Photosensitive composition, cured film, color filter, light shielding film, optical element, solid-state imaging element, infrared sensor, headlamp unit

Abstract

The present invention provides a photosensitive composition capable of forming a cured film having excellent moisture resistance. In addition, a cured film, a color filter, a light shielding film, an optical element, a solid-state imaging element, an infrared sensor, and a headlamp unit using the photosensitive composition are provided. The photosensitive composition contains a black pigment, a resin, a polymerizable compound, and a photopolymerization initiator, the black pigment contains coated particles, the coated particles contain metal-containing particles and a metal oxide coating layer formed by a metal oxide coating the metal-containing particles, and the metal-containing particles are formed of a nitride or an oxynitride of one or more metals selected from zirconium, vanadium, and niobium.

Description

Technical Field

[0001] The present invention relates to a photosensitive composition, a cured film, a color filter, a light-shielding film, an optical element, a solid-state imaging element, an infrared sensor, and a headlamp unit. Background Art

[0002] A color filter used in a liquid crystal display device includes a light-shielding film called a black matrix in order to shield light between colored pixels and improve contrast.

[0003] Furthermore, currently, small and thin camera units are installed in mobile terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants). In solid-state imaging elements such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors, a light shielding film is provided to prevent noise and improve image quality.

[0004] For example, Patent Document 1 discloses a black resin composition for a light-shielding film, which contains a colored resin composition of (A) an alkali-soluble resin, (B) a coloring material, (C) an organic solvent, and (D) a photosensitizer, and contains at least zirconium dioxide compound particles as (B) a coloring material and satisfies specified conditions.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2019 / 059359 Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] The present inventors have studied a cured film (light-shielding film) obtained using the black resin composition for light-shielding film described in Patent Document 1, and have found that the optical properties of the cured film change under a high temperature and high humidity environment and that there is room for improvement in the moisture resistance of the cured film.

[0010] Therefore, the present invention aims to provide a photosensitive composition capable of forming a cured film having excellent moisture resistance. In addition, another object of the present invention is to provide a cured film, a color filter, a light shielding film, an optical element, a solid-state imaging element, an infrared sensor, and a headlamp unit using the photosensitive composition.

[0011] Means for solving technical problems

[0012] As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by the following structure, and have completed the present invention.

[0013] [1]

[0014] A photosensitive composition comprising a black pigment, a resin, a polymerizable compound and a photopolymerization initiator.

[0015] The above black pigment contains coated particles,

[0016] The coated particles include metal-containing particles and a metal oxide coating layer formed of a metal oxide coating the metal-containing particles, and the metal-containing particles are formed of a nitride or an oxynitride of one or more metals selected from zirconium, vanadium and niobium.

[0017] [2]

[0018] The photosensitive composition as described in [1], wherein the metal oxide contains silicon dioxide or aluminum oxide.

[0019] 〔3〕

[0020] The photosensitive composition as described in [1] or [2], wherein the metal oxide contains aluminum oxide.

[0021] [4]

[0022] The photosensitive composition as described in any one of [1] to [3], wherein the black pigment further contains a black pigment which is different from the coated particles and is a nitride or oxynitride of one or more metals selected from titanium, zirconium, vanadium and niobium.

[0023] 〔5〕

[0024] The photosensitive composition according to any one of [1] to [4], wherein the photopolymerization initiator contains an oxime compound.

[0025] [6]

[0026] The photosensitive composition according to any one of [1] to [5], wherein the content of the black pigment is 40 to 70% by mass based on the total solid content of the photosensitive composition.

[0027] 〔7〕

[0028] The photosensitive composition according to any one of [1] to [6], wherein the resin comprises at least one of a resin having a structural unit having a graft chain and containing an acid group and a resin having a radial structure and containing an acid group.

[0029] 〔8〕

[0030] The photosensitive composition according to any one of [1] to [7], wherein the content of the metal oxide coating layer is 3 to 7% by mass based on the total mass of the coated particles.

[0031] 〔9〕

[0032] The photosensitive composition as described in any one of [1] to [8], further comprising water,

[0033] The content of the water is 0.01 to 3.0% by mass based on the total mass of the photosensitive composition.

[0034] 〔10〕

[0035] The photosensitive composition according to any one of [1] to [9], further comprising silica particles.

[0036]

[11]

[0037] A cured film formed using the photosensitive composition according to any one of [1] to

[10] .

[0038]

[12]

[0039] A light-shielding film, which is the cured film described in

[11] .

[0040] 〔13〕

[0041] A color filter comprising the cured film described in

[11] .

[0042]

[14]

[0043] An optical element comprising the cured film described in

[11] .

[0044] 〔15〕

[0045] A solid-state imaging device comprising the cured film described in

[11] .

[0046]

[16]

[0047] An infrared sensor comprising the cured film described in

[11] .

[0048]

[17]

[0049] A headlamp unit is a vehicle headlamp unit, and the headlamp unit comprises:

[0050] light source; and

[0051] a light shielding portion for shielding at least a portion of the light emitted from the light source,

[0052] The light shielding portion includes the cured film described in

[11] .

[0053] Effects of the Invention

[0054] According to the present invention, a photosensitive composition capable of forming a cured film having excellent moisture resistance can be provided. In addition, the present invention can also provide a cured film, a color filter, a light shielding film, an optical element, a solid-state imaging element, an infrared sensor, and a headlamp unit using the above composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 It is a schematic cross-sectional view showing a structural example of a solid-state imaging device.

[0056] Figure 2 It is a magnified representation Figure 1 A schematic cross-sectional view of an imaging unit included in the solid-state imaging device shown.

[0057] Figure 3 It is a schematic cross-sectional view showing a structural example of an infrared sensor.

[0058] Figure 4 It is a schematic diagram showing a structural example of a headlamp unit.

[0059] Figure 5 It is a schematic perspective view showing a structural example of a light shielding portion of a headlight unit.

[0060] Figure 6 It is a schematic diagram showing an example of a light distribution pattern by a light shielding portion of a headlamp unit.

[0061] Figure 7 It is a schematic diagram showing another example of the light distribution pattern by the light shielding portion of the headlight unit. DETAILED DESCRIPTION

[0062] Hereinafter, the present invention will be described in detail.

[0063] Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to these embodiments.

[0064] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0065] Furthermore, in the description of groups (atomic groups) in this specification, the description without mentioning whether they are substituted or unsubstituted includes groups without substituents and groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0066] In addition, "actinic rays" or "radiation" in this specification means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, electron beams, etc. In addition, in this specification, light means actinic rays and radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure based on far ultraviolet rays, X-rays, EUV light, etc., but also drawing based on particle beams such as electron beams and ion beams.

[0067] Furthermore, in this specification, "(meth)acrylate" means acrylate and methacrylate. In this specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. In this specification, "(meth)acryloyl" means acryloyl and methacryloyl. In this specification, "(meth)acrylamide" means acrylamide and methacrylamide. In this specification, "monomer" has the same meaning as "monomer: monomer".

[0068] In this specification, "ppm" means "parts per million (10 -6 ):parts per million, "ppb" means "parts per billion (10 -9 ): parts per billion, "ppt" means "parts per trillion (10 -12 ): parts per trillion.

[0069] In addition, in this specification, the weight average molecular weight (Mw) is a polystyrene conversion value based on the GPC (Gel Permeation Chromatography) method.

[0070] In this specification, the GPC method is based on a method using HLC-8020GPC (manufactured by TOSOH CORPORATION), using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6 mmID×15 cm) as a column, and using THF (tetrahydrofuran) as an eluent.

[0071] Unless otherwise specified, the bonding direction of the divalent group (e.g., -COO-) described in this specification is not limited. For example, when Y in the compound represented by the general formula "XYZ" is -COO-, the above compound can be "XO-CO-Z" or "X-CO-OZ".

[0072] [Photosensitive composition (composition)]

[0073] The photosensitive composition of the present invention (hereinafter, also referred to simply as "composition") is a photosensitive composition containing a black pigment, a resin, a polymerizable compound and a photopolymerization initiator, wherein:

[0074] The above black pigment contains coated particles,

[0075] The coated particles include metal-containing particles and a metal oxide coating layer formed of a metal oxide coating the metal-containing particles, and the metal-containing particles are formed of a nitride or an oxynitride of one or more metals selected from zirconium, vanadium and niobium.

[0076] The mechanism by which the subject of the present invention is solved by using the composition having the above structure is not clear, but the present inventors believe as follows. That is, the coated particles have a structure in which metal-containing particles are coated with a metal oxide coating layer, and therefore have good stability against moisture, and it is believed that by using these coated particles, the moisture resistance of the cured film formed using the composition can also be improved.

[0077] The composition of the present invention also has good dispersibility and patterning properties. Furthermore, the light-shielding film (cured film) formed using the composition of the present invention has good light-shielding properties against visible light and infrared light, and also has good alignment mark visibility.

[0078] Hereinafter, the case where any one of moisture resistance, visible light shielding property, infrared light shielding property and alignment mark visibility of a cured film formed using the composition, and dispersibility and patterning property of the composition is excellent is also referred to as excellent effect of the present invention.

[0079] Hereinafter, the components contained in the composition of the present invention will be described.

[0080] 〔Black Pigment〕

[0081] The composition of the present invention contains a black pigment.

[0082] In this specification, the black pigment refers to a pigment having absorption in the entire wavelength range of 400 to 700 nm.

[0083] In addition, a plurality of pigments that cannot be used as a black pigment alone can be combined and adjusted so that the entire pigment becomes black to obtain a black pigment.

[0084] For example, a plurality of pigments each having a color other than black may be combined and used as a black pigment.

[0085] More specifically, for example, a black pigment that satisfies the evaluation criteria Z described below is preferred.

[0086] First, prepare the following composition, that is, containing a pigment, a transparent resin matrix (acrylic resin, etc.) and a solvent, and the content of the pigment relative to the total solid content is 60% by mass. The obtained composition is applied on a glass substrate so that the film thickness of the dried coating becomes 1 μm, thereby forming a coating. The light-shielding property of the dried coating is evaluated using a spectrophotometer (Hitachi, LTD. UV-3600, etc.). As long as the maximum value of the transmittance in the wavelength 400 to 700 nm of the dried coating is less than 10%, it can be judged that the above-mentioned pigment is a black pigment that meets the evaluation criterion Z.

[0087] When the black pigment contains a plurality of pigments, it is preferred that each of the contained pigments satisfy the evaluation criterion Z.

[0088] From the viewpoint of further improving the effects of the present invention, the content of the black pigment is preferably 20 to 90 mass %, more preferably 40 to 70 mass %, and even more preferably more than 40 mass % and less than 70 mass % based on the total solid content of the composition.

[0089] When two or more black pigments are used, the total content thereof is preferably within the above range.

[0090] In addition, the "light shielding" of using the cured film formed from the composition of the present invention as a light shielding film also includes the concept of attenuating light while passing through the cured film (light shielding film). When the cured film (light shielding film) is used as a light attenuating film having such a function, the content of the black pigment in the composition is also preferably less than the above preferred range.

[0091] <Coated Particles>

[0092] The black pigment contains at least coated particles.

[0093] The coated particles are particles including metal-containing particles and a metal oxide coating layer coating the metal-containing particles.

[0094] The content of the coated particles is preferably 5 to 100% by mass, more preferably 50 to 90% by mass, based on the total mass of the black pigment.

[0095] The content of the coated particles is preferably 5 to 90% by mass, more preferably 25 to 55% by mass, based on the total solid content of the composition.

[0096] (Metallic particles)

[0097] The coated particles contain metal-containing particles.

[0098] The metal-containing particles are formed of nitrides or oxynitrides of one or more metals selected from the group consisting of zirconium, vanadium, and niobium.

[0099] Among them, the metal-containing particles are more preferably formed of zirconium nitride or oxynitride.

[0100] Furthermore, the metal-containing particles may contain both the nitride and the oxynitride.

[0101] From the viewpoint of achieving a better balance between improvement of various properties of the cured film and handleability, the average primary particle size of the metal-containing particles is preferably 0.5 to 400 nm, more preferably 5 to 170 nm, and even more preferably 10 to 100 nm.

[0102] The average primary particle size in the metal-containing particles is an average primary particle size calculated from the specific surface area determined by the BET method.

[0103] The metal-containing particles are formed of nitrides or oxynitrides of one or more metals selected from zirconium, vanadium and niobium, and the above-mentioned metal-containing particles are essentially formed only of a material selected from the above-mentioned nitrides and the above-mentioned oxynitrides (hereinafter also referred to as "specific material").

[0104] The metal-containing particles are substantially formed only of a specific material. For example, in the metal-containing particles, the content of the specific material is 90 to 100 mass % (preferably 95 to 100 mass %, more preferably 99 to 100 mass %) relative to the mass of the metal-containing particles.

[0105] (Metal oxide coating)

[0106] The coated particles include a metal oxide coating layer formed of a metal oxide.

[0107] The metal oxide coating layer is a layer that coats the metal-containing particles.

[0108] The coating with the metal oxide coating layer may cover the entire surface of the metal-containing particle or only a portion thereof. That is, if the metal oxide coating layer is disposed on a portion or more of the surface of the metal-containing particle, a portion of the metal-containing particle may be exposed on the surface.

[0109] The metal oxide coating layer may be directly disposed (coated) on the metal-containing particles or may be disposed (coated) via another layer.

[0110] The presence or absence of coating can be determined using, for example, FE-STEM / EDS (field emission scanning transmission electron microscope with energy dispersive X-ray analyzer).

[0111] The coating amount can be determined using ESCA (Electron Spectroscopy for Chemical Analysis).

[0112] The metal in the metal oxide constituting the metal oxide coating layer is not limited, and may be a typical element metal or a transition metal. Furthermore, the metal may be a semimetal such as silicon.

[0113] Examples of the above-mentioned metals include Al (aluminum), Si (silicon), Zn (zinc), germanium (Ge), hafnium (Hf), gallium (Ga), molybdenum (Mo), titanium (Ti), zirconium (Zr), vanadium (V), tantalum (Ta), niobium (Nb), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn) and silver (Ag).

[0114] Among them, the above-mentioned metal is preferably Al or Si, and more preferably Al.

[0115] The metal oxide may be an oxide of a single metal (for example, the metals described above) or a composite oxide of a plurality of metals.

[0116] The above-mentioned metal oxides include aluminum oxide (Al2O3), silicon dioxide (SiO2), ZnO, GeO2, TiO2, ZrO2, HfO2, Sn2O3, Mn2O3, Ga2O3, Mo2O3, Ta2O5, V2O5 and Nb2O5.

[0117] Among them, the metal oxide preferably contains aluminum oxide or silicon dioxide, and more preferably contains aluminum oxide.

[0118] The above-mentioned metal oxide can be used alone or in combination. Wherein, when using two or more metal oxides, the content of the metal oxide with the highest content is preferably 50% by mass or more, more preferably 80% by mass or more relative to the total mass of the two or more metal oxides. The upper limit is less than 100% by mass.

[0119] The metal oxide coating layer being formed of a metal oxide means that the metal oxide coating layer is substantially formed of only a metal oxide.

[0120] The above-mentioned metal oxide coating layer is essentially formed only by metal oxide. For example, in the metal oxide coating layer, the content of metal oxide (preferably one or both of aluminum oxide and silicon dioxide, more preferably aluminum oxide) is 90 to 100 mass % (preferably 95 to 100 mass %, more preferably 99 to 100 mass %) relative to the total mass of the metal oxide coating layer.

[0121] Furthermore, the content of the metal oxide coating layer is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, and even more preferably 3 to 7% by mass, based on the total mass of the coated particles.

[0122] The content of the metal oxide coating layer was determined by ESCA.

[0123] There is no particular limitation on the method for producing coated particles. For example, the method for producing a powder matrix of black titanium oxynitride coated with a silicon dioxide film, i.e., black titanium oxynitride powder, described in paragraphs 0018 to 0019 and 0025 of Japanese Patent Gazette No. 2015-117302 can be cited, in which the powder matrix of black titanium oxynitride is replaced with the above-mentioned metal-containing particles.

[0124] As another example of the method for producing coated particles, there is a method in which titanium dioxide is replaced with the above-mentioned metal-containing particles in the inorganic treatment step in the surface treatment of titanium dioxide described in paragraph 0059 of JP-A-2017-014522.

[0125] As another example of the method for producing coated particles, there is mentioned a method in which a gas barrier film is formed on the surface of the above-mentioned metal-containing particles instead of particles of lower titanium oxide in Japanese Unexamined Patent Publication No. 08-059240 (Japanese Patent No. 3314542).

[0126] <Other black pigments>

[0127] The composition may contain a black pigment different from the above-mentioned coated particles (hereinafter, also simply referred to as "other black pigment") as the black pigment.

[0128] The content of other black pigments is preferably 0 to 95% by mass, more preferably 10 to 50% by mass, based on the total mass of the black pigments.

[0129] The content of the coated particles is preferably 2 to 60% by mass, more preferably 5 to 35% by mass, based on the total solid content of the composition.

[0130] The other black pigment may be any black pigment other than the coated particles, and may be an inorganic pigment or an organic pigment.

[0131] The other black pigment is preferably a pigment that exhibits black color alone, and more preferably a pigment that exhibits black color alone and absorbs infrared rays.

[0132] Among them, other black pigments that absorb infrared rays have absorption in, for example, the infrared region (preferably a wavelength of 650 to 1300 nm), and other black pigments that have a maximum absorption wavelength in the wavelength region of 675 to 900 nm are also preferred.

[0133] The average primary particle size of the other black pigment is not particularly limited, but is preferably 5 to 100 nm, more preferably 5 to 50 nm, and even more preferably 5 to 30 nm from the viewpoint of achieving a better balance between handleability and temporal stability of the composition (other black pigment does not precipitate).

[0134] The average primary particle size of other black pigments can be measured by the following method. The average primary particle size can be measured using a transmission electron microscope (TEM). As a transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.

