a filter can be cited. The filter pore size of the filter used in the filtration is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

[0362] The organic solvent may contain isomers (compounds having the same number of atoms but different structures), and may contain only one isomer or a plurality of isomers.

[0363] The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0364] The content of the solvent in the photosensitive composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 30 to 90% by mass.

[0365] Furthermore, from the perspective of environmental regulation, the photosensitive composition of the present invention preferably does not substantially contain environmentally regulated substances. In addition, in the present invention, substantially containing no environmentally regulated substances means that the content of 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; halogenated benzenes such as chlorobenzene, etc. These are registered as environmentally regulated substances according to REACH (Registration Evaluation Authorization and Restriction of CHemicals: Chemical Registration, Evaluation, Authorization and Restriction) regulations, PRTR (Pollutant Release and Transfer Register: Pollutant Release and Transfer Registration) law, VOC (Volatile Organic Co mpounds: Volatile Organic Compounds) regulations, etc., and the amount of use or treatment method is strictly regulated. These compounds are sometimes used as solvents when manufacturing the various components used in the photosensitive composition, and are sometimes mixed into the photosensitive composition as residual solvents. From the perspective of human safety and environmental considerations, it is preferred to minimize these substances. As a method for reducing environmentally controlled substances, there can be cited a method in which the system is heated and depressurized to a boiling point above the boiling point of the environmentally controlled substances and the environmentally controlled substances are distilled and removed from the system to reduce the amount. Furthermore, when a small amount of environmentally controlled substances are distilled and removed, it is also effective to azeotropize with a solvent having the same boiling point as the solvent in order to improve efficiency. Furthermore, when containing a compound having free radical polymerizability, in order to suppress the free radical polymerization reaction during the reduced pressure distillation and cross-linking between molecules, an inhibitor may be added and reduced pressure distillation may be performed. These distillation removal methods can be performed at any stage, such as the stage of the product of the raw material reaction (such as the resin solution and the multifunctional monomer solution after polymerization) or the stage of the photosensitive composition prepared by mixing these compounds.

[0366] <<Compounds having a cyclic ether group>>

[0367] The photosensitive composition of the present invention may further contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group, an oxetane group, and the like. The epoxy group may be an alicyclic epoxy group. In addition, an alicyclic epoxy group refers to a monovalent functional group having a cyclic structure formed by condensation of an epoxy ring and a saturated hydrocarbon ring. 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 a compound having one or more epoxy groups in one molecule, and preferably a compound having two or more epoxy groups. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy group contained in the epoxy compound can be, for example, set to 10 or less, or can be set to 5 or less. The lower limit of the epoxy group contained in the epoxy compound is preferably 2 or more. As the epoxy compound, the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, paragraphs 0085 to 0092 of JP-A-2014-089408, the compounds described in JP-A-2017-179172, the xanthene type epoxy resin described in JP-A-2021-195421, and the xanthene type epoxy resin described in JP-A-2021-195422 can also be used.

[0368] The compound having a cyclic ether group may be a low molecular weight compound (e.g., a molecular weight of less than 2000, and further, a molecular weight of 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 a cyclic ether group is preferably 200 to 100000, and more preferably 500 to 50000. The upper limit of the weight average molecular weight is more preferably 10000 or less, particularly preferably 5000 or less, and further preferably 3000 or less.

[0369] Commercially available products of compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (manufactured by NOF CORPORATION, containing epoxy group polymers), etc. Furthermore, compounds described in the examples described later can also be used as compounds having a cyclic ether group.

[0370] 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 preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less. The compound having a cyclic ether group may be used in one kind or in two or more kinds. When two or more kinds are used, it is preferred that their total amount is within the above range.

[0371] <<Curing Accelerator>>

[0372] The photosensitive composition of the present invention may contain a curing accelerator. As a curing accelerator, thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generating agents, isocyanate compounds, alkoxysilane compounds, onium salt compounds, etc. can be cited. As a specific example of a curing accelerator, compounds described in paragraph 0164 of International Publication No. 2022 / 085485, compounds described in Japanese Patent Gazette No. 2021-181406, etc. can be cited. The content of the curing accelerator in the total solid content of the photosensitive composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.

[0373] <<Ultraviolet light absorber>>

[0374] The photosensitive composition of the present invention can contain an ultraviolet absorber. As an ultraviolet absorber, conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, etc. can be cited. As a specific example of such a compound, the compound described in paragraph 0179 of International Publication No. 2022 / 085485, the reactive triazine ultraviolet absorber described in Japanese Patent Publication No. 2021-178918, and the ultraviolet absorber described in Japanese Patent Publication No. 2022-007884 can also be used.

[0375] The content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. In the present invention, only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more ultraviolet absorbers are used, the total amount is preferably within the above range.

[0376] <<Polymerization Inhibitor>>

[0377] 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-tert-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, cerium salts, etc.). Among them, 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% by mass. The polymerization inhibitor may be only one type or two or more types. When there are two or more types, the total amount is preferably within the above range.

[0378] <<Silane coupling agent>>

[0379] The photosensitive composition of the present invention can contain a silane coupling agent. In the present invention, a silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than the hydrolyzable group. In addition, a hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can produce a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, etc., preferably an alkoxy group. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, as a functional group other than a hydrolyzable group, for example, a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetane group, an amino group, a urea group, a thioether group, an isocyanate group, a phenyl group, etc., preferably an amino group, a (meth) acryloyl group and an epoxy group. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-503), etc. In addition, specific examples of silane coupling agents include compounds described in paragraphs 0018 to 0036 of Japanese Patent Publication No. 2009-288703 and compounds described in paragraphs 0056 to 0066 of Japanese Patent Publication No. 2009-242604, which are incorporated into this specification. The content of the silane coupling agent in the total solid content of the photosensitive composition is preferably 0.01 to 15.0% by mass, and more preferably 0.05 to 10.0% by mass. The silane coupling agent may be only one kind or two or more kinds. When there are two or more kinds, the total amount is preferably within the above range.

[0380] <<Surfactants>>

[0381] The photosensitive composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant may be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. Regarding the surfactant, reference may be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which are incorporated into this specification.

[0382] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. From the perspective of uniformity of the thickness of the coating film or liquid saving, a fluorine-based surfactant having a fluorine content within this range is effective and has good solubility in the photosensitive composition.

[0383] As the fluorine-based surfactant, the compounds described in paragraphs 0167 to 0169 of International Publication No. 2022 / 085485 can be used.