[0135] The maximum length of the particle image obtained using a transmission electron microscope (Dmax: the maximum length of two points on the contour of the particle image) and the maximum length perpendicular to the maximum length (DV-max: when the image is sandwiched by two straight lines parallel to the maximum length, the shortest length between two straight lines perpendicularly connected) were measured, and the average value (Dmax×DV-max) was multiplied. 1 / 2 The primary particle diameter of 100 particles was measured by this method, and the arithmetic mean value was taken as the average primary particle diameter of the particles.

[0136] (Inorganic Pigments)

[0137] The inorganic pigment is not particularly limited as long as it is, for example, particles having light-shielding properties and containing an inorganic compound, and a known inorganic pigment can be used.

[0138] The inorganic pigment is preferably a particle (metal particle) containing a metal element of Group 4 such as titanium (Ti) and zirconium (Zr), a metal element of Group 5 such as vanadium (V) and niobium (Nb), or one or more metal elements selected from the group consisting of cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn) and silver (Ag), and more preferably a particle (metal particle) containing titanium and / or zirconium.

[0139] Furthermore, the inorganic pigment is preferably a metal oxide, a metal nitride or a metal oxynitride containing the above-mentioned metal element.

[0140] As the metal oxide, metal nitride, and metal oxynitride, for example, particles containing other atoms may be used. For example, metal nitride particles containing atoms selected from elements of Groups 13 to 17 of the periodic table (preferably oxygen atoms and / or sulfur atoms) may be used.

[0141] The manufacturing method of the above-mentioned metal nitride, metal oxide or metal oxynitride is not particularly limited as long as other black pigments with desired physical properties can be obtained, and a known manufacturing method such as a gas phase reaction method can be used. As the gas phase reaction method, for example, an electric furnace method and a thermal plasma method can be cited, but from the perspective of less mixing of impurities, easy uniformity of the average primary particle size, and high productivity, a thermal plasma method is preferred.

[0142] The metal nitride, metal oxide or metal oxynitride may be subjected to surface modification treatment. For example, the surface modification treatment may be performed using a surface treatment agent having both a silicone group and an alkyl group. Examples of these inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., LTD.) and the like.

[0143] Other black pigments are preferably nitrides or oxynitrides of one or more metals selected from titanium, zirconium, vanadium and niobium, and more preferably nitrides or oxynitrides of one or more metals selected from titanium, zirconium and vanadium. These black pigments may contain both the above-mentioned nitrides and the above-mentioned oxynitrides.

[0144] Titanium-based black pigments such as titanium oxynitride are also called titanium black. Titanium black can be surface-modified as needed to improve dispersibility and suppress cohesion. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconium oxide, and can also be treated with a water-repellent substance shown in Japanese Patent Application Publication No. 2007-302836.

[0145] As a method for producing titanium black, there are, for example, a method of heating and reducing a mixture of titanium dioxide and metallic titanium under a reducing atmosphere (Japanese Patent Publication No. 49-5432), a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride under a reducing atmosphere containing hydrogen (Japanese Patent Publication No. 57-205322), a method of high-temperature reducing titanium dioxide or titanium hydroxide in the presence of ammonium (Japanese Patent Publication No. 60-65069, Japanese Patent Publication No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing them at high temperature in the presence of ammonium (Japanese Patent Publication No. 61-201610), but are not limited to these.

[0146] The average primary particle size of titanium black is not particularly limited, and is preferably 10 to 45 nm, and more preferably 12 to 20 nm. The specific surface area of ​​titanium black is not particularly limited, and in order to achieve the specified water repellency after surface treatment with a water repellent agent, the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 5 to 150 nm. 2 / g, more preferably 20 to 100 m 2 / g.

[0147] Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and 13M-T (product names, manufactured by Mitsubishi Materials Corporation), Tilack D (product name, manufactured by Ako Kasei Co., Ltd.), and MT-150A (product name, manufactured by TAYCA CORPORATION).

[0148] The composition also preferably contains titanium black as a dispersed body containing titanium black and Si atoms. In this embodiment, titanium black is contained in the composition as a dispersed body. The content ratio of Si atoms to Ti atoms in the dispersed body (Si / Ti) is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, based on mass conversion. Among them, the above-mentioned dispersed body includes both titanium black in the state of primary particles and titanium black in the state of agglomerates (secondary particles).

[0149] Furthermore, if the Si / Ti ratio of the dispersion is too small, residues are likely to remain in the removed portion when the coating film using the dispersion is patterned by photolithography or the like, while if the Si / Ti ratio of the dispersion is too large, the light shielding capability tends to decrease.

[0150] In order to change the Si / Ti of the dispersed body (for example, to 0.05 or more), the following method can be used. First, titanium oxide and silicon dioxide particles are dispersed by a disperser to obtain a dispersion, and the mixture is reduced at a high temperature (for example, 850 to 1000° C.), thereby obtaining a dispersed body containing titanium black particles as the main component and containing Si and Ti. Titanium black with adjusted Si / Ti can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of Japanese Patent Application Publication No. 2008-266045.

[0151] The content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed body can be measured, for example, using the method (2-1) or the method (2-3) described in paragraphs 0054 to 0056 of WO2011 / 049090.

[0152] In the dispersed body containing titanium black and Si atoms, the titanium black mentioned above can be used. In addition, in order to adjust the dispersibility, coloring, etc., titanium black can be used as the dispersed body in combination with one or more other black pigments including composite oxides of various metals selected from Cu, Fe, Mn, V and Ni, cobalt oxide, iron oxide, carbon black and aniline black. In this case, the dispersed body including titanium black preferably accounts for 50% by mass or more of all the dispersed bodies.

[0153] Examples of the inorganic pigment include carbon black.

[0154] Examples of carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.

[0155] As carbon black, for example, carbon black produced by a known method such as an oil furnace method can be used, or a commercially available product can be used. Specific examples of commercially available carbon black include organic pigments such as CI Pigment Black 1 and inorganic pigments such as CI Pigment Black 7.

[0156] The carbon black is preferably a surface-treated carbon black. The surface state of the carbon black particles can be modified by the surface treatment, and the dispersion stability in the composition can be improved. Examples of the surface treatment include coating treatment based on a resin, surface treatment for introducing an acidic group, and surface treatment based on a silane coupling agent.

[0157] The carbon black is preferably a carbon black coated with a resin. By coating the surface of the carbon black particles with an insulating resin, the light shielding and insulating properties of the cured film can be improved. In addition, the reliability of the image display device can be improved by reducing leakage current. Therefore, the cured film is preferably used for applications requiring insulating properties.

[0158] Examples of the coating resin include epoxy resins, polyamides, polyamideimides, novolac resins, phenol resins, urea resins, melamine resins, polyurethanes, diallyl phthalate resins, alkylbenzene resins, polystyrene, polycarbonates, polybutylene terephthalate, and modified polyphenylene ethers.

[0159] From the viewpoint of obtaining a more excellent light-shielding property and insulating property of the cured film, the content of the coating resin is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, based on the total of the carbon black and the coating resin.

[0160] (Organic Pigments)

[0161] The organic pigment is not particularly limited as long as it is, for example, particles having light-shielding properties and containing an organic compound, and a known organic pigment can be used.

[0162] In the present invention, examples of the organic pigment include bisbenzofuranone compounds, methine azo compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds or perylene compounds are preferred.

[0163] Examples of the bisbenzofuranone compound include compounds described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234. As the bisbenzofuranone compound, Irgaphor Black (product name) series such as Irgaphor Black S0100CF manufactured by BASF can be used.

[0164] Examples of the perylene compound include compounds described in JP-A-62-1753 and JP-B-63-26784. The perylene compound can be obtained as CI Pigment Black 21, 30, 31, 32, 33, and 34.

[0165] 〔Other color materials〕

[0166] The composition may contain other color materials as color materials other than the black pigment.

[0167] <Black dye>

[0168] The composition may, for example, comprise a black dye.

[0169] As a black dye, for example, a dye that exhibits black alone can be used, for example, pyrazole azo compounds, pyrromethene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzal compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds and pyrrolopyrazole methylene azo compounds can be used.

[0170] Furthermore, as black dyes, for example, reference can be made to compounds described in Japanese Patent Application Publication No. 64-90403, Japanese Patent Application Publication No. 64-91102, Japanese Patent Application Publication No. 01-94301, Japanese Patent Application Publication No. 06-11614, Japanese Patent No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 505950, Japanese Patent Application Publication No. 05-333207, Japanese Patent Application Publication No. 06-35183, Japanese Patent Application Publication No. 06-51115 and Japanese Patent Application Publication No. 06-194828, and the like, and these contents are incorporated into this specification.

[0171] Examples of these black dyes include dyes specified in the color index (CI) of Solvent Black 27 to 47, and dyes specified in the CI of Solvent Black 27, 29, or 34 are preferred.

[0172] In addition, as commercial products of these black dyes, for example, Spilon Black MH, Black BH (above, manufactured by Hodogaya Chemical Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (above, manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Savinyl Black RLSN (above, manufactured by Clariant Chemicals), KAYASET Black KR, K-BL (above, manufactured by Nippon Kayaku CO., LTD.) and the like can be cited. In addition, polymerizable dyes having polymerizability in the molecule can also be used, and as commercial products, for example, RDW series manufactured by Wako Pure Chemical Industries, LTD. can be cited.

[0173] Furthermore, a pigment multimer may be used as the black dye. Examples of the pigment multimer include compounds described in Japanese Patent Application Laid-Open Nos. 2011-213925 and 2013-041097.

[0174] Furthermore, as described above, a plurality of dyes having colors other than black may be combined to be used as black dyes. As such coloring dyes, for example, in addition to color dyes (color dyes) such as R (red), G (green), and B (blue), dyes described in paragraphs 0027 to 0200 of Japanese Patent Application Laid-Open No. 2014-42375 may be used.

[0175] <Coloring agent>

[0176] The composition of the present invention may contain a colorant having a color other than black. The black color material (including the above-mentioned black pigment) having a black color and one or more colorants can be used to adjust the light-shielding properties of the cured film (light-shielding film). In addition, for example, when the cured film is used as a light attenuation film, it is easy to evenly attenuate each wavelength for light containing a wide wavelength component.

[0177] Examples of the colorant include pigments and dyes other than black colorants.

[0178] As a colorant, a colorant or a white colorant can be contained. As a colorant, a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant and an orange colorant can be cited. The colorant or the white colorant can be a pigment or a dye. Pigments and dyes can also be used simultaneously. In addition, the above-mentioned pigment can be any one of an inorganic pigment and an organic pigment. In addition, among the above-mentioned pigments, a material in which a part of an inorganic pigment or an organic-inorganic pigment is substituted with an organic chromophore can also be used. By replacing an inorganic pigment or an organic-inorganic pigment with an organic chromophore, hue design can be easily performed.

[0179] When the composition contains a colorant, the total content of the black colorant and the colorant is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 60% by mass based on the total mass of the solid content of the composition.

[0180] Furthermore, when the cured film formed from the composition of the present invention is used as a light attenuating film, the total content of the black color material and the colorant is also preferably less than the above-mentioned preferred range.

[0181] Furthermore, the mass ratio of the content of the colorant to the content of the black color material (content of the colorant / content of the black color material) is preferably 0.1 to 9.0.

[0182] <Infrared absorber>

[0183] The composition may further contain an infrared absorber.

[0184] The infrared absorber refers to a compound having absorption in the infrared region (preferably a wavelength of 650 to 1300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm.

[0185] Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterrylene compounds, dithiol metal complex compounds, and croconium compounds.

[0186] Phthalocyanine compounds, naphthalocyanine compounds, imine compounds, cyanine compounds, squaryl compounds and crotonium compounds can use compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Publication No. 2010-111750, and the contents are incorporated into this specification. For example, cyanine compounds can refer to "Functional Pigments, Okawara Nobuyuki / Matsuoka Ken / Kitao Teijiro / Hirajima Tsuneaki, Kodansha Scientific Ltd.", and the contents are incorporated into this specification.

[0187] As a colorant having the above-mentioned spectral characteristics, the compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Laid-Open No. 07-164729 and / or the compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Application Laid-Open No. 2002-146254, and the near-infrared absorbing particles formed of microcrystals containing oxides of Cu and / or P and having a number average aggregated particle size of 5 to 200 nm disclosed in paragraphs 0034 to 0067 of Japanese Patent Application Laid-Open No. 2011-164583 can also be used.

[0188] The compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.

[0189] The infrared absorber is preferably a compound that dissolves 1% by mass or more in water at 25° C., more preferably a compound that dissolves 10% by mass or more in water at 25° C. By using such a compound, solvent resistance is improved.

[0190] For pyrrolopyrrole compounds, reference may be made to paragraphs 0049 to 0062 of Japanese Patent Application Publication No. 2010-222557, the contents of which are incorporated herein. For cyanine compounds and squaric acid compounds, reference may be made to paragraphs 0022 to 0063 of International Publication No. 2014 / 088063, paragraphs 0053 to 0118 of International Publication No. 2014 / 030628, paragraphs 0028 to 0074 of Japanese Patent Application Publication No. 2014-59550, paragraphs 0013 to 0091 of International Publication No. 2012 / 169447, and paragraphs 0017 to 0018 of Japanese Patent Application Publication No. 2014-59550. 15-176046, paragraphs 0019 to 0033, Japanese Patent Application Publication No. 2014-63144, paragraphs 0053 to 0099, Japanese Patent Application Publication No. 2014-52431, paragraphs 0085 to 0150, Japanese Patent Application Publication No. 2014-44301, paragraphs 0076 to 0124, Japanese Patent Application Publication No. 2012-8532, paragraphs 0045 to 0078, Japanese Patent Application Publication No. 2014-52431, paragraphs 0085 to 0150, Japanese Patent Application Publication No. 2014-52431, paragraphs 0076 to 0124 ... Paragraphs 0027 to 0067 of Japanese Patent Application Publication No. 2015-172102, paragraphs 0029 to 0067 of Japanese Patent Application Publication No. 2015-172004, paragraphs 0029 to 0085 of Japanese Patent Application Publication No. 2015-40895, paragraphs 0022 to 0036 of Japanese Patent Application Publication No. 2014-126642, paragraphs 001 Paragraphs 1 to 0017, paragraphs 0010 to 0025 of Japanese Patent Application Publication No. 2015-157893, paragraphs 0013 to 0026 of Japanese Patent Application Publication No. 2014-095007, paragraphs 0013 to 0047 of Japanese Patent Application Publication No. 2014-80487, and paragraphs 0007 to 0028 of Japanese Patent Application Publication No. 2013-227403, etc., the contents of which are incorporated into this specification.

[0191] 〔Resin〕

[0192] The composition of the present invention contains a resin.

[0193] The molecular weight of the resin is preferably greater than 3000. When the molecular weight of the resin is polydisperse, the weight average molecular weight is preferably greater than 3000. The resin is preferably dissolved in the composition.

[0194] The above-mentioned resin preferably includes a resin (acid group-containing resin) containing an acid group (for example, a carboxyl group, a sulfonic acid group, a monosulfate group, -OPO(OH)2, a monophosphate group, a boric acid group and / or a phenolic hydroxyl group).

[0195] For example, part or all of a dispersant (described later) that can be contained as a resin in the composition may be an acid group-containing resin, or part or all of an alkali-soluble resin (described later) may be an acid group-containing resin.

[0196] The content of the resin in the composition is preferably 3 to 60% by mass, more preferably 7 to 40% by mass, and even more preferably 10 to 35% by mass, based on the total solid content of the composition.

[0197] The content of the acid group-containing resin is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass, based on the total mass of the resin.

[0198] When two or more resins are used simultaneously, the total content is preferably within the above range.

[0199] Furthermore, the resin preferably contains a resin containing a structural unit containing a graft chain (preferably an acid group-containing resin containing a structural unit containing a graft chain) and / or a resin containing a radial structure (preferably an acid group-containing resin containing a radial structure) as described below.

[0200] <Dispersant>

[0201] The composition preferably contains a dispersant. In the present specification, the dispersant refers to a polymer compound (resin) different from the alkali-soluble resin described later.

[0202] The dispersant preferably contains an acid group (eg, a carboxyl group, a sulfonic acid group, a monosulfate group, -OPO(OH)2, a monophosphate group, a boric acid group and / or a phenolic hydroxyl group).

[0203] The content of the dispersant in the composition is not particularly limited, but is preferably 3 to 60% by mass, more preferably 7 to 40% by mass, and even more preferably 13 to 20% by mass, based on the total solid content of the composition.

[0204] The dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably within the above range.

[0205] Furthermore, the mass ratio of the content of the dispersant (preferably the graft polymer compound and / or radial polymer compound described below) to the content of the black pigment in the composition (content of the dispersant / content of the black pigment) is preferably 0.05 to 1.00, more preferably 0.05 to 0.65, and further preferably 0.15 to 0.35.

[0206] Examples of the dispersant include polyamide amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic acid-based copolymers, naphthalenesulfonic acid formalin condensates, polyoxyethylene alkyl phosphates, polyoxyethylene alkylamines, and pigment derivatives.

[0207] Dispersants can be further classified into linear polymer compounds, terminal-modified polymer compounds, graft polymer compounds, block polymer compounds, and radial polymer compounds according to their structures.

[0208] The dispersant is adsorbed on the surface of the dispersed body such as the black pigment and other pigments used simultaneously as needed (hereinafter, the black pigment and other pigments are also collectively referred to as "pigment"), thereby playing a role in preventing the dispersed body from re-aggregating. Therefore, it is preferably a terminal modified polymer compound containing an anchor site on the pigment surface, a grafted polymer compound (containing a polymer chain), a block polymer compound, or a radial polymer compound.

[0209] The graft-type polymer compound corresponds to a resin containing a structural unit including a graft chain, and the radial polymer compound corresponds to a resin containing a radial structure.

[0210] Furthermore, these dispersants are preferably dispersants further containing an acid group (acid group-containing resin).

[0211] That is, for example, the resin preferably contains a dispersant (resin) containing a structural unit containing a graft chain and containing an acid group, and preferably contains a dispersant (resin) containing an acid group and containing a radial structure and containing an acid group.