[0384] The fluorine-based surfactant can also use a block polymer. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which 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 and propyleneoxy). In addition, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of Japanese Patent Publication No. 2010-032698 or the following compounds can also be exemplified as fluorine-based surfactants used in the present invention.

[0385] [Chemical formula 21]

[0386]

[0387] The weight average molecular weight of the above compound is preferably 3000 to 50000, for example, 14000. In the above compound, % indicating the ratio of the repeating unit is mol %.

[0388] Fluorine-based surfactants can also use fluorine-containing copolymers having a group containing an ethylenically unsaturated bond on the side chain. As specific examples, compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Publication No. 2010-164965, and MEGAFACE RS-101, RS-102, RS-718K, RS-72-K manufactured by DIC Corporation can be cited. In addition, fluorine-based surfactants can also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Publication No. 2015-117327, and fluorine-containing copolymers described in Japanese Patent Publication No. 2022-000494.

[0389] From the viewpoint of environmental regulation, it is also preferable to use the surfactant described in International Publication No. 2020 / 084854 as a substitute for the surfactant having a perfluoroalkyl group with 6 or more carbon atoms.

[0390] It is also preferred to use a fluorine-containing imide salt compound represented by the formula (fi-1) as the surfactant.

[0391] [Chemical formula 22]

[0392]

[0393] In the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, and X a+ Indicates a-valent metal ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH4 + .

[0394] Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), SOLSPERSE 20000 (manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oi1 & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), etc.

[0395] Examples of the silicone surfactant include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie GmbH), etc.

[0396] Furthermore, as the silicone-based surfactant, compounds having the following structures can also be used.

[0397] [Chemical formula 23]

[0398]

[0399] The content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be only one or two or more. When there are two or more, the total amount is preferably within the above range.

[0400] <<Antioxidants>>

[0401] The photosensitive composition of the present invention can contain an antioxidant. Examples of the antioxidant include phenolic compounds, phosphite compounds, thioether compounds, and the like. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Examples of preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Furthermore, the antioxidant is also preferably a compound having a phenolic group and a phosphite group in the same molecule. Furthermore, the antioxidant can also preferably use a phosphorus-based antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphorin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphorin-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite. As commercially available antioxidants, for example, ADEKA STAB A0-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB A0-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION) etc. can be mentioned. In addition, antioxidants can also use compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, compounds described in International Publication No. 2017 / 006600, compounds described in International Publication No. 2017 / 164024, and compounds described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount is preferably within the above range.

[0402] <<Other ingredients>>

[0403] The photosensitive composition of the present invention may contain a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (e.g., conductive particles, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.) as needed. By appropriately containing these ingredients, properties such as film physical properties can be adjusted. These ingredients can use the compounds described in paragraph 0182 of International Publication No. 2022 / 085485.

[0404] In order to adjust the refractive index of the obtained film, the photosensitive composition of the present invention may contain a metal oxide. Examples of the metal oxide include TiO2, ZrO2, Al2O3, SiO2, etc. The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and further preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In addition, the core may be hollow.

[0405] The photosensitive composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include compounds described in paragraph 0183 of International Publication No. 2022 / 085485.

[0406] The photosensitive composition of the present invention also preferably contains substantially no terephthalate. Here, “substantially no” means that the content of terephthalate is 1000 ppb or less, more preferably 100 ppb or less, and particularly preferably 0, based on the total amount of the photosensitive composition.

[0407] The free metal content of the photosensitive composition of the present invention is preferably 100 ppm or less, more preferably 50 ppm or less. In addition, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Methods for reducing free metals or halogens in the photosensitive composition include washing with ion exchange water, filtration, ultrafiltration, purification using ion exchange resins, and the like.

[0408] From the perspective of environmental regulation, the use of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt is sometimes regulated. In the photosensitive composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkylsulfonic acid (especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt, and perfluoroalkylcarboxylic acid (especially 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 further preferably in the range of 0.1 ppb to 300 ppb, relative to 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, by using a compound that can replace perfluoroalkylsulfonic acid and its salt, and a compound that can replace perfluoroalkylcarboxylic acid and its salt, a photosensitive composition substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt can be selected. As compounds that can replace the regulated compounds, for example, compounds that are excluded from the regulated objects due to the difference in the number of carbon atoms of the perfluoroalkyl group can be cited. However, the above content does not prevent the use of perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts. The photosensitive composition of the present invention can contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts within the maximum allowed range.

[0409] The water content of the photosensitive composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

[0410] The photosensitive composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface shape (flatness, etc.) and adjusting the film thickness. The value of the viscosity can be appropriately selected as needed, but for example, it is preferably 0.3mPa·s to 50mPa·s at 25°C, and more preferably 0.5mPa·s to 20mPa·s. As a method for measuring the viscosity, for example, it can be measured using a cone-plate viscometer at a temperature adjusted to 25°C.

[0411] <<Storage Container>>

[0412] There is no particular limitation on the storage container for the photosensitive composition, and a known storage container can be used. Furthermore, as a storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the photosensitive composition, it is also preferred to use a multilayer bottle having an inner wall of the container composed of 6 kinds of 6 layers of resin or a bottle having a 7-layer structure of 6 kinds of resin. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited. Furthermore, for the purpose of preventing metal from dissolving from the inner wall of the container, improving the storage stability of the photosensitive composition, or suppressing the deterioration of the components, the inner wall of the container is also preferably made of glass, stainless steel, etc.

[0413] <Method for preparing photosensitive composition>

[0414] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photosensitive composition, all the components can be dissolved and / or dispersed in a solvent at the same time to prepare the photosensitive composition, or each component can be appropriately prepared as two or more solutions or dispersions as needed, and they can be mixed when used (when applied) to prepare the photosensitive composition.

[0415] In addition, when preparing the photosensitive composition, it is preferred to include a process for dispersing the pigment. In the process for dispersing the pigment, compression, squeezing, impact, shearing, cavitation, etc. can be cited as the mechanical force for the dispersion of the pigment. As specific examples of these processes, bead mill, sand mixer (sand mill), roller mill, ball mill, paint stirrer, micro jet machine, high-speed impeller, sand grinder (Sand grinder), jet mixer, high-pressure wet micronization, ultrasonic dispersion, etc. can be cited. In addition, when the pigment is crushed in the sand mixer (bead mill), it is preferably processed under the following conditions: by using micro beads with a small diameter and increasing the filling rate of micro beads, etc. to improve the crushing efficiency. In addition, it is preferred to remove coarse particles by filtering, centrifugation, etc. after the crushing process. In addition, regarding the process and disperser for dispersing the pigment, the process and disperser described in paragraph 0022 of "Dispersion Technology Collection, JOHOKIKOCO., LTD., July 15, 2005" or "Dispersion Technology and Industrial Practical Application Comprehensive Data Collection Centering on Suspension (Solid / Liquid Dispersion System), Business Development Center Publishing Department, October 10, 1978", and Japanese Patent Publication No. 2015-157893 can be preferably used. In addition, in the process for dispersing the pigment, the particles can be finely processed by a salt milling process. For the materials, equipment, processing conditions, etc. used in the salt milling process, for example, reference can be made to the records of Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629. As materials for beads used for dispersion, zirconium dioxide, agate, quartz, titanium dioxide, tungsten carbide, silicon nitride, aluminum oxide, stainless steel, and glass can be cited. Furthermore, the beads may be inorganic compounds having a Mohs hardness of 2 or more. The photosensitive composition may contain 1 to 10000 ppm of the beads.

[0416] When preparing a photosensitive composition, it is preferred to filter the photosensitive composition with a filter for the purpose of removing impurities or reducing defects. Examples of the type of filter used for filtration and the filtering method include the filters and filtering methods described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485.

[0417] <Film>

[0418] The film of the present invention is a film obtained from the above-mentioned photosensitive composition of the present invention. The film of the present invention can be used in optical filters such as color filters, near infrared transmission filters, and near infrared cut filters.

[0419] The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

[0420] When the film of the present invention is used as a color filter, it is preferred that the film of the present invention has a green, red, blue, cyan, magenta or yellow hue. In addition, the film of the present invention can be preferably used as a colored pixel of a color filter. As colored pixels, red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. can be cited.

[0421] When the film of the present invention is used as a near infrared cut filter, the maximum absorption wavelength of the film of the present invention is preferably present in the range of wavelengths of 700 to 1800 nm, more preferably in the range of wavelengths of 700 to 1300 nm, and further preferably in the range of wavelengths of 700 to 1000 nm. In addition, the transmittance in all ranges of wavelengths of 400 to 650 nm of the film is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. In addition, the transmittance at at least one point in the range of wavelengths of 700 to 1800 nm of the film is preferably 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm, i.e., absorbance Amax / absorbance A550, is preferably 20 to 500, more preferably 50 to 500, further preferably 70 to 450, and particularly preferably 100 to 400.

[0422] When the film of the present invention is used as a near-infrared transmission filter, the film of the present invention preferably has any one of the following spectral characteristics (i1) to (i5), for example.

[0423] (i1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1500 nm. A film having such spectral characteristics can shield light in the wavelength range of 400 to 640 nm and transmit light with a wavelength exceeding 750 nm.

[0424] (i2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm. A film having such spectral characteristics can shield light in the wavelength range of 400 to 750 nm and transmit light with a wavelength exceeding 850 nm.

[0425] (i3): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. A film having such spectral characteristics can shield light in the wavelength range of 400 to 830 nm and transmit light with a wavelength exceeding 950 nm.

[0426] (i4): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. A film having such spectral characteristics can shield light in the wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1050 nm.

[0427] (i5): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm. A film having such spectral characteristics can shield light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength exceeding 1150 nm.

[0428] <Optical filter>

[0429] The optical filter of the present invention has the above-mentioned film of the present invention. As the type of the optical filter, a color filter, a near infrared cut filter and a near infrared transmission filter can be cited, and a color filter is preferred. The color filter preferably has the film of the present invention as its pixel, and more preferably has the film of the present invention as a colored pixel.

[0430] In the optical filter, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness of the pixels contained in the optical filter is preferably 5 μm or less, more preferably 1 μm or less, and further preferably 0.6 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

[0431] The width of the pixel contained in the filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and further preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, further preferably 1.0 μm or less, and further preferably 0.8 μm or less. In addition, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

[0432] The filter may be provided with a protective layer on the surface of the film of the present invention. By providing a protective layer, various functions such as oxidation resistance, low reflection, hydrophilicity / hydrophobicity, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. 。 As a method for forming the protective layer, there can be cited a method of coating a resin composition for forming the protective layer, a chemical vapor deposition method, a method of attaching a formed resin with an adhesive material, etc. As components constituting the protective layer, there can be cited (meth) acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, carbamate resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al2O3, Mo, SiO2, Si2N4, etc., and two or more of these components can be contained. For example, in the case of a protective layer for the purpose of preventing oxidation, the protective layer preferably contains a polyol resin, SiO2 and Si2N4. Furthermore, in the case of a protective layer for the purpose of reducing reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

[0433] When the coating resin composition forms a protective layer, as the coating method of the photosensitive composition, known methods such as spin coating, casting, screen printing, inkjet can be used. The organic solvent contained in the photosensitive composition can use a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When the protective layer is formed by chemical vapor deposition, as chemical vapor deposition, known chemical vapor deposition (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used.

[0434] The protective layer may contain organic / inorganic particles, absorbents of light of specific wavelengths (e.g., ultraviolet rays, near infrared rays, etc.), refractive index adjusters, antioxidants, adhesion agents, surfactants and other additives as needed. As examples of organic / inorganic particles, for example, polymer particles (e.g., silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silicon dioxide, calcium carbonate, barium sulfate, etc. can be cited. The absorbent of light of specific wavelengths can use known absorbents. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, relative to the total mass of the protective layer.

[0435] Furthermore, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Laid-Open No. 2017-151176 can also be used.

[0436] The optical filter may have a structure in which pixels are embedded in spaces partitioned by partition walls, for example, in a grid pattern.

[0437] The optical filter of the present invention can be used in optical sensors such as solid-state imaging devices, image display devices, and the like.

[0438] <Optical filter manufacturing method>

[0439] The method for manufacturing an optical filter preferably includes the following steps: a step of forming a photosensitive composition layer on a support using the photosensitive composition of the present invention; a step of exposing the photosensitive composition layer in a pattern; and a step of developing and removing the unexposed portion of the photosensitive composition layer to form a pattern (pixel). If necessary, a step of baking the photosensitive composition layer (pre-baking step) and a step of baking the developed pattern (pixel) (post-baking step) may be provided.