[0212] The dispersant may contain a curable group.

[0213] Examples of the curable group include ethylenically unsaturated groups (eg, (meth)acryloyl, vinyl, and styryl groups) and cyclic ether groups (eg, epoxy, oxetanyl, and the like), but are not limited thereto.

[0214] Among them, from the viewpoint of enabling polymerization control in a radical reaction, the curable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group.

[0215] The dispersant containing a curable group preferably contains at least one selected from a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and / or a polyether structure, and when the dispersant contains a structural unit containing a graft chain as described later, the graft chain may contain a polyester structure and / or a polyether structure.

[0216] Regarding the resin, it is more preferable that the polymer chain contains a polyester structure.

[0217] The dispersant is preferably a dispersant containing a structural unit having a graft chain (graft-type polymer compound). In addition, in this specification, the meaning of "structural unit" is the same as the meaning of "repeating unit".

[0218] This dispersant (grafted polymer compound) containing a structural unit containing a graft chain has an affinity with a solvent due to the graft chain, so the dispersibility of the pigment and the dispersion stability after time (stability over time) are excellent. In addition, due to the presence of the graft chain, the dispersant containing a structural unit containing a graft chain has an affinity with a polymerizable compound or other resins that can be used simultaneously. As a result, residue is not easily generated in alkali development.

[0219] If the graft chain is longer, the steric repulsion effect is enhanced and the dispersibility of the pigment is improved. On the other hand, if the graft chain is too long, the adsorption force to the pigment decreases, and there is a tendency for the dispersibility of the pigment to decrease. Therefore, the number of atoms other than hydrogen atoms in the graft chain is preferably 40 to 10,000, the number of atoms other than hydrogen atoms is more preferably 50 to 2,000, and the number of atoms other than hydrogen atoms is further preferably 60 to 500.

[0220] Here, the graft chain means the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the terminal of the group branched from the main chain.

[0221] The graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly(meth)acrylate structure (eg, a poly(meth)acrylic acid structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and a polyether structure.

[0222] In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility of the pigment, etc., the graft chain is preferably a graft chain containing at least one selected from a polyester structure, a polyether structure and a poly(meth)acrylate structure, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.

[0223] As such a macromonomer containing a graft chain (a monomer having a polymer structure and bonding to the main chain of the copolymer to form a graft chain), for example, a macromonomer containing a reactive double bond group can be preferably used.

[0224] As commercially available macromonomers which correspond to the structural units containing graft chains contained in the dispersant and can be preferably used for the synthesis of the dispersant, for example, AA-6, AA-10, AB-6, AS-6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30 and AK-32 (all product names, manufactured by TOAGOSEI CO., LTD.), and BLEMMER PP-100, BLEMMER PP-500, BLEMMER PP-800, BLEMMER PP-1000, BLEMMER 55-PET-800, BLEMMER PME-4000, BLEMMER PSE-400, BLEMMER PSE-1300 and BLEMMER 43PAPE-600B (all product names, manufactured by NOFCORPORATION) can be used. Among them, AA-6, AA-10, AB-6, AS-6, AN-6 or BLEMMER PME-4000 is preferred.

[0225] The above-mentioned dispersant preferably contains at least one structure selected from polymethyl acrylate, polymethyl methacrylate and cyclic or chain polyester, more preferably contains at least one structure selected from polymethyl acrylate, polymethyl methacrylate and chain polyester, and further preferably contains at least one structure selected from polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure and polyvalerolactone structure. The dispersant may be a dispersant containing the above-mentioned structure alone, or may be a dispersant containing a plurality of the above-mentioned structures.

[0226] Here, the polycaprolactone structure refers to a structure containing a ring-opened ε-caprolactone structure as a repeating unit, and the polyvalerolactone structure refers to a structure containing a ring-opened δ-valerolactone structure as a repeating unit.

[0227] Specific examples of dispersants containing a polycaprolactone structure include dispersants in which j and k are 5 in the following formula (1) and the following formula (2). Specific examples of dispersants containing a polyvalerolactone structure include dispersants in which j and k are 4 in the following formula (1) and the following formula (2).

[0228] Examples of the dispersant containing a polymethyl acrylate structure include X in the following formula (4): 5 is a hydrogen atom and R 4 In addition, as a dispersant containing a polymethyl methacrylate structure, for example, X in the following formula (4) can be cited: 5 is methyl and R 4 It is a methyl dispersant.

[0229] Structural units containing grafted chains

[0230] The structural unit containing a graft chain in the dispersant preferably contains a structural unit represented by any one of the following formulae (1) to (4).

[0231] [Chemical formula 1]

[0232]

[0233] [Chemical formula 2]

[0234]

[0235] In formula (1) to formula (4), Q 1 is a group represented by any one of Formula (QX1), Formula (QNA) and Formula (QNB), Q 2 is a group represented by any one of formula (QX2), formula (QNA) and formula (QNB), Q 3 is a group represented by any one of Formula (QX3), Formula (QNA) and Formula (QNB), Q 4 It is a group represented by any one of Formula (QX4), Formula (QNA) and Formula (QNB).

[0236] In formula (QX1) to formula (QX4), formula (QNA), and formula (QNB), *a represents a bonding position on the main chain side, and *b represents a bonding position on the side chain side.

[0237] In formulas (1) to (4), W 1 , W 2 , W 3 and W 4 Each independently represents a single bond, an oxygen atom or NH.

[0238] In formulas (1) to (4) and (QX1) to (QX4), X 1 , X 2 , X 3 , X 4 and X 5 Each independently represents a hydrogen atom or a monovalent organic group. From the viewpoint of synthetic limitations, X 1 , X 2 , X 3 , X 4 and X 5 Preferably, each of them is independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (carbon number), more preferably, each of them is independently a hydrogen atom or a methyl group, and even more preferably, a methyl group.

[0239] In formula (1) to formula (4), Y 1 , Y 2 , Y 3and Y 4 Each of Y independently represents a single bond or a divalent linking group, and the structure of the linking group is not particularly limited. 1 , Y 2 , Y 3 and Y 4 Specific examples of the divalent linking group represented by include the following linking groups (Y-1) to (Y-23).

[0240] In the following linking groups, A represents the same as W in formula (1) to formula (4). 1 ~W 4 B represents the bonding position of any one of A. 1 ~W 4 The bonding position of the group on the opposite side of any one.

[0241] [Chemical formula 3]

[0242]

[0243] In formulas (1) to (4), Z 1 , Z 2 , Z 3 and Z 4 Each independently represents a monovalent substituent. The structure of the substituent is not particularly limited, and specific examples thereof include alkyl, hydroxy, alkoxy, aryloxy, heteroaryloxy, alkylthio, arylthio, heteroarylthio, and amino groups.

[0244] Among them, Z is particularly preferred from the viewpoint of improving dispersibility. 1 , Z 2 , Z 3 and Z 4 The substituent represented is preferably a group having a steric repulsive effect, and more preferably each independently is an alkyl group or an alkoxy group having 5 to 24 carbon atoms, and particularly preferably each independently is a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms. In addition, the alkyl group included in the alkoxy group may be any of a linear, branched, and cyclic type.

[0245] And, Z 1 , Z 2 , Z 3 and Z 4 The substituent represented is also preferably a group containing a curable group such as a (meth)acryloyl group. Examples of the group containing the curable group include "-O-alkylene-(-O-alkylene-) AL-(meth)acryloyloxy". AL represents an integer of 0 to 5, preferably 1. The above-mentioned alkylene groups preferably each independently have 1 to 10 carbon atoms. When the above-mentioned alkylene groups have a substituent, the substituent is preferably a hydroxyl group.

[0246] The above-mentioned substituent may be a group containing an onium structure.

[0247] The group containing an onium structure is a group having an anion part and a cation part. Examples of the anion part include an oxygen anion (-O - ) partial structure. In the repeating units represented by formula (1) to formula (4), the oxygen anion (-O - ) is preferably directly bonded to the end of the repeating structure with n, m, p or q attached, and in the repeating unit represented by formula (1), it is more preferably bonded to the end of the repeating structure with n attached (i.e., -(-OC j H 2j -CO-) n -right end) directly bonded.

[0248] Examples of the cation of the cation portion of the group containing an onium structure include ammonium cations. When the cation portion is an ammonium cation, the cation portion is a cation containing a cationic nitrogen atom (>N + Cationic nitrogen atom (>N + <) is preferably bonded to 4 substituents (preferably organic groups), of which 1 to 4 are preferably alkyl groups having 1 to 15 carbon atoms. Furthermore, one or more (preferably 1) of the 4 substituents is also preferably a group containing a curable group. Examples of the group containing the curable group that can become the above-mentioned substituent include the above-mentioned "-O-alkylene-(-O-alkylene-) AL -(meth)acryloyloxy".

[0249] In formula (1) to formula (4), n, m, p and q are each independently an integer of 1 to 500.

[0250] In formula (1) and formula (2), j and k each independently represent an integer of 2 to 8. From the viewpoint of temporal stability and developability of the composition, j and k in formula (1) and formula (2) are preferably integers of 4 to 6, and more preferably 5.

[0251] Furthermore, in formula (1) and formula (2), n and m are preferably integers greater than 1, more preferably integers greater than 2, and still more preferably integers greater than 6. Furthermore, when the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of the polyvalerolactone structure is preferably an integer greater than 2.

[0252] In formula (3), R3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, there are a plurality of R 3 They may be the same as or different from each other.

[0253] In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent structure is not particularly limited. 4 It is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. 4 When X is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and further preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (4), when q is 2 to 500, there are a plurality of X in the graft copolymer. 5 and R 4 They may be the same as or different from each other.

[0254] Furthermore, the dispersant may contain two or more structural units having different structures and containing graft chains. That is, the dispersant molecule may contain structural units represented by formulas (1) to (4) having different structures, and in formulas (1) to (4), when n, m, p and q each represent an integer greater than 2, in formulas (1) and (2), the side chain may contain structures having different j and k, and in formulas (3) and (4), a plurality of R may exist in the molecule. 3 , R 4 and X 5 They may be the same as or different from each other.

[0255] Furthermore, from the viewpoint of the temporal stability and developability of the composition, the structural unit represented by formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B).

[0256] [Chemical formula 4]

[0257]

[0258] In formula (3A) or formula (3B), X 3 , Y 3 , Z 3 The meaning of p is the same as that of X in formula (3) 3 , Y 3 , Z 3 and p have the same meanings and the preferred ranges are also the same.

[0259] In the dispersant, the content of the structural unit containing a graft chain (for example, the structural unit represented by the above formula (1) to formula (4)) is preferably 2 to 100% by mass, more preferably 6 to 100% by mass, based on the mass conversion of all repeating units of the dispersant. Among them, the total content of the structural unit represented by the above formula (1) and n is an integer of 6 or more and the structural unit represented by the above formula (2) and m is an integer of 6 or more is preferably 2 to 100% by mass, more preferably 6 to 100% by mass, based on the mass conversion of all repeating units of the dispersant.

[0260] When the structural unit containing a graft chain is contained within the above range, the dispersibility of the pigment is high, and the developability when forming a light-shielding film is good.

[0261] Hydrophobic structural unit

[0262] Furthermore, the dispersant also preferably contains a hydrophobic structural unit that is different from (i.e., not equivalent to) the structural unit containing the grafted chain. In this specification, the hydrophobic structural unit is a structural unit that does not have an acid group (e.g., a carboxyl group, a sulfonic acid group, a monosulfate group, -OPO(OH)2, a monophosphate group, a boric acid group and / or a phenolic hydroxyl group, etc.).

[0263] The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and more preferably a structural unit derived from a compound having a ClogP value of 1.2 to 8. This can more reliably demonstrate the effects of the present invention.

[0264] The ClogP value is a value calculated by the program "CLOGP" that can be obtained from Daylight Chemical Information System, Inc. The program provides the value of "calculated logP" calculated by the fragment method (fragment approach) of Hansch, Leo (refer to the following document). The fragment method divides the chemical structure into partial structures (fragments) according to the chemical structure of the compound, and the logP contribution amount allocated to the fragment is totaled to calculate the logP value of the compound. The details are described in the following document. In this specification, the ClogP value calculated by the program CLOGP v4.82 is used.

[0265] AJLeo,Comprehensive Medicinal Chemistry,Vol.4,C.Hansch,PGSammnens,JBTaylor and CARamsden,Eds.,p.295,Pergamon Press,1990C.Hansch&A.J.Leo.SUbstituent Constants For Correlation Analysis in Chemistryand Biology.John Wiley&Sons.AJLeo.Calculating logPoct fromstructure.Chem.Rev.,93,1281-1306,1993.

[0266] logP represents the common logarithm of the partition coefficient P (Partition Coefficient), which is a physical property value that quantitatively represents how a certain organic compound is distributed in the equilibrium of a two-phase system of oil (usually 1-octanol) and water, and is represented by the following formula.

[0267] logP=log(Coil / Cwater)

[0268] Wherein, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase.

[0269] If the logP value is based on 0 and increases in a positive direction (plus), the oil solubility increases, and if the absolute value increases in a negative direction (minus), the water solubility increases. It has a negative correlation with the water solubility of organic compounds and is widely used as a parameter for estimating the hydrophilicity of organic compounds.

[0270] The dispersant preferably contains, as the hydrophobic structural unit, one or more structural units selected from structural units derived from monomers represented by the following formulae (i) to (iii).

[0271] [Chemical formula 5]

[0272]

[0273] In the above formulae (i) to (iii), R 1 , R 2 and R 3 Each independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, and the like).

[0274] R 1 , R2 and R 3 It is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. 2 and R 3 A hydrogen atom is more preferred.

[0275] X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

[0276] L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group), a divalent aromatic group (e.g., an arylene group, a substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR—), a 31 -, where R 31 is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and combinations thereof.

[0277] The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of the substituent include halogen atoms, aromatic groups, and heterocyclic groups.

[0278] The number of carbon atoms in the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

[0279] The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. The above heterocyclic ring may be condensed with other rings (heterocyclic ring, aliphatic ring or aromatic ring, etc.). In addition, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thio group (=S), an imino group (=NH), a substituted imino group (=NR 32 , where R 32 is an aliphatic group, an aromatic group or a heterocyclic group).

[0280] L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is -(OCH2CH2) n - represents that n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

[0281] Examples of Z include aliphatic groups (e.g., alkyl groups, substituted alkyl groups), aromatic groups (e.g., aryl groups, substituted aryl groups), heterocyclic groups, and combinations thereof. These groups may include oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino groups (—NR—), and the like. 31 -, where R 31 is an aliphatic group, an aromatic group or a heterocyclic group) or a carbonyl group (-CO-).

[0282] The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 10. The aliphatic group also includes ring-assembled hydrocarbon groups and cross-linked cyclic hydrocarbon groups. Examples of the ring-assembled hydrocarbon group include bicyclohexyl, perhydronaphthyl, biphenyl and 4-cyclohexylphenyl. Examples of the cross-linked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2]octane ring and bicyclo[3.2.1]octane ring, etc.); homoblendane, adamantane, tricyclo[5.2.1.0 2,6 ]Decane and tricyclic [4.3.1.1 2,5 ] undecane ring and other tricyclic hydrocarbon rings and tetracyclic [4.4.0.1 2,5 .1 7,10 ] dodecane and perhydro-1,4-methylene-5,8-methylenenaphthalene ring and other four-ring hydrocarbon rings. In addition, the cross-linked cyclic hydrocarbon rings also include condensed hydrocarbon rings, for example, a condensed ring formed by condensing multiple 5- to 8-membered cycloalkane rings such as perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene and perhydrophenanthrene rings.

[0283] The aliphatic group is preferably a saturated aliphatic group as compared to an unsaturated aliphatic group. Furthermore, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

[0284] The number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10. In addition, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.

[0285] The heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be fused with another heterocyclic ring, an aliphatic ring, or an aromatic ring. In addition, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thio group (=S), an imino group (=NH), a substituted imino group (=NR 32 , where R 32 is an aliphatic group, an aromatic group or a heterocyclic group).

[0286] Here, the heterocyclic group does not have an acid group as a substituent.

[0287] In the above formula (iii), R 4 , R 5 and R 6 R each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, and a propyl group), Z, or LZ. L and Z have the same meanings as those of the above groups. 4 , R 5 and R 6 It is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0288] As the monomer represented by the above formula (i), R 1 , R 2 and R 3 A compound in which L is a hydrogen atom or a methyl group, L is a single bond or an alkylene group or a divalent linking group containing an oxyalkylene structure, X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group.

[0289] Furthermore, as the monomer represented by the above formula (ii), R 1 A compound in which L is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. 4 , R 5 and R 6 A compound wherein R is a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group or an aromatic group.

[0290] Typical examples of the compounds represented by formula (i) to formula (iii) include radical polymerizable compounds selected from acrylates, methacrylates, styrenes, and the like.

[0291] In addition, as representative compounds represented by formula (i) to formula (iii), for example, the compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417 can be referred to, and the contents thereof are incorporated into the present specification.

[0292] In the dispersant, the content of the hydrophobic structural unit is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on all repeating units of the dispersant. When the content is within the above range, a pattern can be formed sufficiently.

[0293] Functional groups that can interact with pigments, etc.

[0294] The dispersant can introduce a functional group capable of interacting with a pigment or the like (eg, a black pigment). The dispersant preferably further contains a structural unit including a functional group capable of interacting with a pigment or the like.

[0295] Examples of the functional group capable of interacting with a pigment or the like include an acid group, a basic group, a coordinating group, and a reactive functional group.

[0296] When the dispersant contains an acid group, a base, a coordinating group or a reactive functional group, it preferably contains a structural unit having an acid group, a structural unit having a base, a structural unit having a coordinating group or a reactive structural unit, respectively.

[0297] In particular, when the dispersant further contains an alkali-soluble group such as a carboxyl group as an acid group, developability for pattern formation by alkali development can be imparted to the dispersant.