[0440] In the process of forming a photosensitive composition layer, a photosensitive composition layer is formed on a support using the photosensitive composition of the present invention. As a support, there is no particular limitation and it can be appropriately selected according to the purpose. For example, a glass substrate, a silicon substrate, etc. can be cited, preferably a silicon substrate. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. can also be formed on the silicon substrate. In addition, a black matrix is ​​sometimes formed on the silicon substrate to isolate each pixel. In addition, in order to improve the adhesion with the upper layer, prevent the diffusion of substances or flatten the surface of the substrate, a primer layer can be provided on the silicon substrate. When measured with diiodomethane, the surface contact angle of the primer layer is preferably 20 to 70°. And, when measured with water, it is preferably 30 to 80°.

[0441] As a method for applying the photosensitive composition, a known method can be used. For example, the coating method described in paragraph 0207 of International Publication No. 2022 / 085485 can be used.

[0442] The photosensitive composition layer formed on the support can be dried (prebaked). When the film is manufactured by a low-temperature process, prebaking is not required. When prebaking is performed, the prebaking temperature is preferably below 150°C, more preferably below 120°C, and further preferably below 110°C. The lower limit can be set to above 50°C, for example, and can also be set to above 80°C. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, etc.

[0443] Next, the photosensitive composition layer formed on the support is exposed in a pattern. For example, a stepper or scanner is used to expose the photosensitive composition layer through a mask having a predetermined mask pattern, thereby exposing the photosensitive composition layer in a pattern. Thus, the exposed portion can be cured.

[0444] As radiation (light) that can be used during exposure, g-rays, i-rays, etc. can be cited. In addition, light with a wavelength of 300nm or less (preferably light with a wavelength of 180 to 300nm) can also be used. As light with a wavelength of 300nm or less, KrF rays (wavelength 248nm), ArF rays (wavelength 193nm), etc. can be cited, preferably KrF rays (wavelength 248nm). In addition, a light source with a long wavelength of more than 300nm can also be used. As a light source, an electrodeless ultraviolet lamp system, ultraviolet and infrared mixed curing can be used.

[0445] Furthermore, during exposure, light can be continuously irradiated for exposure, or pulsed irradiation can be performed for exposure (pulse exposure). In addition, pulse exposure refers to an exposure method in which light irradiation and pause are repeated for a short period of time (e.g., less than milliseconds) to perform exposure.

[0446] For example, the irradiation amount (exposure amount) is preferably 0.03 to 2.5 J / cm 2 , more preferably 0.05 to 1.0 J / cm 2 The oxygen concentration during exposure can be appropriately selected. In addition to exposure under the atmosphere, exposure can also be performed in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high oxygen atmosphere with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be appropriately set, usually from 1000 W / m 2 ~100000W / m2 (For example, 5000W / m 2 , 15000W / m 2 or 35000W / m 2 The oxygen concentration and exposure illuminance can be appropriately combined, for example, the oxygen concentration can be set to 10% by volume and the illuminance can be set to 10000 W / m 2 , oxygen concentration 35 volume % and illumination 20000W / m 2 wait.

[0447] Next, the unexposed portion of the photosensitive composition layer is removed by development to form a pattern (pixel). The unexposed portion of the photosensitive composition layer can be removed by development using a developer. As a result, the unexposed portion of the photosensitive composition layer in the exposure step is dissolved in the developer, and only the photocured portion remains. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removability of the residue, the process of shaking off the developer every 60 seconds and then supplying a new developer can be repeated multiple times.

[0448] The developer may be an organic solvent, an alkali developer, or the like, and an alkali developer may be preferably used. As for the developer and the cleaning (rinsing) method after development, the developer or the cleaning method described in paragraph 0214 of International Publication No. 2022 / 085485 may be used.

[0449] It is preferred that additional exposure treatment or heating treatment (post-baking) is performed after development and drying. Additional exposure treatment or post-baking is a curing treatment after development for fully curing it. The heating temperature in the post-baking is preferably 100 to 240°C, more preferably 200 to 240°C, for example. The film after development can be post-baked continuously or intermittently using a heating mechanism such as a heating plate or a convection oven (hot air circulation dryer), a high-frequency heater, etc. in a manner that meets the above conditions so that the film meets the above conditions. In the case of additional exposure treatment, the light used for exposure is preferably light with a wavelength of less than 400nm. In addition, the additional exposure treatment can be performed by the method described in Korean Patent Gazette No. 10-2017-0122130.

[0450] <Solid-state imaging device>

[0451] The solid-state imaging device of the present invention has the above-mentioned film of the present invention. The structure of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, and examples thereof include the following structures.

[0452] The structure of the solid-state imaging element is as follows: a plurality of photodiodes and transfer electrodes of polysilicon or the like including a light-receiving area constituting the solid-state imaging element (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) are provided on a substrate, a light-shielding film having only the light-receiving portion of the photodiode opened is provided on the photodiode and the transfer electrode, a device protection film composed of silicon nitride or the like formed in a manner covering the entire surface of the light-shielding film and the light-receiving portion of the photodiode is provided on the light-shielding film, and a color filter is provided on the device protection film. Furthermore, it may be a structure having a focusing mechanism (e.g., a microlens, etc., the same below) on the device protection film and below the color filter (on the side close to the substrate) or a structure having a focusing mechanism on the color filter. Furthermore, the color filter may have a structure in which each color pixel is embedded in a space separated by a partition wall, for example, in a grid shape. It is preferred that the refractive index of the partition wall at this time is lower than the refractive index of each color pixel. As an example of an imaging device having such a structure, the devices described in Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, and International Publication No. 2018 / 043654 can be cited. In addition, as shown in Japanese Patent Publication No. 2019-211559, an ultraviolet absorption layer can also be provided in the structure of the solid-state imaging element to improve light resistance. The imaging device having the solid-state imaging element of the present invention can be used as a vehicle-mounted camera or a surveillance camera in addition to being able to be used in a digital camera or an electronic device having an imaging function (such as a mobile phone).

[0453] <Image Display Device>

[0454] The image display device of the present invention has the above-mentioned film of the present invention. As the image display device, a liquid crystal display device or an organic electroluminescent display device can be cited. The definition of the image display device or the details of each image display device are recorded in, for example, "Electronic Display Device (written by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)", "Display Device (written by Junsho Ibuki, Sangyo Tosho Publishing Co., Ltd., published in 1989)" and the like. In addition, regarding the liquid crystal display device, it is recorded in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., published in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology".

[0455] Example

[0456] Hereinafter, the present invention will be described in more detail by giving examples. The materials, usage amounts, ratios, processing contents, processing steps etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0457] <Production of Dispersion Liquid>

[0458] The materials listed in the following table were mixed to obtain a mixed solution. The obtained mixed solution was dispersed using Ultra Apex Mill manufactured by KOTOBUKIKOGYOU.CO., LTD. as a circulation type dispersion device (bead mill) to produce a dispersion. The unit of the added amount in the table is part by mass.

[0459] [Table 1]

[0460]

[0461] [Table 2]

[0462]

[0463] The details of the materials described in the above table are as follows: Resins B-1 to B-4 are materials corresponding to polymerizable compounds having a weight average molecular weight of 3,000 or more.

[0464] (pigment)

[0465] PG7: CI Pigment Green 7 (green pigment)

[0466] PG36: CI Pigment Green 36 (green pigment)

[0467] PG58: CI Pigment Green 58 (green pigment)

[0468] PG59: CI Pigment Green 59 (green pigment)

[0469] PG63: CI Pigment Green 63 (green pigment)

[0470] PY129: CI Pigment Yellow 129 (yellow pigment)

[0471] PY138: CI Pigment Yellow 138 (yellow pigment)

[0472] PY139: CI Pigment Yellow 139 (yellow pigment)

[0473] PY150: CI Pigment Yellow 150 (yellow pigment)

[0474] PY185: CI Pigment Yellow 185 (yellow pigment)

[0475] PY215: CI Pigment Yellow 215 (yellow pigment)

[0476] PY231: CI Pigment Yellow 231 (yellow pigment)

[0477] PY233: CI Pigment Yellow 233 (yellow pigment)

[0478] PR177: CI Pigment Red 177 (red pigment)

[0479] PR254: CI Pigment Red 254 (red pigment)

[0480] PR264: CI Pigment Red 264 (red pigment)

[0481] PR272: CI Pigment Red 272 (red pigment)

[0482] PR291: CI Pigment Red 291 (red pigment)

[0483] PB15:3:CI Pigment Blue 15:3 (blue pigment)

[0484] PB15:4:CI Pigment Blue 15:4 (blue pigment)

[0485] PB15:6:CI Pigment Blue 15:6 (blue pigment)

[0486] PB16: CI Pigment Blue 16 (blue pigment)

[0487] PV23: CI Pigment Violet 23 (Purple Pigment)

[0488] P-23: Compound of the following structure (pyrrolopyrrole compound, near infrared absorbing pigment)

[0489] P-24: Compound of the following structure (squaric acid compound, near infrared absorbing pigment)

[0490] [Chemical formula 24]

[0491]

[0492] (Dispersing aid)

[0493] Syn-1: Compound with the following structure (pigment derivative)

[0494] [Chemical formula 25]

[0495]

[0496] Syn-2: Polyethyleneimine (EPOMIN SP-006 (manufactured by NIPPON SHOKUBAI CO., LTD.))

[0497] Syn-3: Compound with the following structure (pigment derivative)

[0498] [Chemical formula 26]

[0499]

[0500] Syn-4: Compound with the following structure (pigment derivative)

[0501] [Chemical formula 27]

[0502]

[0503] Syn-5: Compound with the following structure (pigment derivative)

[0504] [Chemical formula 28]

[0505]

[0506] Syn-6: Compound with the following structure (pigment derivative)

[0507] [Chemical formula 29]

[0508]

[0509] Syn-7: Compound with the following structure (pigment derivative)

[0510] [Chemical formula 30]

[0511]

[0512] Syn-8: Compound with the following structure (pigment derivative)

[0513] [Chemical formula 31]

[0514]

[0515] (resin)

[0516] B-1: Resin with the following structure (polymerizable compound with a weight average molecular weight of 3,000 or more. The value indicated on the main chain is the molar ratio, and the value indicated on the side chain is the number of repeating units. Weight average molecular weight 20,000, acid value 66.6 mgKOH / g)

[0517] [Chemical formula 32]

[0518]

[0519] B-2: Resin with the following structure (polymerizable compound with a weight average molecular weight of 3,000 or more. The value indicated on the main chain is the molar ratio, and the value indicated on the side chain is the number of repeating units. Weight average molecular weight 23,000, acid value 59.6 mgKOH / g)

[0520] [Chemical formula 33]

[0521]

[0522] B-3: Resin with the following structure (polymerizable compound with a weight average molecular weight of 3000 or more. The value indicated on the main chain is the molar ratio, and the value indicated on the side chain is the number of repeating units. Weight average molecular weight 16000, acid value 67 mgKOH / g)

[0523] [Chemical formula 34]

[0524]

[0525] B-4: Resin having the following structure (polymerizable compound having a weight average molecular weight of 3,000 or more. Weight average molecular weight of 18,000, acid value of 82.1 mgKOH / g)

[0526] [Chemical formula 35]

[0527]

[0528] (Solvent)

[0529] D-1: Propylene glycol monomethyl ether acetate

[0530] D-2: Cyclopentanone

[0531] D-3: Propylene glycol monomethyl ether

[0532] <Production of Photosensitive Composition>

[0533] The materials described in the following table were mixed to produce a photosensitive composition. The unit of the numerical value of the addition amount in the table is part by mass.

[0534] [Table 3]

[0535]

[0536] [Table 4]

[0537]

[0538] [Table 5]

[0539]

[0540] [Table 6]

[0541]

[0542] [Table 7]

[0543]

[0544] [Table 8]

[0545]

[0546] [Table 9]

[0547]

[0548] [Table 10]

[0549]

[0550] [Table 11]

[0551]

[0552] [Table 12]

[0553]

[0554] The details of the materials described in the above table are as follows: Resins C-1 and C-2 are materials corresponding to polymerizable compounds having a weight average molecular weight of 3,000 or more.

[0555] (Dispersion liquid)

[0556] Green dispersions 1 to 13: the above Green dispersions 1 to 13

[0557] Yellow dispersions 1 to 12: Yellow dispersions 1 to 12 mentioned above

[0558] Red dispersions 1 to 10: the above-mentioned Red dispersions 1 to 10

[0559] Blue dispersions 1 to 9: the above-mentioned Blue dispersions 1 to 9

[0560] Violet dispersions 1 to 3: Violet dispersions 1 to 3 mentioned above

[0561] IR dispersions 1 and 2: IR dispersions 1 and 2 mentioned above

[0562] (Polymerizable compound)

[0563] M-1: A mixture of compounds of the following structures (compound on the left: compound on the right = 7:3 (molar ratio))

[0564] [Chemical formula 36]

[0565]

[0566] M-2: Compound with the following structure

[0567] [Chemical formula 37]

[0568]

[0569] M-3: Compound with the following structure

[0570] [Chemical formula 38]

[0571]

[0572] M-4: Compound with the following structure

[0573] [Chemical formula 39]

[0574]

[0575] M-5: ARONIX M-521 (polyacid-modified acrylic oligomer, manufactured by TOAGOSEI CO., LTD.)