[0298] That is, if an alkali-soluble group is introduced into the dispersant, the polymer compound as the dispersant that helps disperse the pigment, etc. in the above composition contains alkali solubility. Regarding the composition containing such a dispersant, the light-shielding film formed by exposure has excellent light-shielding properties, and the alkali developability of the unexposed part is improved.

[0299] Furthermore, when the dispersant contains a structural unit containing an acid group, the dispersant tends to be compatible with the solvent and the coating properties tend to be improved.

[0300] This is presumably because the acid group in the acid group-containing structural unit easily interacts with the pigment, etc., so that the dispersant stably disperses the pigment, etc., and the viscosity of the dispersant in which the pigment, etc. is dispersed is lowered, so that the dispersant itself also easily disperses stably.

[0301] Among them, the structural unit containing an alkali-soluble group as an acid group can be the same structural unit as the above-mentioned structural unit containing the grafted chain, or it can be a different structural unit, but the structural unit containing an alkali-soluble group as an acid group is a structural unit different from the above-mentioned hydrophobic structural unit (that is, it is not equivalent to the above-mentioned hydrophobic structural unit).

[0302] The acid group that can form an interactive functional group with the pigment etc. includes carboxyl group, sulfonic acid group, monosulfate group, -OPO(OH)2, monophosphate group, boric acid group and phenolic hydroxyl group etc., preferably at least one of carboxyl group, sulfonic acid group and -OPO(OH)2, more preferably carboxyl group. Carboxyl group has good adsorption force to pigment etc. and high dispersibility.

[0303] That is, the dispersant preferably further includes a structural unit containing at least one of a carboxyl group, a sulfonic acid group, and -OPO(OH) 2 .

[0304] The dispersant may have one or two or more acid group-containing structural units.

[0305] The dispersant may or may not contain a structural unit containing an acid group. However, when the structural unit containing an acid group is contained, the content of the structural unit containing an acid group is preferably 3 to 95% by mass relative to all repeating units of the dispersant, and is more preferably 5 to 92% by mass from the viewpoint of suppressing damage to image strength due to alkali development.

[0306] Examples of bases that can form a functional group that interacts with a pigment include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Tertiary amino groups are preferred from the viewpoint of good adsorption to the pigment and high dispersibility. The dispersant may contain one or more of these bases.

[0307] The dispersant may or may not contain a base-containing structural unit. However, when the dispersant contains the base-containing structural unit, the content of the base-containing structural unit is preferably 0.01 to 50% by mass relative to all repeating units of the dispersant, and is more preferably 0.01 to 30% by mass from the viewpoint of suppressing development inhibition, etc.

[0308] As the coordination group and reactive functional group that can form an interactive functional group with the pigment, for example, acetoacetoxy, trialkoxysilyl, isocyanate, acid anhydride and acyl chloride can be cited. From the viewpoint of good adsorption to the pigment and high dispersibility of the pigment, the preferred functional group is acetoacetoxy. The dispersant can have one or more of these groups.

[0309] The dispersant may or may not contain a structural unit containing a ligand or a structural unit containing a reactive functional group. However, when contained, the content of these structural units is preferably 10 to 80% by mass relative to all repeating units of the dispersant, and is more preferably 20 to 60% by mass from the viewpoint of suppressing hindrance to developability, etc.

[0310] When the above-mentioned dispersant contains functional groups capable of interacting with pigments, etc. in addition to the grafted chains, it is sufficient to contain the above-mentioned various functional groups capable of interacting with pigments, etc., and there is no particular restriction on how these functional groups are introduced. However, the dispersant preferably contains one or more structural units selected from the structural units derived from monomers represented by the following formulas (iv) to (vi).

[0311] [Chemical formula 6]

[0312]

[0313] In formula (iv) to formula (vi), R 11 , R 12 and R 13 Each independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, and the like).

[0314] In formula (iv) to formula (vi), R 11 , R 12 and R 13 It is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. 12 and R 13 A hydrogen atom is more preferred.

[0315] X1 in formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

[0316] Furthermore, Y in the formula (v) represents a methine group or a nitrogen atom.

[0317] Furthermore, L1 in formula (iv) to (v) represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above formula (i).

[0318] L1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L1 may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is -(OCH2CH2) n - represents that n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

[0319] In formulae (iv) to (vi), Z1 represents a functional group capable of interacting with a pigment or the like in addition to the graft chain, and is preferably a carboxyl group or a tertiary amino group, and more preferably a carboxyl group.

[0320] In formula (vi), R 14 , R 15 and R 16 Each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, and a propyl group), -Z1, or L1-Z1. L1 and Z1 have the same meanings as those of L1 and Z1 above, and the preferred examples are also the same. 14 , R 15 and R 16 It is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0321] As the monomer represented by formula (iv), R 11 , R 12 and R 13 A compound in which each of them is independently a hydrogen atom or a methyl group, L1 is an alkylene group or a divalent linking group containing an oxyalkylene structure, X1 is an oxygen atom or an imino group, and Z1 is a carboxyl group.

[0322] Furthermore, as the monomer represented by formula (v), R 11 The compound wherein L1 is a hydrogen atom or a methyl group, L2 is an alkylene group, Z2 is a carboxyl group, and Y is a methine group.

[0323] Furthermore, as the monomer represented by formula (vi), R 14 , R 15 and R 16 The compound wherein each of them is independently a hydrogen atom or a methyl group, and Z1 is a carboxyl group.

[0324] Representative examples of the monomers (compounds) represented by formula (iv) to formula (vi) are shown below.

[0325] Examples of the monomer include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in its molecule (e.g., 2-hydroxyethyl methacrylate) and succinic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in its molecule and phthalic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in its molecule and tetrahydroxyphthalic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in its molecule and trimellitic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in its molecule and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxybenzyl acrylamide.

[0326] From the viewpoint of interaction with pigments, etc., stability over time and permeability to developer, the content of the structural unit containing a functional group capable of interacting with pigments, etc. is preferably 0.05 to 90 mass %, more preferably 1.0 to 80 mass %, and even more preferably 10 to 70 mass % relative to all repeating units of the dispersant.

[0327] Other structural units

[0328] Furthermore, in order to improve various properties such as image strength, without impairing the effects of the present invention, the dispersant may also have other structural units having various functions different from the structural units containing graft chains, the hydrophobic structural units and the structural units containing functional groups capable of forming interactions with pigments, etc. (for example, structural units containing functional groups having affinity for the solvent described later).

[0329] Examples of such other structural units include structural units derived from radical polymerizable compounds selected from acrylonitriles and methacrylonitris.

[0330] The dispersant may contain one or more of these other structural units, and the content thereof is preferably 0 to 80% by mass, more preferably 10 to 60% by mass, based on all repeating units of the dispersant. A content within the above range can maintain sufficient pattern forming properties.

[0331] Furthermore, as the dispersant, for example, the resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, and these contents are incorporated into this specification.

[0332] The polymer compound used as a dispersant may also be a resin containing a radial structure (radial polymer compound). The radial polymer compound preferably contains an acid group (e.g., a carboxyl group, a sulfonic acid group, a monosulfate group, -OPO(OH)2, a monophosphate group, a boric acid group and / or a phenolic hydroxyl group, etc.). That is, the radial polymer compound is preferably an acid group-containing resin containing a radial structure.

[0333] The radial polymer compound is preferably a compound represented by the following general formula (X), for example.

[0334] (A 1 -R 2 -) n R 1 (-P 1 ) m (X)

[0335] In the above general formula (X), A 1 represents a monovalent organic group containing at least one site selected from an organic pigment structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a carbamate group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. n A 1 It can be the same or different.

[0336] That is, the above A 1 It represents a monovalent organic group containing at least one structure having the ability to adsorb pigments such as an organic dye structure and a heterocyclic structure and a functional group having the ability to adsorb pigments such as an acidic group, a group having a basic nitrogen atom, a urea group, a carbamate group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group.

[0337] In addition, in the following description, the site having the ability to adsorb the pigment (the above-mentioned structure and functional group) is appropriately collectively referred to as an "adsorption site".

[0338] The above adsorption site is in 1A 1 It is sufficient that at least one type is contained, and two or more types may be contained.

[0339] Furthermore, in the present invention, the "monovalent organic group containing at least one adsorption site" is a monovalent organic group formed by bonding the aforementioned adsorption site to an organic linking group consisting of 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, 1 to 400 hydrogen atoms, and 0 to 40 sulfur atoms. In addition, when the adsorption site itself can constitute a monovalent organic group, the adsorption site itself can be A 1 The monovalent organic group represented by

[0340] First, the following pairs constitute the above A 1 The adsorption site is described below.

[0341] Examples of the above-mentioned “organic pigment structure” include phthalocyanine-based, insoluble azo-based, azo lake-based, anthraquinone-based, quinacridone-based, dioxazine-based, diketopyrrolopyrrole-based, anthrapyridine-based, anthranthrone-based, indanthrone-based, flavanthrone-based, pyranthrone-based, perylene-based, and thioindigo-based pigment structures.

[0342] In addition, examples of the above-mentioned "heterocyclic structure" include thiophene, furan, xanthane, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone and anthraquinone.

[0343] In addition, the above-mentioned "organic pigment structure" or "heterocyclic structure" may also have a substituent, and as the above-mentioned substituent, for example, an alkyl group having 1 to 20 carbon atoms such as methyl and ethyl, an aryl group having 6 to 16 carbon atoms such as phenyl and naphthyl, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acyloxy group having 1 to 6 carbon atoms such as acetoxy, an alkoxy group having 1 to 20 carbon atoms such as methoxy and ethoxy, a halogen atom such as chlorine and bromine, an alkoxycarbonyl group having 2 to 7 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, and cyclohexyloxycarbonyl, a cyano group, and a carbonate group such as tert-butyl carbonate, etc., can be cited. Among them, these substituents can be bonded to the organic pigment structure or heterocyclic structure via a linking group composed of the following structural units or a combination of the above-mentioned structural units.

[0344] [Chemical formula 7]

[0345]

[0346] Examples of the “acidic group” include a carboxyl group, a sulfonic acid group, a monosulfate group, —OPO(OH) 2 , a monophosphate group, a boric acid group, and a phenolic hydroxyl group.

[0347] In addition, the acidic group corresponds to the above-mentioned acid group.

[0348] Examples of the "group having a basic nitrogen atom" include amino (-NH2), substituted imino (-NHR 8 or -NR 9R 10 , where R 8 , R 9 and R 10 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms. ), a guanidine group represented by the following formula (a1) and an amidine group represented by the following formula (a2).

[0349] [Chemical formula 8]

[0350]

[0351] In formula (a1), R 11 and R 12 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

[0352] In formula (a2), R 13 and R 14 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

[0353] Among them, amino (-NH2), substituted imino (-NHR 8 、-NR 9 R 10 , where R 8 , R 9 and R 10 Each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ) The guanidine group represented by the above formula (a1) [In the formula (a1), R 11 and R 12 Each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group. ] or an amidino group represented by the above formula (a2) [In the formula (a2), R 13 and R 14 Each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group, etc.

[0354] Examples of the "urea group" include -NR 15 CONR 16 R 17 (Among them, R 15 , R 16 and R 17 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms. ).

[0355] Examples of the above-mentioned "carbamate group" include -NHCOOR 18 、-NR19 COOR 20 ,-OCONHR 21 and-OCONR 22 R 23 (Among them, R 18 , R 19 , R 20 , R 21 , R 22 and R 23 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms. ) and the like.

[0356] Examples of the “group having a coordinating oxygen atom” include an acetylacetonate group and a crown ether.

[0357] Examples of the above-mentioned "hydrocarbon group having 4 or more carbon atoms" include alkyl groups having 4 or more carbon atoms, aryl groups having 6 or more carbon atoms, and aralkyl groups having 7 or more carbon atoms. Preferably, it is an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. More preferably, it is an alkyl group having 4 to 15 carbon atoms (for example, octyl, dodecyl, etc.), an aryl group having 6 to 15 carbon atoms (for example, phenyl, naphthyl, etc.), or an aralkyl group having 7 to 15 carbon atoms (for example, benzyl, etc.).

[0358] Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.

[0359] The organic linking group bonded to the above-mentioned adsorption site is preferably a single bond or an organic linking group composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms, and the organic linking group may be unsubstituted or may further have a substituent.

[0360] Specific examples of the organic linking group include the following structural units or groups composed of a combination of the above structural units.

[0361] [Chemical formula 9]

[0362]

[0363] When the above-mentioned organic linking group has a substituent, examples of the above-mentioned substituent include alkyl groups having 1 to 20 carbon atoms such as methyl and ethyl groups, aryl groups having 6 to 16 carbon atoms such as phenyl and naphthyl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamide groups, N-sulfonylamide groups, acyloxy groups having 1 to 6 carbon atoms such as acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl, ethoxycarbonyl and cyclohexyloxycarbonyl groups, cyano groups, and carbonate groups such as tert-butyl carbonate.

[0364] In the above, as the above A 1 , preferably a monovalent organic group containing at least one site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms.

[0365] As the above A 1 , more preferably a monovalent organic group represented by the following general formula (b).

[0366] [Chemical formula 10]

[0367]

[0368] In the above general formula (b), B 1 represents the above-mentioned adsorption site (i.e., a site selected from an organic pigment structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a carbamate group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group), R 24 represents a single bond or an (a+1)-valent organic linking group. a represents an integer from 1 to 10, and a B 1 It can be the same or different.

[0369] As the above B 1 The adsorption site represented by may be A constituting the above general formula (X) 1 The adsorption site is the same as the adsorption site, and the preferred examples are also the same.

[0370] Among them, a moiety selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferred.

[0371] R 24 It represents a single bond or an (a+1)-valent organic linking group, and a represents 1 to 10, preferably 1 to 3.

[0372] The (a+1)-valent organic linking group includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms, and may be unsubstituted or may further have a substituent.

[0373] Specific examples of the (a+1)-valent organic linking group include the following structural units or groups composed of a combination of the above structural units (which may form a ring structure).

[0374] [Chemical formula 11]

[0375]

[0376] As R 24 , preferably a single bond or an (a+1)-valent organic linking group composed of 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms and 0 to 10 sulfur atoms, more preferably a single bond or an (a+1)-valent organic linking group composed of 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, particularly preferably a single bond or an (a+1)-valent organic linking group composed of 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms and 0 to 5 sulfur atoms.

[0377] In the above, when the (a+1)-valent organic linking group has a substituent, examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as methyl and ethyl, aryl groups having 6 to 16 carbon atoms such as phenyl and naphthyl, hydroxyl groups, amino groups, carboxyl groups, sulfonamide groups, N-sulfonylamide groups, acyloxy groups having 1 to 6 carbon atoms such as acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl, ethoxycarbonyl and cyclohexyloxycarbonyl, cyano groups, and carbonate groups such as tert-butyl carbonate.

[0378] In the above general formula (X), R 2 represents a single bond or a divalent organic linking group. 2 It can be the same or different.

[0379] The divalent organic linking group includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms, and may be unsubstituted or may further have a substituent.

[0380] Specific examples of the divalent organic linking group include the following structural units or groups composed of a combination of the above structural units.

[0381] [Chemical formula 12]

[0382]

[0383] As R 2 , preferably a single bond or a divalent organic linking group consisting of 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms and 0 to 10 sulfur atoms, more preferably a single bond or a divalent organic linking group consisting of 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, particularly preferably a single bond or a divalent organic linking group consisting of 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms and 0 to 5 sulfur atoms.

[0384] In the above, when the divalent organic linking group has a substituent, examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as methyl and ethyl groups, aryl groups having 6 to 16 carbon atoms such as phenyl and naphthyl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamide groups, N-sulfonylamide groups, acyloxy groups having 1 to 6 carbon atoms such as acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl, ethoxycarbonyl and cyclohexyloxycarbonyl groups, cyano groups, and carbonate groups such as tert-butyl carbonate.

[0385] In the above general formula (X), R 1 It represents an organic linking group with a valence of (m+n). m+n satisfies 3 to 10.

[0386] As the above R 1 The (m+n)-valent organic linking group represented includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms, and may be unsubstituted or may further have a substituent.

[0387] Specific examples of the (m+n)-valent organic linking group include the following structural units or groups composed of a combination of the above structural units (which may form a ring structure).

[0388] [Chemical formula 13]

[0389]

[0390] The (m+n)-valent organic linking group is preferably a group consisting of 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms and 0 to 10 sulfur atoms, more preferably a group consisting of 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms and 0 to 7 sulfur atoms, and still more preferably a group consisting of 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms and 0 to 5 sulfur atoms.

[0391] In the above, when the (m+n)-valent organic linking group has a substituent, examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as methyl and ethyl groups, aryl groups having 6 to 16 carbon atoms such as phenyl and naphthyl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamide groups, N-sulfonylamide groups, acyloxy groups having 1 to 6 carbon atoms such as acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl, ethoxycarbonyl and cyclohexyloxycarbonyl groups, cyano groups, and carbonate groups such as tert-butyl carbonate.

[0392] The above R 1 Specific examples of the (m+n)-valent organic linking group [Specific Example (1) to Specific Example (17)] are shown below. However, the present invention is not limited to these.

[0393] [Chemical formula 14]

[0394]

[0395] [Chemical formula 15]

[0396]

[0397] Among the above-mentioned specific examples, the most preferred (m+n)-valent organic linking groups are the following groups from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

[0398] [Chemical formula 16]

[0399]

[0400] In the above general formula (X), m represents 1 to 8. m is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.

[0401] Furthermore, in the above general formula (X), n represents 2 to 9. n is preferably 2 to 8, more preferably 2 to 7, and even more preferably 3 to 6.

[0402] In the general formula (X), P 1represents a polymer skeleton and can be selected from known polymers according to the purpose. 1 It can be the same or different.