[0576] (resin)

[0577] C-1: Resin with the following structure (polymerizable compound with a weight average molecular weight of 3000 or more. The numerical value indicated on the main chain is a molar ratio. Weight average molecular weight 11000, acid value 69.2 mgKOH / g)

[0578] [Chemical formula 40]

[0579]

[0580] C-2: Resin with the following structure (polymerizable compound with a weight average molecular weight of 3,000 or more. The values ​​indicated on the main chain are molar ratios. Weight average molecular weight: 21,000, acid value: 80 mgKOH / g)

[0581] [Chemical formula 41]

[0582]

[0583] (Photopolymerization Initiator)

[0584] I-1 to I-21: Compounds of the following structures

[0585] [Chemical formula 42]

[0586]

[0587] [Chemical formula 43]

[0588]

[0589] [Chemical formula 44]

[0590]

[0591] IC-1: Compound with the following structure

[0592] [Chemical formula 45]

[0593]

[0594] (Surfactant)

[0595] W-1: KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant)

[0596] (Inhibitor)

[0597] Q-1: p-Methoxyphenol

[0598] (additive)

[0599] S-1: Karenz MTBD1 (manufactured by SHOWA DENKO KK, multifunctional thiol compound)

[0600] S-2: Karenz MTPE1 (manufactured by SHOWA DENKO KK, multifunctional thiol compound)

[0601] S-3: Karenz MTNR1 (manufactured by SHOWA DENKO KK, a multifunctional thiol compound)

[0602] S-4: Karenz MTTPMB (manufactured by SHOWA DENKO KK, multifunctional thiol compound)

[0603] E-1: 2,2'-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct

[0604] E-2: PIONIN D-6112-W (manufactured by Takemoto Oil & Fat Co., Ltd., nonionic surfactant)

[0605] (Solvent)

[0606] D-1: Propylene glycol monomethyl ether acetate

[0607] D-2: Cyclopentanone

[0608] D-4: Butyl acetate

[0609] D-5: Propylene glycol diacetate

[0610] <Performance Evaluation>

[0611] (Exposure sensitivity, adhesion, and residue evaluation)

[0612] Each photosensitive composition obtained above was applied to an 8-inch (203.2 mm) silicon wafer with a primer layer by spin coating so that the film thickness after coating was 0.4 μm, and then 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 at an illumination of 35000 W / m using a KrF scanning exposure machine through a mask having a 0.5 μm square pattern. 2 , exposure 20~200mJ / cm 2 The exposed layer was exposed to light (KrF line) with a wavelength of 248 nm. Next, the exposed composition layer was spray developed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. After that, pure water was used and rinsed by rotary spraying to form pixels. The obtained pixels were observed using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corporation) at a magnification of 20,000 times. Based on the observed images, the adhesion and residue were evaluated according to the following criteria.

[0613] -Evaluation criteria for exposure sensitivity-

[0614] The exposure amount required to achieve a pattern line width of 0.7 μm was calculated, and the exposure sensitivity was evaluated according to the following criteria.

[0615] 5: Exposure is 60mJ / cm 2 the following

[0616] 4: Exposure exceeds 60mJ / cm 2 And 100mJ / cm 2 the following

[0617] 3: Exposure exceeds 100mmJ / cm 2 And 150mJ / cm 2 the following

[0618] 2: Exposure exceeds 150mmJ / cm 2 And less than 200mJ / cm2

[0619] 1: Exposure exceeds 200mmJ / cm 2

[0620] -Adhesion Evaluation-

[0621] The obtained pixels were observed under an optical microscope at 100 mJ / cm 2 1071×1071 portions of the portion exposed with an exposure amount of 1071×1071 were counted, and the number of peeled pixels was counted. Adhesion was determined based on the number of peeled pixels according to the following criteria.

[0622] 5: The number of stripped pixels is less than 10

[0623] 4: The number of stripped pixels is more than 10 and less than 20

[0624] 3: The number of stripped pixels is more than 20 and less than 50

[0625] 2: The number of stripped pixels is more than 50 and less than 200

[0626] 1: The number of stripped pixels exceeds 200

[0627] -Evaluation criteria for residues-

[0628] The pixels after development were evaluated for residue according to the following criteria.

[0629] 5: Good pixel linearity, little residue between pixels

[0630] 4: Due to the residue around the pixels, the linearity of the pattern is slightly poor, but there is little residue between pixels.

[0631] 3: The linearity of the pattern is poor due to the residue around the pixels, but there is little residue between pixels.

[0632] 2: Due to the residue around the pixels, the pattern linearity is poor and there are many residues between pixels

[0633] 1: The pixels are not developed and cannot form pixels

[0634] (Evaluation of moisture resistance)

[0635] On a silicon wafer having a grid structure with a pitch of 0.7 μm, a grid width of 120 nm, and a grid height of 0.4 μm, each of the photosensitive compositions obtained above was applied by spin coating so that the film thickness after coating was 0.4 μm, and then 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 at an illumination of 35000 W / m using a KrF scanning exposure machine through a mask having a 0.5 μm square pattern. 2 、Exposure 100mJ / cm 2The exposed layer was exposed to light (KrF line) with a wavelength of 248 nm. Next, the exposed composition layer was spray developed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. After that, pure water was used and rinsed by rotary spraying to prepare an evaluation substrate with a pattern embedded in the grid. The evaluation substrate was maintained for 168 hours at 110°C and 85% humidity using a highly accelerated life (HAST) tester (manufactured by ESPEC CORP., HAST CHAMBER EHS221). The substrate after the moisture resistance test was cut, and the cross-sectional shape was observed using a scanning electron microscope (SEM) S-4800 (manufactured by Hitachi High-Tech Corporation.), and the moisture resistance was evaluated according to the following criteria.

[0636] 5: The pattern is embedded in the grid and no voids are observed.

[0637] 4: The pattern is embedded in the grid, but there are slight gaps.

[0638] 3: The pattern is embedded in the grid, but there are gaps.

[0639] 2: The pattern is embedded in the grid but peeled from it.

[0640] 1: The pattern is completely peeled off and does not exist in the grid.

[0641] [Table 13]

[0642] Exposure sensitivity Adhesion Residue Moisture resistance Example 1 3 4 4 4 Example 2 4 4 4 5 Example 3 3 4 4 4 Example 4 3 4 4 4 Example 5 4 4 4 5 Example 6 3 3 4 4 Example 7 3 3 3 3 Example 8 3 3 3 3 Example 9 3 3 3 3 Example 10 3 5 4 4 Embodiment 11 5 5 5 5 Example 12 3 5 4 4 Embodiment 13 5 5 5 5 Embodiment 14 5 5 3 5 Embodiment 15 5 5 3 5 Example 16 5 5 3 5 Embodiment 17 5 5 3 5 Embodiment 18 4 4 4 5 Embodiment 19 4 4 4 5 Embodiment 20 5 5 5 5 Embodiment 21 5 5 5 5 Embodiment 22 4 4 4 5 Embodiment 23 4 4 4 5 Embodiment 24 4 4 4 5 Embodiment 25 4 4 4 5 Embodiment 26 4 4 4 5 Embodiment 27 4 4 4 5 Embodiment 28 4 4 4 5 Embodiment 29 4 4 4 5 Embodiment 30 4 4 4 5 Embodiment 31 4 4 4 5 Embodiment 32 4 4 4 5 Embodiment 33 4 4 4 5 Embodiment 34 4 4 4 5 Embodiment 35 4 4 4 5 Embodiment 36 4 4 4 5 Embodiment 37 4 4 4 5 Embodiment 38 4 4 4 5 Embodiment 39 4 4 4 5 Embodiment 40 4 4 4 5

[0643] [Table 14]

[0644] Exposure sensitivity Adhesion Residue Moisture resistance Embodiment 41 4 4 4 5 Embodiment 42 4 4 4 5 Embodiment 43 4 4 4 5 Embodiment 44 4 4 4 5 Embodiment 45 4 4 4 5 Embodiment 46 4 4 3 5 Embodiment 47 4 4 3 5 Embodiment 48 4 4 3 5 Embodiment 49 4 4 4 5 Embodiment 50 4 5 5 5 Embodiment 51 4 5 5 5 Embodiment 52 4 4 4 5 Embodiment 53 5 5 5 5 Embodiment 54 5 5 5 5 Embodiment 55 5 5 4 5 Embodiment 56 4 4 4 5 Embodiment 57 4 4 4 5 Embodiment 58 4 4 4 5 Embodiment 59 4 4 4 5 Embodiment 60 4 4 4 5 Embodiment 61 4 4 4 5 Embodiment 62 5 4 4 5 Embodiment 63 4 3 4 5 Embodiment 64 3 3 4 5 Embodiment 65 4 4 4 5 Embodiment 66 4 4 4 5 Embodiment 67 4 4 3 5 Embodiment 68 4 3 3 5 Embodiment 69 4 4 4 5 Embodiment 70 4 4 4 5 Embodiment 71 5 5 4 5 Embodiment 72 5 5 4 5 Embodiment 73 4 4 4 5 Embodiment 74 4 4 4 5 Embodiment 75 4 4 4 5 Embodiment 76 4 4 4 5 Embodiment 77 4 4 4 5 Embodiment 78 4 4 4 5 Embodiment 79 4 4 4 5 Embodiment 80 4 4 4 5

[0645] [Table 15]

[0646] Exposure sensitivity Adhesion Residue Moisture resistance Embodiment 81 4 4 4 5 Embodiment 82 4 4 4 5 Embodiment 83 4 4 4 5 Embodiment 84 4 4 4 5 Embodiment 85 4 4 4 5 Embodiment 86 5 5 4 5 Embodiment 87 5 5 5 5 Embodiment 88 4 4 4 5 Embodiment 89 4 4 4 5 Embodiment 90 4 4 4 5 Embodiment 91 4 4 4 5 Embodiment 92 4 4 4 5 Embodiment 93 4 4 4 5 Embodiment 94 4 4 4 5 Embodiment 95 4 4 4 5 Embodiment 96 4 4 4 5 Embodiment 97 5 5 5 5 Embodiment 98 5 5 5 5 Embodiment 99 5 5 5 5 Embodiment 100 5 5 5 5 Embodiment 101 5 5 5 5 Embodiment 102 5 5 5 5 Embodiment 103 5 5 5 5 Embodiment 104 5 5 5 5 Embodiment 105 5 5 5 5 Embodiment 106 5 5 5 5 Embodiment 107 5 5 5 5 Embodiment 108 5 5 5 5 Embodiment 109 5 5 5 5 Embodiment 110 5 5 5 5 Embodiment 111 5 5 5 5 Embodiment 112 5 5 5 5 Embodiment 113 5 5 5 5 Embodiment 114 5 5 5 5 Embodiment 115 5 5 5 5 Embodiment 116 5 5 5 5 Embodiment 117 5 5 5 5 Embodiment 118 5 5 5 5 Embodiment 119 5 5 5 5 Embodiment 120 5 5 5 5

[0647] [Table 16]

[0648] Exposure sensitivity Adhesion Residue Moisture resistance Embodiment 121 5 5 5 5 Embodiment 122 5 5 5 5 Embodiment 123 3 4 4 4 Embodiment 124 4 4 4 5 Embodiment 125 3 4 4 4 Embodiment 126 3 4 4 4 Embodiment 127 3 4 4 4 Embodiment 128 4 4 4 5 Embodiment 129 3 4 4 4 Embodiment 130 3 4 4 4 Embodiment 131 3 4 4 4 Embodiment 132 4 4 4 5 Embodiment 133 3 4 4 4 Embodiment 134 3 4 4 4 Embodiment 135 3 4 4 4 Embodiment 136 4 4 4 5 Embodiment 137 3 4 4 4 Embodiment 138 3 4 4 4 Embodiment 139 3 4 4 4 Embodiment 140 4 4 4 5 Embodiment 141 3 4 4 4 Embodiment 142 3 4 4 4 Embodiment 143 3 4 4 4 Embodiment 144 4 4 4 5 Embodiment 145 3 4 4 4 Embodiment 146 3 4 4 4 Comparative Example 1 1 1 2 2

[0649] As shown in the above table, the coloring composition of the example can form a pixel excellent in moisture resistance and adhesion.