[0403] In order to form a high molecular skeleton, the polymer is preferably at least one selected from a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a carbamate polymer, an amide polymer, an epoxy polymer, a silicone polymer, and a modified product or copolymer thereof [for example, a copolymer containing a polyether / polycarbamate copolymer, a copolymer of a polyether / vinyl monomer, etc. (which may be any of a random copolymer, a block copolymer, and a graft copolymer).], more preferably at least one selected from a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a carbamate polymer, and a modified product or copolymer thereof, and further preferably a polymer or copolymer of a vinyl monomer.

[0404] Furthermore, the polymer is preferably soluble in an organic solvent. If the polymer has low affinity for an organic solvent, for example, when used as a pigment dispersant, the polymer has weak affinity for a dispersion medium, and may fail to ensure an adsorption layer that allows for sufficiently stable dispersion.

[0405] The above-mentioned vinyl monomer is not particularly limited, and preferably includes, for example, (meth)acrylates, crotonates, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth)acrylonitrile or vinyl monomers having an acidic group.

[0406] Preferred examples of these vinyl monomers are described below.

[0407] Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tert-octyl (meth)acrylate, dodecyl (meth)acrylate, propyl (meth)acrylate, and tert-butyl (meth)acrylate. Octadecyl (meth)acrylate, acetoxyethyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-chloroethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, vinyl (meth)acrylate, 2-phenylvinyl (meth)acrylate, 1-propylene (meth)acrylate, allyl (meth)acrylate, 2-aryloxyethyl (meth)acrylate, propargyl (meth)acrylate, benzyl (meth)acrylate, diethylene glycol monomethyl (meth)acrylate, diethylene glycol monoethyl (meth)acrylate, triethylene glycol monomethyl (meth)acrylate, triethylene glycol monoethyl (meth)acrylate, acid polyethylene glycol monomethyl ether, (meth)acrylate polyethylene glycol monoethyl ether, (meth)acrylate β-phenoxyethoxyethyl, (meth)acrylate nonylphenoxy polyethylene glycol, (meth)acrylate dicyclopentenyl, (meth)acrylate dicyclopentenyloxyethyl, (meth)acrylate trifluoroethyl, (meth)acrylate octafluoropentyl, (meth)acrylate perfluorooctylethyl, (meth)acrylate dicyclopentyl, (meth)acrylate tribromophenyl, (meth)acrylate tribromophenyloxyethyl and (meth)acrylate-γ-butyrolactone, etc.

[0408] Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

[0409] Examples of the vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.

[0410] Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

[0411] Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

[0412] Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

[0413] Examples of the (meth)acrylamides include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-(2-methoxyethyl) (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth)acrylamide, (meth)acryloyl morpholine, diacetone acrylamide, N-methylol acrylamide, N-ethylol acrylamide, vinyl (meth)acrylamide, N,N-diallyl (meth)acrylamide, and N-allyl (meth)acrylamide.

[0414] Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected by a group that can be deprotected by an acidic substance (e.g., t-Boc, etc.), methyl vinylbenzoate, and α-methylstyrene.

[0415] Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.

[0416] Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

[0417] Examples of olefins include ethylene, propylene, isobutylene, butadiene, and isoprene.

[0418] Examples of maleimides include maleimide, butylmaleimide, cyclohexylmaleimide, and phenylmaleimide.

[0419] Also usable are (meth)acrylonitrile, a vinyl-substituted heterocyclic group (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, and the like.

[0420] In addition to the above compounds, for example, vinyl monomers having functional groups such as carbamate groups, urea groups, sulfonamide groups, phenol groups, and imide groups can also be used. As such monomers having carbamate groups or urea groups, for example, they can be appropriately synthesized by the addition reaction of isocyanate groups with hydroxyl groups or amino groups. Specifically, they can be appropriately synthesized by the addition reaction of a monomer containing an isocyanate group with a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or by the addition reaction of a monomer containing a hydroxyl group or a monomer containing a primary or secondary amino group with a monoisocyanate.

[0421] Examples of the vinyl monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.

[0422] As the vinyl monomer with carboxyl, (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and acrylic acid dimer etc. can be cited. In addition, it is also possible to utilize the monomer with hydroxyl such as (meth) 2-hydroxyethyl acrylate and the addition reaction product of cyclic anhydride such as maleic anhydride or phthalic anhydride, cyclohexane dicarboxylic anhydride and ω-carboxyl-polycaprolactone mono(meth) acrylate etc. In addition, as the precursor of carboxyl, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, citraconic anhydride can be used. In addition, among them, from the viewpoints of copolymerizability, cost, solubility, etc., (meth) acrylic acid is particularly preferred.

[0423] In addition, examples of vinyl monomers having a sulfonic acid group include 2-acrylamide-2-methylpropanesulfonic acid, and examples of vinyl monomers having -OPO(OH)2 include mono(2-acryloyloxyethyl) phosphate and mono(1-methyl-2-acryloyloxyethyl) phosphate.

[0424] Furthermore, as the vinyl monomer having an acidic group, a phenolic hydroxyl group-containing vinyl monomer, a sulfonamide group-containing vinyl monomer, or the like can also be used.

[0425] Among the compounds represented by the above general formula (X), compounds represented by the following general formula (X-2) are preferred.

[0426] (A 2 -R 4 -S-) n R 3 (-SR 5 -P 2 ) m (X-2)

[0427] In the above general formula (X-2), A 2represents a monovalent organic group containing at least one site selected from an organic pigment structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a carbamate group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. n A 2 It can be the same or different.

[0428] In addition, A 2 The meaning of is the same as that of A in the above general formula (X) 1 The meanings are the same and the preferred aspects are also the same.

[0429] In the above general formula (X-2), R 4 , R 5 Each independently represents a single bond or a divalent organic linking group. 4 can be the same or different. 5 It can be the same or different.

[0430] As R 4 , R 5 The divalent organic linking group represented by is used in conjunction with R 2 The divalent organic linking group represented is the same as exemplified above, and the preferred embodiments are also the same.

[0431] In the above general formula (X-2), R 3 It represents an organic linking group with a valence of (m+n). m+n satisfies 3 to 10.

[0432] As the above R 3 The (m+n)-valent organic linking group represented includes a group consisting of 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms and 0 to 20 sulfur atoms, and may be unsubstituted or may further have a substituent.

[0433] As the above R 3 Specifically, the (m+n)-valent organic linking group represented by is used in the same manner as R 1 The same (m+n)-valent organic linking group as exemplified for the (m+n)-valent organic linking group represented by , and preferred aspects are also the same.

[0434] In the general formula (X-2), m represents 1 to 8. m is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.

[0435] Furthermore, in the general formula (X-2), n represents 2 to 9. n is preferably 2 to 8, more preferably 2 to 7, and even more preferably 3 to 6.

[0436] Furthermore, P in the general formula (X-2) 2 represents a polymer skeleton and can be selected from known polymers according to the purpose. 2 The preferred embodiment of the polymer is the same as P in the above general formula (X). 1 same.

[0437] Among the compounds represented by the general formula (X-2), the most preferred are the following R 3 , R 4 , R 5 , P 2 , m and n are all satisfied.

[0438] R 3 : The above specific example (1), specific example (2), specific example (10), specific example (11), specific example (16) or specific example (17)

[0439] R 4 : A divalent organic linking group consisting of "1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms and 0 to 5 sulfur atoms" which is composed of a single bond or the following structural units or a combination of the above structural units (which may have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as methyl and ethyl, an aryl group having 6 to 16 carbon atoms such as phenyl and naphthyl, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acyloxy group having 1 to 6 carbon atoms such as acetoxy, an alkoxy group having 1 to 6 carbon atoms such as methoxy and ethoxy, a halogen atom such as chlorine and bromine, an alkoxycarbonyl group having 2 to 7 carbon atoms such as methoxycarbonyl, ethoxycarbonyl and cyclohexyloxycarbonyl, a cyano group, and a carbonate group such as tert-butyl carbonate.)

[0440] [Chemical formula 17]

[0441]

[0442] R 5 : single bond, vinyl, propenyl, the following group (a) or the following group (b)

[0443] In addition, in the following groups, R 25 represents a hydrogen atom or a methyl group, and l represents 1 or 2.

[0444] [Chemical formula 18]

[0445]

[0446] P 2 : Polymers or copolymers of vinyl monomers, ester polymers, ether polymers or urethane polymers and modified products thereof

[0447] m:1~3

[0448] n:3~6

[0449] Specific examples of the dispersant include "DA-7301" manufactured by Kusumoto Chemicals, LTD., "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 111 (phosphoric acid-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)" manufactured by BYK Chemie, and "BYK-P104, P105 (polymer copolymer)" manufactured by BYK Chemie. EFKA 4047, 4050-4010-4165 (polyurethane series), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) made by EFKA, "AJISPER PB821, PB822, PB880, PB881" manufactured by Fine-Techno Co., Inc., "FLOREN TG-710 (urethane oligomer)", "Polyflow No.50E, No.300 (acrylic copolymer)" manufactured by KYOEISHA CHEMICAL Co., LTD., "DISPARLONKS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725" manufactured by Kusumoto Chemicals, LTD., "DEMOL RN, N (naphthalenesulfonic acid formalin condensation product), MS, C, SN-B (aromatic sulfonic acid formalin condensation product)" manufactured by Kao Corporation, "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN 86 (stearylamine acetate)", "SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer containing a functional part at the terminal), 24000, 28000, 32000, 38500 (graft copolymer)" manufactured by The Lubrinzol Corporation, "Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikkol Chemicals Co., Ltd., "Kawaken Fine Chemicals Co., Ltd.", LTD., HINOAKUTO T-8000E, etc., Shin-Etsu Chemical Co., LTD., polyorganosiloxane polymer KP-341, Yusho Co Ltd. "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester and other nonionic surfactants, "W004, W005, W017" and other anionic surfactants, Morishita & Co., LTD. "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", SAN NOPCO LIMITED "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" and other polymer dispersants, Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 manufactured by ADEKA CORPORATION, and Ionet (product name) S-20 manufactured by Sanyo Chemical Industries, LTD., etc. In addition, Acrybase FFS-6752 and Acrybase FFS-187 can also be used.

[0450] Furthermore, it is also preferable to use an amphoteric resin containing an acid group and a base. The amphoteric resin preferably has an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more (more preferably, an acid value of 5 to 100 mgKOH / g and an amine value of 5 to 100 mgKOH / g).

[0451] Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, and BYK-9076 manufactured by BYK-Chemie GmbH, and AJISPER PB821, AJISPER PB822, and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc.

[0452] These dispersants may be used alone or in combination of two or more.

[0453] In addition, as a dispersant, for example, the dispersants described in paragraphs 0127 to 0129 of Japanese Patent Application Laid-Open No. 2013-249417 can be referred to, and the contents are incorporated into this specification.

[0454] Furthermore, as the dispersant, for example, in addition to the above-mentioned dispersants, the graft copolymer described in paragraphs 0037 to 0115 of JP-A-2010-106268 (paragraphs 0075 to 0133 of the corresponding US Patent Application Publication No. 2011 / 0124824) can be used, and these contents can be cited and incorporated into the present specification.

[0455] In addition to the above, a dispersant containing a constituent component having a side chain structure in which an acidic group is bonded via a linking group as described in paragraphs 0028 to 0084 of Japanese Patent Application Publication No. 2011-153283 (paragraphs 0064 to 0122 of the corresponding U.S. Patent Application Publication No. 2011 / 0279759) can also be used, and these contents can be cited and incorporated into this specification.

[0456] Physical properties of dispersants

[0457] The acid value of the dispersant is preferably in the range of 5 to 250 mgKOH / g, more preferably 10 to 225 mgKOH / g, further preferably 30 to 200 mgKOH / g, and particularly preferably 35 to 200 mgKOH / g.

[0458] As long as the acid value of the dispersant is 250 mgKOH / g or less, the pattern peeling during the development when the light-shielding film is formed can be more effectively suppressed. In addition, as long as the acid value of the dispersant is 5 mgKOH / g or more, the alkali developability is better. In addition, when the acid value of the dispersant is 10 mgKOH / g or more, the sedimentation of the pigment etc. can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability of the composition can be further improved.

[0459] Furthermore, the acid value of the dispersant is within the above range, and it is also preferred that the dispersant has substantially no amine value (for example, the amine value is 0 mgKOH / g or more and less than 5 mgKOH / g).

[0460] When the dispersant has substantially no acid value (for example, when the acid value is 0 mgKOH / g or more and less than 5 mgKOH / g), the amine value of the dispersant is preferably 5 to 250 mgKOH / g, more preferably 10 to 200 mgKOH / g, and further preferably 30 to 100 mgKOH / g.

[0461] The weight average molecular weight of the dispersant is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, further preferably 6,000 to 100,000, and particularly preferably 10,000 to 50,000.

[0462] The dispersant can be synthesized according to a known method.

[0463] <Alkali-soluble resin>

[0464] The composition preferably contains an alkali-soluble resin. In the present specification, the alkali-soluble resin refers to a resin containing a group that promotes alkali solubility (alkali-soluble group, for example, an acid group such as a carboxyl group), and refers to a resin different from the dispersant described above.

[0465] For example, the alkali-soluble resin preferably does not substantially contain a structural unit containing a graft chain (typically, a structural unit represented by any one of the above formulas (1) to (4), more typically, a structural unit in which n is an integer greater than 6 in formula (1) and a structural unit in which m is an integer greater than 6 in formula (2)). The above “does not substantially contain” means that the content of the structural unit containing a graft chain is 0 to 2% by mass relative to all repeating units of the alkali-soluble resin. Furthermore, for example, the alkali-soluble resin is also preferably not the above-mentioned radial polymer compound.

[0466] The content of the alkali-soluble resin in the composition is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and even more preferably 1 to 20% by mass, based on the total solid content of the composition.

[0467] The alkali-soluble resin may be used alone or in combination of two or more. When two or more alkali-soluble resins are used in combination, the total content is preferably within the above range.

[0468] Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic acid / (meth)acrylamide copolymer resins, epoxy resins, and polyimide resins.

[0469] Examples of the alkali-soluble resin include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.

[0470] Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or their anhydrides; and polycarboxylic acid monoesters such as mono(2-(meth)acryloyloxyethyl)phthalate.

[0471] Examples of copolymerizable ethylenically unsaturated compounds include methyl (meth)acrylate, etc. Compounds described in paragraph 0027 of JP-A-2010-97210 and paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the contents are incorporated into this specification.

[0472] Furthermore, a copolymerizable ethylenically unsaturated compound and a compound containing an ethylenically unsaturated group in a side chain may be used in combination. The ethylenically unsaturated group is preferably a (meth) acrylic group. The acrylic resin containing an ethylenically unsaturated group in a side chain is obtained by, for example, reacting the carboxyl group of a carboxyl-containing acrylic resin with an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group.

[0473] The alkali-soluble resin is also preferably an alkali-soluble resin containing a curable group.

[0474] Examples of the curable group include the curable group that can contain the above-mentioned dispersant, and the preferred range is also the same.

[0475] The alkali-soluble resin containing curable group is preferably an alkali-soluble resin having a curable group in a side chain. As the alkali-soluble resin containing curable group, for example, DIANAL NR series (Mitsubishi Rayon Co., Ltd. system), Photomer6173 (polyurethane acrylic oligomer containing COOH, Diamond Shamrock Co., Ltd. system), VISCOAT R-264, KS RESIST 106 (all OSAKA ORGANIC CHEMICAL INDUSTRY LTD. system), CYCLOMER P series (for example ACA230AA), PLACCEL CF200 series (all Daicel Corporation. system), Ebecryl3800 (DAICEL-ALLNEX LTD. system) and ACRYCURE RD-F8 (NIPPON SHOKUBAI CO., LTD. system) etc. can be cited.

[0476] As the alkali-soluble resin, for example, free radical polymers containing carboxyl groups in the side chains described in Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 54-92723, Japanese Patent Publication No. 59-53836 and Japanese Patent Publication No. 59-71048 can be used; European Patent No. 99 Acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group as described in Gazette No. 3966, European Patent No. 1204000 and Japanese Patent Publication No. 2001-318463; polyvinyl pyrrolidone; polyethylene oxide; alcohol-soluble nylon and polyethers obtained by reacting 2,2-bis-(4-hydroxyphenyl)-propane with epichlorohydrin; and polyimide resins as described in International Publication No. 2008 / 123097; etc.

[0477] As the alkali-soluble resin, for example, compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can also be used, and the above contents are incorporated into the present specification.

[0478] As the alkali-soluble resin, for example, a polyimide precursor can also be used. The polyimide precursor refers to a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to addition polymerization reaction at 40 to 100°C.

[0479] As the polyimide precursor, for example, a resin containing a repeating unit represented by formula (1) can be cited. The following polyimide precursor can be cited, that is, a polyimide precursor containing, for example, an amic acid structure represented by the following formula (2), and an imide structure represented by the following formula (3) formed by ring closure of a part of the imide of the amic acid structure and the following formula (4) formed by ring closure of all the imides as the structure of the polyimide precursor.

[0480] In addition, in this specification, the polyimide precursor which has an amic acid structure may be called a polyamic acid.

[0481] [Chemical formula 19]

[0482]

[0483] [Chemical formula 20]

[0484]

[0485] [Chemical formula 21]

[0486]

[0487] [Chemical formula 22]

[0488]

[0489] In the above formula (1), n ​​represents 1 or 2, and when n is 1, R1 represents a trivalent organic group having 2 to 22 carbon atoms, and when n is 2, R1 represents a tetravalent organic group having 2 to 22 carbon atoms.

[0490] In the above formulae (2) to (4), R1 represents a trivalent organic group having 2 to 22 carbon atoms.

[0491] In the above formulae (1) to (4), R2 represents a divalent organic group having 1 to 22 carbon atoms.

[0492] Specific examples of the polyimide precursor include compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, compounds described in paragraphs 0022 to 0039 of JP-A-2016-122101, and compounds described in paragraphs 0061 to 0092 of JP-A-2016-68401, and the like, and the contents thereof are incorporated into the present specification.

[0493] From the viewpoint of achieving a more excellent pattern shape of a patterned light-shielding film obtained using the composition, the alkali-soluble resin preferably contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor.

[0494] As the polyimide resin containing an alkali-soluble group, for example, a known polyimide resin containing an alkali-soluble group can be used. As the above-mentioned polyimide resin, for example, the resin described in paragraph 0050 of Japanese Patent Publication No. 2014-137523, the resin described in paragraph 0058 of Japanese Patent Publication No. 2015-187676, and the resin described in paragraphs 0012 to 0013 of Japanese Patent Publication No. 2014-106326, etc., the above contents are incorporated into this specification.

[0495] Alkali-soluble resins such as [benzyl (meth)acrylate / (meth)acrylic acid / other addition-polymerizable vinyl monomers as required] copolymers and [allyl (meth)acrylate / (meth)acrylic acid / other addition-polymerizable vinyl monomers as required] copolymers are preferred because they have an excellent balance among film strength, sensitivity, and developability.

[0496] The other addition polymerizable vinyl monomers may be used alone or in combination of two or more.

[0497] From the viewpoint of obtaining a more excellent moisture resistance of the light-shielding film, the copolymer preferably has a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth)acryloyl group.

[0498] For example, as the above-mentioned other addition polymerizable vinyl monomers, a monomer having a curable group can be used, thereby introducing the curable group into the copolymer. In addition, a curable group (preferably an ethylenically unsaturated group such as a (meth)acryloyl group) can be introduced into a part or all of one or more of the units derived from (meth)acrylic acid in the copolymer and / or the units derived from the above-mentioned other addition polymerizable vinyl monomers.

[0499] Examples of the other addition polymerizable vinyl monomers include methyl (meth)acrylate, styrene-based monomers (hydroxystyrene, etc.), and ether dimers.

[0500] Examples of the ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).

[0501] [Chemical formula 23]

[0502]

[0503] In the general formula (ED1), R 1 and R 2 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.

[0504] [Chemical formula 24]

[0505]

[0506] In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As specific examples of the general formula (ED2), reference can be made to the description of, for example, Japanese Patent Application Laid-Open No. 2010-168539.

[0507] As specific examples of the ether dimer, for example, reference can be made to paragraph 0317 of JP-A-2013-29760, the contents of which are incorporated herein. The ether dimer may be present in one type or in two or more types.

[0508] The alkali-soluble resin is also preferably a Cardo resin.

[0509] The weight average molecular weight of the alkali-soluble resin is preferably 4,000 to 300,000, more preferably 5,000 to 200,000.

[0510] The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g, more preferably 50 to 200 mgKOH / g.

[0511] 〔Polymerizable compounds〕

[0512] The composition of the present invention contains a polymerizable compound.

[0513] In the present specification, the polymerizable compound is a compound that polymerizes under the action of a polymerization initiator described below, and is a component different from the dispersant and alkali-soluble resin described below.

[0514] In addition, the polymerizable compound is a component different from the compound containing an epoxy group described later.

[0515] The content of the polymerizable compound in the composition is not particularly limited, but is preferably 1 to 35% by mass, more preferably 4 to 25% by mass, and further preferably 8 to 20% by mass relative to the total solid content of the composition. The polymerizable compound may be used alone or in combination of two or more. When two or more polymerizable compounds are used, the total content is preferably within the above range.

[0516] The polymerizable compound is preferably a low molecular weight compound. The low molecular weight compound referred to herein is preferably a compound having a molecular weight of 3,000 or less.

[0517] The polymerizable compound is preferably a compound containing an ethylenically unsaturated group.

[0518] That is, the composition of the present invention preferably contains a low molecular weight compound containing an ethylenically unsaturated group as a polymerizable compound.

[0519] The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more, further preferably a compound containing three or more, and particularly preferably a compound containing five or more. The upper limit is, for example, 15 or less. Examples of the ethylenically unsaturated group include vinyl, allyl, and (meth)acryloyl.

[0520] As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the contents thereof are incorporated into the present specification.

[0521] The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a multimer thereof.

[0522] The polymerizable compound is preferably a tri- to penta-functional (meth)acrylate compound, and more preferably a tri- to hexa-functional (meth)acrylate compound.

[0523] The polymerizable compound is also preferably a compound having one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher at normal pressure. For example, reference may be made to the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970, the contents of which are incorporated herein.

[0524] The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available product: KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and a structure in which the (meth)acryloyl group of these is connected with an ethylene glycol residue or a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer company Inc.). These oligomer types can also be used. In addition, NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, KAYARAD DPEA-12, KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), ARONIX M-305, ARONIX M-510 (manufactured by TOAGOSEI Co., Ltd.), and VISCOAT #802 (manufactured by Osaka Organic Chemical Industry Ltd.) can be used.

[0525] Preferred embodiments of the polymerizable compound are shown below.

[0526] The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and -OPO(OH)2. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a polymerizable compound having an acid group is preferably obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. It is further preferred that the aliphatic polyhydroxy compound is a compound of pentaerythritol and / or dipentaerythritol in the ester. As commercially available products, for example, ARONIX TO-2349, M-305, M-510, and M-520 manufactured by TOAGOSEI CO., LTD. can be cited.

[0527] The polymerizable compound also preferably does not contain an acid group.

[0528] The content of the polymerizable compound not containing an acid group is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 75 to 100% by mass, based on the total mass of the polymerizable compound.

[0529] The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, the photopolymerization performance is good and the curing property is excellent.

[0530] As for the polymerizable compound, a compound containing a caprolactone structure is also a preferred embodiment.

[0531] The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying a polyol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among them, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferred.

[0532] [Chemical formula 25]

[0533]

[0534] In formula (Z-1), all six Rs are groups represented by the following formula (Z-2), or 1 to 5 of the six Rs are groups represented by the following formula (Z-2), and the remainder are groups represented by the following formula (Z-3).

[0535] [Chemical formula 26]

[0536]

[0537] In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.

[0538] [Chemical formula 27]

[0539]

[0540] In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

[0541] The polymerizable compound containing a caprolactone structure is commercially available, for example, from Nippon Kayaku CO., LTD. as the KAYARADDPCA series, and DPCA-20 (in the above formulas (Z-1) to (Z-3), m=1, the number of groups represented by the formula (Z-2)=2, R 1 All of the compounds are hydrogen atoms), DPCA-30 (in the above formula (Z-1) to formula (Z-3), m = 1, the number of groups represented by formula (Z-2) = 3, R 1 All of the compounds are hydrogen atoms), DPCA-60 (in the above formula (Z-1) to formula (Z-3), m = 1, the number of groups represented by formula (Z-2) = 6, R 1 All of the compounds are hydrogen atoms) and DPCA-120 (in the above formulas (Z-1) to (Z-3), m = 2, the number of groups represented by formula (Z-2) = 6, R 1 All hydrogen atoms) etc.

[0542] As the polymerizable compound, a compound represented by the following formula (Z-6) can also be used.

[0543] [Chemical formula 28]

[0544]

[0545] In formula (Z-6), E each independently represents -(CH2) y -CH2-O-, -(CH2) y -CH(CH3)-O-, -(CH2) y -CH2-CO-O-, -(CH2) y -CH(CH3)-CO-O-, -CO-(CH2) y -CH2-O-, -CO-(CH2) y -CH(CH3)-O-, -CO-(CH2) y -CH2-CO-O- or -CO-(CH2) y -CH(CH3)-CO-O-. The right-side bonding position of these groups is preferably the bonding position on the X side.

[0546] y each independently represents an integer of 1-10.

[0547] X's each independently represent a (meth)acryloyl group or a hydrogen atom.

[0548] p each independently represents an integer of 0 to 10.

[0549] q represents an integer from 0 to 3.

[0550] In formula (Z-6), the total number of (meth)acryloyl groups is preferably (3+2q) or (4+2q).

[0551] p is preferably an integer of 0-6, more preferably an integer of 0-4.

[0552] The total of each p is preferably 0 to (40+20q), more preferably 0 to (16+8q), and further preferably 0 to (12+6q).

[0553] The compound represented by formula (Z-6) may be used alone or in combination of two or more.

[0554] The total content of the compound represented by formula (Z-6) in the polymerizable compound is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 80 to 100% by mass.

[0555] Among the compounds represented by formula (Z-6), a pentaerythritol derivative, a dipentaerythritol derivative, a tripentaerythritol derivative and / or a tetrapentaerythritol derivative is more preferred.

[0556] Furthermore, the polymerizable compound may contain a cardo skeleton.

[0557] As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-diarylfluorene skeleton is preferred.

[0558] The polymerizable compound containing a cardo skeleton is not limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD.) and Ogsol (manufactured by Osaka Gas Chemicals Co., LTD.).

[0559] The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. Examples of such a polymerizable compound include NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0560] The content of ethylenically unsaturated groups in the polymerizable compound (the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is preferably 5.0 mmol / g or more. The upper limit is not particularly limited, but is usually 20.0 mmol / g or less.

[0561] When the composition contains a plurality of polymerizable compounds and the double bond equivalents of the compounds are different, the value obtained by summing up the products of the mass ratios of all polymerizable compounds and the double bond equivalents of the polymerizable compounds is preferably within the above range.

[0562] 〔Photopolymerization initiator〕

[0563] The above composition contains a photopolymerization initiator.

[0564] The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity in the ultraviolet region to the visible light region is preferred. In addition, it can be an activator that generates active free radicals by reacting with a sensitizer excited by light, or it can be an initiator that initiates cationic polymerization according to the type of the polymerizable compound.

[0565] Furthermore, the photopolymerization initiator preferably has a wavelength of at least 50 (l·mol) in the range of 300 to 800 nm (more preferably 330 to 500 nm). -1 cm -1 ) of the compound having a molar absorption coefficient of .

[0566] The content of the photopolymerization initiator in the composition is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1.5 to 8% by mass, based on the total solid content of the composition.

[0567] The photopolymerization initiator may be used alone or in combination of two or more. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

[0568] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.

[0569] As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and the contents are incorporated into the present specification.

[0570] As the photopolymerization initiator, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

[0571] As the hydroxyacetophenone compound, for example, Omnirad 184, Omnirad 1173, Omnirad 500, Omnirad 2959 and Omnirad 127 (product names, all manufactured by IGM Resins BV) can be used. These products correspond to IRGACURE 184, IRGACURE 1173, IRGACURE 500, IRGACURE 2959 and IRGACURE 127 (former product names, previously manufactured by BASF), respectively.

[0572] As the aminoacetophenone compound, for example, commercially available products Omnirad 907, Omnirad 369, and Omnirad 379EG (product names, all manufactured by IGM Resins BV) can be used. These products correspond to IRGACURE 907, IRGACURE 369, and IRGACURE 379EG (former product names, formerly manufactured by BASF), respectively.

[0573] As the aminoacetophenone compound, for example, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wave light source such as a wavelength of 365 nm or a wavelength of 405 nm can be used.

[0574] As the acylphosphine compound, for example, commercially available products Omnirad 819 and Omnirad TPO H (product names, both manufactured by IGM Resins BV) can be used. These products correspond to IRGACURE 819 and IRGACURE TPO (former product names, previously manufactured by BASF), respectively.

[0575] (Oxime Compounds)

[0576] The photopolymerization initiator is more preferably an oxime ester polymerization initiator (oxime compound). In particular, an oxime compound is preferred because it has high sensitivity and high polymerization efficiency and can easily increase the content of the colorant in the composition.

[0577] The content of the oxime compound is preferably 10 to 100% by mass, more preferably 40 to 100% by mass, and even more preferably 80 to 100% by mass, based on the total mass of the polymerization initiator.

[0578] As the oxime compound, for example, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, or the compounds described in JP-A-2006-342166 can be used.

[0579] Examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

[0580] In addition, examples include compounds described in JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, Japanese Patent Publication No. 2000-66385, Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2004-534797 and Japanese Patent Publication No. 2006-342166, etc.

[0581] Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) is also preferred. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), Adeka Arkls NCI-831, Adeka Arkls NCI-930 (manufactured by ADEKA CORPORATION), or N-1919 (a photoinitiator containing a carbazole / oxime ester skeleton (manufactured by ADEKA CORPORATION)) can also be used.

[0582] Furthermore, as oxime compounds other than those described above, compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole; compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced at the benzophenone site; compounds described in Japanese Patent Publication No. 2010-15025 and U.S. Patent Application Publication No. 2009-292039 in which a nitro group is introduced at the pigment site; ketone oxime compounds described in International Publication No. 2009-131189 pamphlet; and compounds described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule; compounds described in Japanese Patent Publication No. 2009-221114 having a maximum absorption wavelength at 405 nm and good sensitivity to a g-ray light source; etc.

[0583] For example, paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and the contents are incorporated into this specification.

[0584] Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1): In addition, the NO bond of the oxime compound may be an (E)-form oxime compound, an (Z)-form oxime compound, or a mixture of the (E)-form and the (Z)-form oxime compound.

[0585] [Chemical formula 29]

[0586]

[0587] In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

[0588] In formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

[0589] Examples of the monovalent non-metallic atomic group include alkyl, aryl, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic, alkylthiocarbonyl, and arylthiocarbonyl. Furthermore, these groups may have one or more substituents. Furthermore, the aforementioned substituents may be further substituted by other substituents.

[0590] Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

[0591] In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group, and more preferably an aryl group or a heterocyclic group. These groups may have one or more substituents. As the substituent, for example, the above-mentioned substituents can be mentioned.

[0592] In formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, cycloalkylene group or alkynylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituents include the substituents described above.

[0593] As the photopolymerization initiator, an oxime compound containing a fluorine atom can also be used. Specific examples of the oxime compound containing a fluorine atom include compounds described in Japanese Unexamined Patent Publication No. 2010-262028; compounds 24, 36 to 40 described in Japanese Unexamined Patent Publication No. 2014-500852; and compound (C-3) described in Japanese Unexamined Patent Publication No. 2013-164471; etc. This content is incorporated into this specification.

[0594] As the photopolymerization initiator, compounds represented by the following general formula (1) to formula (4) can also be used.

[0595] [Chemical formula 30]

[0596]

[0597] [Chemical formula 31]

[0598]

[0599] In formula (1), R 1 and R 2 Each independently represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and in R 1 and R 2 In the case of a phenyl group, the phenyl groups may be bonded to each other to form a fluorenyl group, and R 3 and R 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0600] In formula (2), R 1 , R 2 , R 3 and R 4 The meaning of is the same as R in formula (1) 1 , R 2 , R 3 and R 4 has the same meaning, R 5 Indicates -R 6 、-OR 6 、-SR 6、-COR 6 、-CONR 6 R 6 、-NR 6 COR 6 、-OCOR 6 、-COOR 6 ,-SCOR 6 、-OCSR 6 ,-COSR 6 ,-CSOR 6 , -CN, halogen atom or hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

[0601] In formula (3), R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and R 3 and R 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0602] In formula (4), R 1 , R 3 and R 4 The meaning of is the same as R in formula (3) 1 , R 3 and R 4 has the same meaning, R 5 Indicates -R 6 、-OR 6 、-SR 6 、-COR 6 、-CONR 6 R 6 、-NR 6 COR 6 、-OCOR 6 、-COOR 6 ,-SCOR 6 、-OCSR 6 ,-COSR 6 ,-CSOR 6 , -CN, halogen atom or hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

[0603] In the above formula (1) and formula (2), R 1 and R 2 Preferably, it is methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. 3 Preferably, it is methyl, ethyl, phenyl, tolyl or xylyl. 4 It is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. 5 Preferably, it is methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond.

[0604] Furthermore, in the above formula (3) and formula (4), R 1 R is preferably methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. 3 Preferably, it is methyl, ethyl, phenyl, tolyl or xylyl. 4 It is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. 5 Preferably, it is methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond.

[0605] Specific examples of the compounds represented by formula (1) and formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466, the contents of which are incorporated herein.

[0606] Specific examples of the oxime compound preferably used in the above composition are shown below. Among the oxime compounds shown below, an oxime compound represented by general formula (C-13) is more preferred.

[0607] Furthermore, as the oxime compound, for example, the compounds described in Table 1 of International Publication No. 2015-036910 can also be used, and the above contents are incorporated into the present specification.

[0608] [Chemical formula 32]

[0609]

[0610] [Chemical formula 33]

[0611]

[0612] The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm.

[0613] From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000.

[0614] The molar absorption coefficient of the compound can be measured by a known method, and is preferably measured by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g / L using ethyl acetate.

[0615] The photopolymerization initiators may be used in combination of two or more types as necessary.

[0616] Furthermore, as the photopolymerization initiator, for example, compounds described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2008-260927, paragraphs 0033 to 0037 of Japanese Patent Application Laid-Open No. 2010-97210, and paragraph 0044 of Japanese Patent Application Laid-Open No. 2015-68893 can also be used, and the above contents are incorporated into this specification.

[0617] 〔Inhibitor〕

[0618] The composition may contain a polymerization inhibitor.

[0619] As the polymerization inhibitor, for example, a known polymerization inhibitor can be used. As the polymerization inhibitor, for example, phenol-based polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4-methoxynaphthol, etc.); hydroquinone-based polymerization inhibitors (for example, hydroquinone, 2,6- di-tert-butylhydroquinone, etc.); quinone-based polymerization inhibitors (e.g., benzoquinone, etc.); free radical-based polymerization inhibitors (e.g., 2,2,6,6-tetramethylpiperidinium 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidinium 1-oxyl free radical, etc.); nitrobenzene-based polymerization inhibitors (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors (e.g., phenothiazine, 2-methoxyphenothiazine, etc.); etc.

[0620] Among them, phenol-based polymerization inhibitors or radical-based polymerization inhibitors are preferred from the viewpoint that the composition has a more excellent effect.

[0621] The polymerization inhibitor is particularly effective when used together with a resin containing a curable group.

[0622] The content of the polymerization inhibitor in the composition is preferably 0.0001 to 0.5 mass %, more preferably 0.001 to 0.2 mass %, and further preferably 0.008 to 0.05 mass % relative to the total solid content of the composition. The polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.

[0623] The ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition (content of the polymerization inhibitor / content of the polymerizable compound (mass ratio)) is preferably 0.00005 to 0.02, and more preferably 0.0001 to 0.005.