[0650] In each example, even when the surfactant W-1 was changed to the surfactants W-2 to W-45 shown below, the same effects were obtained.

[0651] W-2: FZ-2122 (manufactured by Dow Corning Toray Co., Ltd., silicone-based surfactant)

[0652] W-3: BYK-322 (manufactured by BYK-Chemie GmbH, silicone-based surfactant)

[0653] W-4: BYK-323 (manufactured by BYK-Chemie GmbH, silicone-based surfactant)

[0654] W-6: BYK-3760 (manufactured by BYK-Chemie GmbH, silicone-based surfactant)

[0655] W-7: BYK-UV3510 (manufactured by BYK-Chemie GmbH, silicone-based surfactant)

[0656] W-8: KF-6001 (Shin-Etsu Chemical Co., Ltd., silicone surfactant)

[0657] W-9: MEGAFACE F-477 (DIC Corporation, fluorine-based surfactant)

[0658] W-10: MEGAFACE F-554 (DIC Corporation, fluorine-based surfactant)

[0659] W-11: MEGAFACE F-555-A (DIC Corporation, fluorine-based surfactant)

[0660] W-12: MEGAFACE F-556 (DIC Corporation, fluorine-based surfactant)

[0661] W-13: MEGAFACE F-557 (DIC Corporation, fluorine-based surfactant)

[0662] W-14: MEGAFACE F-558 (DIC Corporation, fluorine-based surfactant)

[0663] W-15: MEGAFACE F-559 (DIC Corporation, fluorine-based surfactant)

[0664] W-16: MEGAFACE F-560 (DIC Corporation, fluorine-based surfactant)

[0665] W-17: MEGAFACE F-561 (DIC Corporation, fluorine-based surfactant)

[0666] W-18: MEGAFACE F-563 (DIC Corporation, fluorine-based surfactant)

[0667] W-19: MEGAFACE F-565 (DIC Corporation, fluorine-based surfactant)

[0668] W-20: MEGAFACE F-568 (DIC Corporation, fluorine-based surfactant)

[0669] W-21: MEGAFACE F-575 (DIC Corporation, fluorine-based surfactant)

[0670] W-22: MEGAFACE R-01 (DIC Corporation, fluorine-based surfactant)

[0671] W-23: MEGAFACE R-40 (DIC Corporation, fluorine-based surfactant)

[0672] W-24: MEGAFACE R-40-LM (DIC Corporation, fluorine-based surfactant)

[0673] W-25: MEGAFACE R-41 (DIC Corporation, fluorine-based surfactant)

[0674] W-26: MEGAFACE R-41-LM (DIC Corporation, fluorine-based surfactant)

[0675] W-27: MEGAFACE R-94 (DIC Corporation, fluorine-based surfactant)

[0676] W-28: MEGAFACE DS-21 (DIC Corporation, fluorine-based surfactant)

[0677] W-29: MEGAFACE RS-43 (DIC Corporation, fluorine-based surfactant)

[0678] W-30: MEGAFACE RS-72-K (DIC Corporation, fluorine-based surfactant)

[0679] W-31: MEGAFACE RS-90 (DIC Corporation, fluorine-based surfactant)

[0680] W-32: MEGAFACE TF-1956 (DIC Corporation, fluorine-based surfactant)

[0681] W-33: Futurgent 208G (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0682] W-34: Futurgent 215M (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0683] W-35: Futurgent 245F (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0684] W-36: Futurgent 601AD (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0685] W-37: Futurgent 60iADH2 (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0686] W-38: Futurgent 602A (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0687] W-39: Futurgent 610FM (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0688] W-40: Futurgent 710FL (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0689] W-41: Futurgent 710FM (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0690] W-42: Futurgent 710FS (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0691] W-43: Futurgent FTX-218 (NEOS COMPANY LIMITED, fluorine-based surfactant)

[0692] W-44: PF-6320 (manufactured by OMNOVA Solutions Inc., fluorine-based surfactant)

[0693] W-45: BYK-330 (manufactured by BYK-Chemie gmbH, silicone-based surfactant)

Claims

1. A photosensitive composition comprising a color material, a polymerizable compound and a photopolymerization initiator, The content of the color material in the total solid content of the photosensitive composition is 40% by mass or more, The polymerizable compound contains a polymerizable compound B1 having a weight average molecular weight of 3000 or more, The content of the polymerizable compound B1 in the total mass of the polymerizable compound is 50 mass % or more, The photopolymerization initiator contains a compound represented by formula (1), In formula (1), X 1 represents a divalent linking group containing at least one selected from the group consisting of an aromatic ring and a heterocyclic ring, R 1 represents a hydrogen atom or an acyl group, R 2 represents an alkyl group or an aryl group, R 3 and R 4 each independently represents a hydrogen atom or an alkyl group, Alk 1 Alk 2 Each independently represents an alkyl group, R 3 With R 4 are optionally bonded to form a ring, Alk 1 With Alk 2 are optionally bonded to form a ring, n represents 0 or 1.

2. The photosensitive composition according to claim 1, wherein X in formula (1) 1 is a group represented by any of the formulae (X-1) to (X-13), In the formula, R X1 ~R X9 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

3. The photosensitive composition according to claim 2, wherein X in formula (1) 1 It is a group represented by the above formula (X-2) or formula (X-6).

4. The photosensitive composition according to claim 1 or 2, wherein The polymerizable compound B1 contains a repeating unit having a graft chain.

5. The photosensitive composition according to claim 1 or 2, wherein The polymerizable compound B1 contains a repeating unit having an ethylenically unsaturated bond-containing group in a side chain and a repeating unit having a graft chain.

6. The photosensitive composition according to claim 4, wherein The graft chain includes a repeating unit of at least one structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylic acid structure.

7. The photosensitive composition according to claim 1 or 2, wherein The content of the color material in the total solid content of the photosensitive composition is 50% by mass or more.

8. The photosensitive composition according to claim 1 or 2, wherein The color material contains color index pigment red 272. 9 . The photosensitive composition according to claim 1 , further comprising a polymerization inhibitor. 10 . The photosensitive composition according to claim 1 , further comprising a silicone surfactant.

11. A film obtained by using the photosensitive composition according to claim 1 or 2.

12. An optical filter comprising the film according to claim 11. 13 . An image display device comprising the film according to claim 11 . 14 . A solid-state imaging element comprising the film according to claim 11 .

Images