[0624] 〔Surfactant〕

[0625] The composition may contain a surfactant, which helps improve the coating properties of the composition.

[0626] When the composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.003 to 0.5% by mass, and even more preferably 0.005 to 0.1% by mass based on the total solid content of the composition.

[0627] The surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably within the above range.

[0628] Examples of the surfactant include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants.

[0629] For example, if the composition contains a fluorine-based surfactant, the liquid properties (especially fluidity) of the composition are further improved. That is, when a film is formed using a composition containing a fluorine-based surfactant, the surface tension between the coated surface and the coating liquid is reduced to improve the wettability of the coated surface and improve the coating property of the coated surface. Therefore, even if a thin film of about several μm is formed with a small amount of liquid, it is more effective to form a film of uniform thickness with small uneven thickness.

[0630] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 7 to 25% by mass. Fluorine-based surfactants having a fluorine content within this range are effective in terms of uniformity of thickness of the coating film and / or liquid saving, and also have good solubility in the composition.

[0631] Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, and MEGAFACE F781F (all manufactured by DIC CORPORATION); Fluorad FC430, Fluorad FC431, and Fluorad FC171 (all manufactured by Sumitomo 3M Limited); Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393 and Surflon KH-40 (all manufactured by Asahi Glass Co., LTD.); and PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA Solutions Inc.), etc.

[0632] As the fluorine-based surfactant, a block polymer can also be used, and specific examples thereof include compounds described in Japanese Unexamined Patent Application Publication No. 2011-89090.

[0633] 〔Solvent〕

[0634] The composition preferably contains a solvent.

[0635] As the solvent, for example, a known solvent can be used.

[0636] The content of the solvent in the composition is preferably an amount of 10 to 90% by mass, more preferably 10 to 45% by mass, and even more preferably 20 to 40% by mass based on the solid content of the composition.

[0637] The solvent may be used alone or in combination of two or more. When two or more solvents are used in combination, the total solid content of the composition is preferably adjusted to be within the above range.

[0638] Examples of the solvent include water and organic solvents.

[0639] <Organic solvents>

[0640] Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate, but are not limited thereto. However, there are cases where aromatic hydrocarbons (such as toluene) as organic solvents are preferably reduced for environmental reasons (for example, relative to the total amount of organic solvents, it can be set to 50 mass ppm (parts per million) or less, it can be set to 10 mass ppm or less, and it can also be set to 1 mass ppm or less). In the present invention, an organic solvent with a low metal content can be used, and the metal content of the organic solvent can be selected to be, for example, 10 mass ppb (parts per billion) or less. If necessary, organic solvents of the mass ppt (parts per trillion) level can also be used, such as those provided by TOYO Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015). As a method for removing impurities such as metals from an organic solvent, for example, distillation (molecular distillation and thin film distillation, etc.) or filtration using a filter can be cited. The filter pore size of the filter used for 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. The organic solvent may contain isomers (compounds with the same number of atoms but different structures). Furthermore, the isomers may contain only one or more. The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and it is also preferred that the peroxide is substantially not contained.

[0641] <Water>

[0642] When the composition contains water, the content (water content) is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.1 to 1.0% by mass relative to the total mass of the composition from the viewpoint of excellent storage stability of the composition.

[0643] It is considered that when the water content is 3.0% by mass or less (more preferably 1.0% by mass or less) relative to the total mass of the composition, it is possible to suppress excessive adsorption of water into the pigment (black pigment, etc.) and hinder the adsorption of the resin (especially the dispersant), and it is easy to maintain the state of the pigment dispersed in the composition, thereby improving the storage stability of the composition.

[0644] On the other hand, as long as the water content is 0.01% by mass or more (preferably 0.1% by mass or more), the water is appropriately adsorbed into the pigment (black pigment, etc.), so the resin (especially the dispersant) is not excessively adsorbed into only a part of the pigment (black pigment, etc.), and is easily uniformly adsorbed into all the pigments (black pigment, etc.). Therefore, it is considered that the storage stability of the composition can be improved even when the resin (especially the dispersant) is not excessively added to the composition.

[0645] The water content of the composition can be measured by Karl Fischer method.

[0646] 〔Silica particles〕

[0647] The composition may contain silica particles (particles of silicon dioxide).

[0648] In addition, the silica particles are a material different from the above-mentioned black pigment. That is, the silica particles are not included in the black pigment even if they are black.

[0649] It is considered that, when the composition contains silica particles, the silica particles tend to be localized on the surface of a cured film (light-shielding film) formed using the composition, and appropriate concavities and convexities can be formed on the surface of the cured film (light-shielding film), thereby suppressing the reflectivity of the cured film (light-shielding film).

[0650] The content of the silica particles is preferably 0.1 to 16.0% by mass, more preferably 1.0 to 10.0% by mass, and even more preferably 3.0 to 8.5% by mass, based on the total solid content of the composition.

[0651] The composition may contain only one type of silica particles or two or more types. When containing two or more types, the total amount thereof is preferably within the above range.

[0652] From the viewpoint of achieving more excellent effects of the present invention, the average primary particle size of the silica particles is preferably 1 to 200 nm, more preferably 10 to 100 nm, and even more preferably 15 to 78 nm.

[0653] In addition, in this specification, the average primary particle size of silica particles means the average primary particle size of particles measured by the following method. The average primary particle size can be measured using a scanning electron microscope (SEM).

[0654] The maximum length of the particle image obtained using SEM (Dmax: the maximum length of two points on the contour of the particle image) and the maximum length perpendicular to the maximum length (DV-max: when the image is sandwiched by two straight lines parallel to the maximum length, the shortest length between two straight lines perpendicularly connected) were measured, and the average value (Dmax × DV-max) was multiplied. 1 / 2 The primary particle diameter of 100 particles was measured by this method, and the arithmetic mean value was taken as the average primary particle diameter of the particles.

[0655] The refractive index of the silica particles is not particularly limited, but is preferably 1.10 to 1.60, more preferably 1.15 to 1.45, from the viewpoint of obtaining a more excellent low reflectivity of a cured film.

[0656] Furthermore, the silica particles may be hollow particles or solid particles.

[0657] Hollow particles refer to particles with a cavity inside the particle. Hollow particles can be a structure in which the particle consists of an internal cavity and a shell surrounding the cavity. In addition, hollow particles can also be a structure in which there are multiple cavities inside the particle.

[0658] Solid particles refer to particles in which there is substantially no cavity inside the particles.

[0659] The porosity of the hollow particles is preferably 3% or more, and the porosity of the solid particles is preferably less than 3%.

[0660] Examples of solid particles (silica particles as solid particles) include silica particles of IPA-ST, IPA-ST-L, IPA-ST-ZL, MIBK-ST, MIBK-ST-L, CHO-ST-M, PGM-AC-2140Y, and PGM-AC-4130Y (manufactured by Nissan Chemical Corporation).

[0661] It is considered that hollow particles have a cavity inside and have a smaller specific gravity than particles without a hollow structure, and therefore in a coating film formed using the curable composition, the hollow particles float to the surface and further enhance the effect localized on the surface of the cured film.

[0662] Moreover, the refractive index of the hollow particles themselves is lower than that of particles without a hollow structure. For example, when the hollow particles are composed of silicon dioxide, the hollow particles have air with a low refractive index (refractive index = 1.0), so the refractive index of the particles themselves becomes 1.2 to 1.4, which is significantly lower than that of ordinary silicon dioxide (refractive index = 1.6). Therefore, it is considered that, by forming a cured film using a composition containing hollow particles, the hollow particles with a low refractive index are concentrated on the surface of the cured film, and an AR (Anti-Reflection) type low reflection effect can be obtained, thereby improving the low reflectivity of the cured film.

[0663] Examples of the hollow particles (silica particles as hollow particles) include hollow particles described in Japanese Patent Application Laid-Open No. 2001-233611 and Japanese Patent No. 3272111.

[0664] As the hollow silica particles, for example, THRULYA4110 (product name, manufactured by JGC Catalystsand Chemicals Ltd.) can also be used.

[0665] As the silica particles, beaded silica particles, which are particle aggregates of a plurality of silica particles connected in a chain, can be used. The beaded silica particles are preferably beaded silica particles in which a plurality of spherical colloidal silica particles having an average primary particle size of 5 to 50 nm are connected by silica containing a metal oxide.

[0666] Examples of the beaded colloidal silica particles include silica sols described in Japanese Patent No. 4328935 and Japanese Patent Application Laid-Open No. 2013-253145.

[0667] The silica particles may contain components other than silica as necessary. The silica content in the silica particles is preferably 75 to 100% by mass, preferably 90 to 100% by mass, and more preferably 99 to 100% by mass, relative to the total mass of the silica particles.

[0668] From the viewpoint of obtaining a cured film with more excellent transmittance, the silica particles are preferably modified silica particles containing silica and a coating layer coating the silica.

[0669] <Coating layer>

[0670] The coating layer is a layer that coats the silicon dioxide constituting the silicon dioxide particles. The coating layer may coat the entire surface of the silicon dioxide or only a portion of the surface.

[0671] The coating layer may be disposed directly on the surface of the silicon dioxide, or may be disposed with another layer interposed between the coating layer and the silicon dioxide.

[0672] As the coating layer, it is preferred to contain at least one group selected from a group containing a silicon atom, a group containing a fluorine atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a (meth)acryloyl group, a glycidoxy group and an amino group. Among them, from the viewpoint of a more excellent effect of the present invention and / or the viewpoint of being able to further suppress the generation of residues when forming a patterned cured film, it is more preferred to contain at least one group selected from a group containing a silicon atom, a group containing a fluorine atom, an alkyl group which may have a substituent and an aryl group which may have a substituent, and it is further preferred to contain at least one group selected from a group containing a silicon atom and a group containing a fluorine atom.

[0673] The silicon atom in the group containing silicon atoms mentioned here does not include silicon atoms bonded to silicon dioxide via oxygen atoms. For example, when a silane coupling agent is used to produce modified silica particles, silicon atoms derived from a hydrolyzable silyl group bonded to silicon dioxide via an oxygen atom do not correspond to silicon atoms in the group containing silicon atoms, and when a silylating agent is used to produce modified silica particles, silicon atoms derived from a silylating agent bonded to silicon dioxide via an oxygen atom do not correspond to silicon atoms in the group containing silicon atoms.

[0674] As a more specific example, even when the trimethoxysilyl group of 3-methacryloxypropyltrimethoxysilane is reacted with silica to produce modified silica having a methacryl group, the silicon atom derived from the trimethoxysilyl group reacting with silica does not correspond to the silicon atom in the group containing the silicon atom of the coating layer. Similarly, even when hexamethyldisilazane is reacted with silica to produce modified silica particles having an alkyl (methyl) group, the silicon atom derived from the hexamethyldisilazane reacting with silica does not correspond to the silicon atom in the group containing the silicon atom of the coating layer.

[0675] The group containing a silicon atom and the group containing a fluorine atom are preferably groups contained in the repeating unit represented by the general formula (1) described later (preferably S in the general formula (1) S1 In other words, the coating layer preferably comprises a polymer containing a repeating unit represented by the general formula (1).

[0676] The coating layer may partially contain the above polymer, or the coating layer may be the above polymer itself. The content of the above polymer is preferably 10 to 100 mass %, preferably 70 to 100 mass %, and more preferably 95 to 100 mass % relative to the total mass of the coating layer.

[0677] The repeating unit represented by the general formula (1) contained in the above polymer is shown below.

[0678] [Chemical formula 34]

[0679]

[0680] In the general formula (1), R S1 It represents an alkyl group which may have a substituent or a hydrogen atom.

[0681] The alkyl group may be linear or branched, and may be a ring structure as a whole or may partially contain a ring structure.

[0682] The carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 3. When the alkyl group has a substituent, the preferred carbon number here means the carbon number including the carbon number that may be present in the substituent.

[0683] Among them, R S1 Preferred is a hydrogen atom or a methyl group.

[0684] In the general formula (1), L S1 It represents a single bond or a divalent linking group.

[0685] Examples of the divalent linking group include -O-, -CO-, -COO-, -S-, -SO2-, -NR N -(R N represents a hydrogen atom or an alkyl group), a divalent hydrocarbon group (an alkylene group, an alkenylene group (e.g., -CH=CH-) or an alkynylene group (e.g., -C≡C-, etc.) and an arylene group), -SiR SX 2-(R SX represents a hydrogen atom or a substituent) and a group formed by combining one or more groups selected from these.

[0686] If possible, the divalent linking group may have a substituent, and the substituent of the divalent linking group may be S described below. S1 The group represented by may also partially contain S S1 The group of the group represented.

[0687] Among them, the divalent linking group is preferably a group formed by combining a group selected from an ester group and an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms).

[0688] Among them, the divalent linking group is preferably a group represented by *A-CO-O-*B or *A-CO-O-alkylene-*B.

[0689] *B represents the same as S in the general formula (1) S1 The bonding position of *A is opposite to that of *B.

[0690] The alkylene group may be straight-chain or branched. Furthermore, the alkylene group may be a cyclic structure as a whole or may contain a cyclic structure partially. The alkylene group is preferably straight-chain.

[0691] The carbon number of the alkylene group is preferably 1 to 10, more preferably 1 to 3. When the alkylene group has a substituent, the preferred carbon number here refers to the carbon number including the carbon number that may be present in the substituent. The alkylene group is preferably unsubstituted.

[0692] In the general formula (1), S S1 represents a substituent.

[0693] The substituent preferably contains a silicon atom or a fluorine atom. That is, the substituent is preferably a group containing a silicon atom or a group containing a fluorine atom.

[0694] The substituent is preferably an unsubstituted alkyl group, a fluoroalkyl group or a group represented by the general formula (SS1) described below, and more preferably a fluoroalkyl group or a group represented by the general formula (SS1) described below.

[0695] As S S1 The unsubstituted alkyl group of the substituent represented by the above may be linear or branched, and may be a cyclic structure as a whole or may partially contain a cyclic structure.

[0696] The unsubstituted alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

[0697] As S S1 The alkyl portion of the fluoroalkyl group of the substituent represented by the above may be linear or branched, and the alkyl portion may be a cyclic structure as a whole or may partially contain a cyclic structure.

[0698] The alkyl moiety has preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms.

[0699] The above-mentioned alkyl moiety also preferably has no substituent other than a fluorine atom.

[0700] The number of fluorine atoms contained in the fluoroalkyl group is preferably 1 to 30, more preferably 5 to 20.

[0701] It is also preferred that the above-mentioned fluoroalkyl group is in its entirety or in part a perfluoroalkyl group.

[0702] As S S1 The groups represented by the general formula (SS1) of the substituent represented are as follows.

[0703] *-L S2 -O-SiR S2 3 (SS1)

[0704] In the general formula (SS1), * represents a bonding position.

[0705] In the general formula (SS1), R S2 It represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

[0706] The number of carbon atoms in the hydrocarbon group is 1 to 20, preferably 1 to 10, and more preferably 1 to 5. When the hydrocarbon group has a substituent, the number of carbon atoms referred to here means the number of carbon atoms including the number of carbon atoms that may be present in the substituent.

[0707] The above-mentioned hydrocarbon group is preferably an alkyl group.

[0708] The alkyl group may be linear or branched, and may be a ring structure as a whole or may partially contain a ring structure.

[0709] There are multiple R S2 They may be the same or different.

[0710] In the general formula (SS1), L S2 It represents a single bond or a divalent linking group.

[0711] As L in the general formula (SS1) S2 Examples of the divalent linking group in the formula (1) include: S1 The group mentioned as an example of a divalent linking group in .

[0712] And, L S2 The divalent linking group in the formula may contain one or more (e.g., 1 to 1000) -SiR S2 2-O-. In addition, the above-mentioned -SiR S2 2-O-R S2 With the above R S2 same.

[0713] From the viewpoint of further improving the effect of the present invention, S S1 More preferred is a group represented by the general formula (2).

[0714] The groups represented by the general formula (2) are shown below.

[0715] [Chemical formula 35]

[0716]

[0717] In the general formula (2), * represents a bonding position.

[0718] In the general formula (2), sa represents an integer of 1 to 1,000.

[0719] In the general formula (2), R S3 It represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the general formula (3) described later.

[0720] In the general formula (2), there are multiple R S3 They may be the same or different.

[0721] As can be S3 The hydrocarbon group represented by the above-mentioned R S2 represents a hydrocarbon group which may have a substituent.

[0722] Among them, R bonded to Si at the right end in the general formula (2) S3 Preferably, they are each independently the above-mentioned hydrocarbon group.

[0723] When sa in the general formula (2) is 1, "-(-SiR S3 2-O-) sa -" S3 Preferably, each of them is independently a group represented by the general formula (3) described below.

[0724] “-(-SiR S3 2-O-) sa -"There are "2×sa" R S3 In the formula (3), R S3 The number is preferably 0-1000, more preferably 0-10, and even more preferably 0-2.

[0725] will be able to be S3 The groups represented by the general formula (3) are shown below.

[0726] [Chemical formula 36]

[0727]

[0728] In the general formula (3), * represents a bonding position.

[0729] In the general formula (3), sb represents an integer of 0 to 300.

[0730] In the general formula (3), R S4 It represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

[0731] In the general formula (3), there are multiple R S4 They may be the same or different.

[0732] As can be S4 The hydrocarbon group represented by the above-mentioned R S2 represents a hydrocarbon group which may have a substituent.

[0733] The polymer contained in the coating layer may contain a repeating unit other than the repeating unit represented by the general formula (1).

[0734] The repeating unit other than the repeating unit represented by the above general formula (1) is preferably a (meth)acrylic repeating unit.

[0735] The molecular weight of the repeating unit other than the repeating unit represented by the above general formula (1) is preferably 86 to 1,000, more preferably 100 to 500.

[0736] In the polymer contained in the coating layer, the content of the repeating unit represented by the general formula (1) is preferably 10 to 100 mass %, more preferably 60 to 100 mass %, and more preferably 90 to 100 mass % based on all the repeating units from the viewpoint of further improving the effects of the present invention.

[0737] It is preferred that the polymer contained in the coating layer does not substantially contain a repeating unit having an ethylenically unsaturated group and / or a repeating unit having a hydrolyzable silyl group.

[0738] Substantially containing no repeating units means that, in the polymer contained in the coating layer, the content of the repeating unit having an ethylenically unsaturated group and the repeating unit having a hydrolyzable silyl group is independently 1.0% by mass or less (preferably 0.1% by mass or less) based on all the repeating units.

[0739] The coating layer composed of a polymer containing a repeating unit represented by the general formula (1) can be formed, for example, by the following method.

[0740] First, a silane coupling agent (such as 3-methacryloxypropyltrimethoxysilane) containing an ethylenically unsaturated group (such as a (meth)acryloyl group, a vinyl group, and a styrene group) is reacted with silica to form a polymer precursor layer containing an ethylenically unsaturated group on the surface of silica. Next, the ethylenically unsaturated group of the polymer precursor layer, the ethylenically unsaturated group of the monomer corresponding to the repeating unit represented by the general formula (1), and the ethylenically unsaturated group of other monomers containing an ethylenically unsaturated group added as needed are polymerized to form a coating layer containing a polymer containing a repeating unit represented by the general formula (1).

[0741] Furthermore, the group containing fluorine atoms can be a group contained in a coating layer without a polymer, for example, a layer formed by using a silane coupling agent containing a group containing fluorine atoms. At this time, as a specific example of the group containing fluorine atoms, a fluoroalkyl group can be mentioned, preferably a perfluoroalkyl group.

[0742] The number of carbon atoms of the fluoroalkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3 from the viewpoint of being able to further suppress defects of the cured film.

[0743] The coating layer having a group containing a fluorine atom and not having a polymer can be formed, for example, by reacting a silane coupling agent containing a fluoroalkyl group (such as trifluoropropyltrimethoxysilane) with silicon dioxide. That is, the coating layer may be formed using a silane coupling agent containing a fluoroalkyl group.

[0744] The coating layer having an alkyl group which may have a substituent may be a coating layer having no polymer, and an example thereof may be a layer formed using a silylating agent.

[0745] In the alkyl group which may have a substituent, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 2 or more, and further preferably 3 or more from the viewpoint of further excellent transmittance of the cured film, and more preferably 10 or less, and further preferably 8 or less from the viewpoint of further excellent uniformity of the cured film.

[0746] The alkyl group may have any structure of a linear, branched, or cyclic structure, but is preferably a linear structure from the viewpoint of further improving the effects of the present invention.

[0747] Specific examples of the alkyl group include methyl, ethyl, isopropyl, n-butyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, and cyclohexyl.

[0748] In the alkyl group which may have a substituent, as the substituent, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-epoxypropyl group, and the like can be given.

[0749] The coating layer having an alkyl group which may have a substituent can be formed, for example, by reacting a silylating agent (hexamethyldisilazane or the like) containing an alkyl group with silicon dioxide. That is, the coating layer may be formed using a silylating agent containing an alkyl group.

[0750] The coating layer having an aryl group which may have a substituent may be a coating layer having no polymer, and for example, a layer formed using a silane coupling agent containing an aryl group which may have a substituent may be mentioned.

[0751] In the aryl group which may have a substituent in the coating layer, the number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 20 or less, and further preferably 12 or less from the viewpoint of further improving the uniformity of the cured film.

[0752] The aryl group may be a monocyclic ring or may have a condensed ring structure of two or more rings, but is preferably a monocyclic ring from the viewpoint of further improving the effects of the present invention.

[0753] Specific examples of the aryl group include a phenyl group, a 2,6-diethylphenyl group, a 3,5-ditrifluoromethylphenyl group, a naphthyl group, and a biphenyl group.

[0754] In the aryl group which may have a substituent, as the substituent, a p-phenylyl group, an N-phenyl-3-aminopropyl group, and the like can be mentioned.

[0755] The coating layer having an aryl group which may have a substituent can be formed, for example, by reacting a silane coupling agent containing an aryl group with silicon dioxide. That is, the coating layer may be a layer formed using a silane coupling agent containing an aryl group.

[0756] The coating layer having a (meth)acryloyl group may be a coating layer without a polymer, and may be formed, for example, by reacting a silane coupling agent containing a (meth)acryloyl group (such as 3-methacryloxypropyltrimethoxysilane) with silicon dioxide. That is, the coating layer may also be a layer formed using a silane coupling agent containing a (meth)acryloyl group.

[0757] Furthermore, the coating layer having a glycidoxy group may be a coating layer without a polymer, and can be formed, for example, by reacting a silane coupling agent containing a glycidoxy group (such as 3-glycidoxypropyltrimethoxysilane) with silicon dioxide. That is, the coating layer may also be a layer formed using a silane coupling agent containing a glycidoxy group.

[0758] Furthermore, the coating layer having amino groups may be a coating layer without a polymer, and may be formed, for example, by reacting an amino group-containing silane coupling agent (such as 3-aminopropyltrimethoxysilane) with silicon dioxide. That is, the coating layer may be a layer formed using an amino group-containing silane coupling agent.

[0759] In the modified silica particles, from the viewpoint of more excellent effects of the present invention, the content of the coating layer is preferably 2% by mass or more, preferably 6% by mass or more, and more preferably 8% by mass or more relative to the total mass of the modified silica particles. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 15% by mass or less.

[0760] 〔Ultraviolet light absorber〕

[0761] The composition of the present invention may or may not contain a UV absorber.

[0762] When the composition contains a UV absorber, its content is preferably more than 0% by mass and less than 5% by mass relative to the total mass of the solid content. From the viewpoint of improving curability, it is more preferably less than 4% by mass, and further preferably less than 3% by mass.

[0763] The ultraviolet absorber referred to herein is a compound other than a photopolymerization initiator and has a wavelength of 50 (l·mol) in the range of 300 to 800 nm (more preferably 330 to 500 nm). -1 cm -1 ) or above.

[0764] Examples of the ultraviolet absorber include conjugated diene compounds, and may be a compound represented by the following formula (I).

[0765] [Chemical formula 37]

[0766]

[0767] In formula (I), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 They may be the same as or different from each other, but they do not both represent hydrogen atoms.

[0768] In formula (I), R 3 and R 4 Each independently represents an electron withdrawing group. The electron withdrawing group is a Hammett substituent constant σ p An electron withdrawing group having a value of 0.20 or more and 1.0 or less.

[0769] R of the ultraviolet absorber represented by formula (I) 1 ~R 4For the description of the formula (I), reference can be made to paragraphs 0024 to 0033 of International Publication No. 2009 / 123109 (paragraphs 0040 to 0059 of the corresponding U.S. Patent Application Publication No. 2011 / 0039195), which are incorporated into this specification. For the compound represented by formula (I), reference can be made to the description of the exemplary compounds (1) to (14) of paragraphs 0034 to 0037 of International Publication No. 2009 / 123109 (paragraph 0060 of the corresponding U.S. Patent Application Publication No. 2011 / 0039195), which are incorporated into this specification. Specific examples of the ultraviolet absorber represented by formula (I) include the following compounds.

[0770] [Chemical formula 38]

[0771]

[0772] 〔Other optional ingredients〕

[0773] The composition may also contain any other components other than the above components. For example, particle components other than the above, ultraviolet absorbers, silane coupling agents, sensitizers, co-sensitizers, crosslinking agents, curing accelerators, thermosetting accelerators, plasticizers, diluents and fat-sensitizing agents can be cited. Furthermore, the composition may contain known additives such as adhesion promoters and other auxiliary agents (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusters and chain transfer agents) on the substrate surface as needed, or may not contain them.

[0774] For example, these components can be referred to in paragraphs 0183 to 0228 of Japanese Patent Application Publication No. 2012-003225 (paragraphs 0237 to 0309 of the corresponding specification of U.S. Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0102, 0103 to 0104, and 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and paragraphs 0159 to 0184 of Japanese Patent Application Publication No. 2013-195480, and the like, and these contents are incorporated into the specification of the present application.

[0775] [Method for producing the composition]

[0776] Regarding the composition, a color material composition (color material dispersion) containing a black pigment is produced, and the obtained color material composition is preferably further mixed with other components to obtain a composition.

[0777] The color material composition is preferably prepared by mixing a black color material, a resin, and a solvent. Furthermore, it is also preferred that the color material composition contain a polymerization inhibitor.

[0778] The color material composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like).

[0779] When preparing the composition, each component may be blended at once, or each component may be dissolved or dispersed in a solvent and then blended sequentially. Furthermore, the order of adding and the operating conditions during blending are not particularly limited.

[0780] In order to remove foreign matter and reduce defects, it is preferred to utilize a filter to filter the composition. As a filter, for example, as long as it is a filter that has always been used for filtering purposes, it can be used without particular restrictions. For example, filters based on fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high density, ultra-high molecular weight) can be cited. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0781] The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, further preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. If it is within this range, clogging of the filter of the pigment (including black pigment) can be suppressed, and fine foreign matter such as impurities and aggregates contained in the pigment can be reliably removed.

[0782] When using filters, different filters can be combined. In this case, filtration through the first filter can be performed only once or twice or more. When combining different filters to perform filtration more than twice, it is preferred that the pore size after the second filtration is the same as or larger than the pore size of the first filtration. In addition, first filters with different pore sizes can be combined within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, it can be selected from various filters provided by NIHON PALL LTD., Toyo Roshi Kaisha, LTD., Nihon Entegris KK (formerly Mykrolis Corporation) and KITZ MICROFILTER CORPORATION.

[0783] The second filter may be made of the same material as the first filter. The pore size of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and even more preferably 0.3 to 6.0 μm.

[0784] The composition preferably does not contain impurities such as metals, halogen-containing metal salts, acids, bases, etc. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, further preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably substantially free (below the detection limit of the measuring device).

[0785] The impurities can be measured using an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Electric Corporation, Agilent 7500cs model).

[0786] [Manufacturing of Cured Film]

[0787] By curing the composition layer formed using the composition of the present invention, a cured film (including a patterned cured film) can be obtained.

[0788] The method for producing the cured film is not particularly limited, but preferably includes the following steps.

[0789] Composition layer forming step

[0790] Exposure process

[0791] Development process

[0792] Hereinafter, each step will be described.

[0793] [Composition layer forming step]

[0794] In the composition layer forming step, a composition is applied to a support body etc. before exposure to form a layer (composition layer) of the composition. As a support body, for example, a solid-state imaging element substrate having an imaging element (light-receiving element) such as a CCD or CMOS disposed on a substrate (e.g., a silicon substrate) can be used. In addition, as required, an undercoat layer for improving the close fit with the upper layer, preventing the diffusion of substances and flattening the substrate surface can be provided on the support body.

[0795] As an applicable method for the composition on the support, various coating methods such as slit coating, inkjet, spin coating, cast coating, roll coating and screen printing can be applied. The film thickness of the composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and further preferably 0.2 to 3 μm. Regarding the drying (prebaking) of the composition layer coated on the support, for example, it can be carried out at a temperature of 50 to 140° C. for 10 to 300 seconds using a hot plate, an oven, etc.

[0796] [Exposure process]

[0797] In the exposure step, the composition layer (dried film) formed in the composition layer forming step is exposed by irradiating actinic rays or radiation, and the light-irradiated composition layer is cured.

[0798] As a method of light irradiation, it is preferable to perform light irradiation through a photomask having patterned openings.

[0799] The exposure is preferably performed by irradiation with radiation. The radiation that can be used for exposure is preferably ultraviolet rays such as g-rays, h-rays or i-rays, and the light source is preferably a high-pressure mercury lamp. The irradiation intensity is preferably 5 to 1500 mJ / cm 2 , more preferably 10 to 1000 mJ / cm 2 .

[0800] When the composition contains a thermal polymerization initiator, the composition layer may be heated in the exposure step. The heating temperature is not particularly limited, but is preferably 80 to 250° C. The heating time is preferably 30 to 300 seconds.

[0801] In addition, when the composition layer is heated in the exposure step, it can also serve as a post-heating step described later. In other words, when the composition layer is heated in the exposure step, the method for producing a cured film does not need to include a post-heating step.

[0802] 〔Development process〕

[0803] The development step is a step of developing the composition layer after exposure to form a cured film. The development step dissolves the composition layer in the portion not irradiated with light in the exposure step, leaving only the photocured portion, thereby obtaining a patterned cured film.

[0804] The type of developer used in the development step is not particularly limited, but an alkaline developer that does not damage the imaging element and circuit of the substrate is preferred.

[0805] The development temperature is, for example, 20 to 30°C.

[0806] The developing time is, for example, 20 to 90 seconds. In order to more effectively remove the residue, in recent years, 120 to 180 seconds is sometimes implemented. Furthermore, in order to further improve the removability of the residue, the process of shaking off the developer every 60 seconds and further resupplying the developer is sometimes repeated several times.

[0807] The alkali developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass).

[0808] Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among which, an organic base is preferred).

[0809] When used as an alkali developer, a washing treatment with water is usually performed after development.

[0810] 〔Post-baking〕

[0811] After the exposure process, a heat treatment (post-baking) is preferably performed. Post-baking is a heat treatment after development for complete curing. The heating temperature is preferably 240°C or less, more preferably 220°C or less. The lower limit is not particularly limited, but if efficient and effective processing is considered, it is preferably 50°C or more, more preferably 100°C or more.

[0812] Post-baking can be performed continuously or batchwise using a heating mechanism such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater.

[0813] The above-mentioned post-baking is preferably carried out in an atmosphere of low oxygen concentration. Its oxygen concentration is preferably 19 volume % or less, more preferably 15 volume % or less, further preferably 10 volume % or less, particularly preferably 7 volume % or less, and most preferably 3 volume % or less. The lower limit is not particularly limited, and is actually 10 volume ppm or more.

[0814] Furthermore, the curing may be completed by changing to the post-baking by heating as described above and irradiating with UV (ultraviolet rays).

[0815] At this time, the above-mentioned composition preferably also contains a UV curing agent. The UV curing agent is preferably a UV curing agent that can be cured at the exposure wavelength of the polymerization initiator added for the photolithography process based on the usual i-ray exposure, that is, a wavelength shorter than 365nm. As a UV curing agent, for example, Omnirad 2959 manufactured by IGM Resins BV can be cited (corresponding to IRGACURE2959 (former product name, previously manufactured by BASF)). In the case of UV irradiation, the composition layer is preferably a material that cures at a wavelength of less than 340nm. The lower limit of the wavelength is not particularly limited, and is usually above 220nm. In addition, the exposure amount of UV irradiation is preferably 100 to 5000mJ, more preferably 300 to 4000mJ, and further preferably 800 to 3500mJ. In order to perform low-temperature curing more effectively, the UV curing process is preferably performed after the exposure process. The exposure light source preferably uses an ozone-free mercury lamp.

[0816] [Physical properties of cured film and uses of cured film]

[0817] [Physical properties of cured film]

[0818] The cured film formed using the composition of the present invention (especially, the composition of the present invention containing a black color material) can be preferably used as a light-shielding film.

[0819] From the viewpoint of excellent light shielding properties, the optical density (OD: Optical Density) per 1.5 μm film thickness in the wavelength range of 400 to 700 nm of the cured film is preferably more than 2.0, more preferably more than 3.0. The upper limit is not particularly limited, but is usually preferably 10 or less.

[0820] In this specification, the optical density per 1.5 μm film thickness in the wavelength region of 400 to 700 nm exceeds 2.0 means that the optical density per 1.5 μm film thickness exceeds 2.0 in the entire wavelength region of 400 to 700 nm.

[0821] Furthermore, the cured film (light-shielding film) preferably has good light-shielding properties for light in the infrared region, for example, the optical density per 1.5 μm film thickness in light of a wavelength of 940 nm is preferably greater than 2.0, more preferably greater than 3.0. In addition, the upper limit is not particularly limited, but is preferably generally 10 or less.

[0822] Moreover, when the cured film is used as a light attenuating film, the optical density is preferably smaller than the above value.

[0823] In this specification, as a method for measuring the optical density of a cured film, first, a cured film is formed on a glass substrate, and the optical density per a predetermined film thickness is calculated using a spectrophotometer (UV-3600, manufactured by Hitachi, Ltd., etc.).

[0824] Furthermore, even in the state of the composition layer (dried film) obtained by applying the composition and drying it, the film thickness and optical density generally do not change significantly compared to the state of the cured film obtained by subsequently exposing and curing it. In this case, the optical density of the composition layer (dried film) can be measured by the above-mentioned measurement method, and the obtained value can be used as the optical density of the cured film.

[0825] The film thickness of the cured film is, for example, preferably 0.1 to 4.0 μm, more preferably 1.0 to 2.5 μm. Depending on the application, the cured film may be a thin film or a thick film compared to this range.

[0826] Furthermore, when the cured film is used as a light attenuating film, the light shielding property can be adjusted by using a thinner film (e.g., 0.1 to 0.5 μm) than the above range. In this case, the optical density per 1.0 μm film thickness in the wavelength region of 400 to 700 nm (and / or light with a wavelength of 940 nm) is preferably 0.1 to 1.5, and more preferably 0.2 to 1.0.

[0827] The reflectance of the cured film is preferably less than 8%, more preferably less than 6%, and further preferably less than 4%. The lower limit is 0% or more.

[0828] The reflectivity mentioned here is obtained by using a VAR unit of a JASCO Corporation spectrometer V7200 (product name) to inject light with a wavelength of 400 to 1100 nm at an incident angle of 5°, and obtaining a reflection spectrum. Specifically, the reflectivity of light with a wavelength showing the maximum reflectivity within the wavelength range of 400 to 1100 nm is set as the reflectivity of the cured film.

[0829] Furthermore, the above-mentioned cured film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smart phones and digital cameras; OA (Office Automation) equipment such as multi-function printers and scanners; industrial equipment such as surveillance cameras, barcode readers and automatic teller machines (ATMs), high-speed cameras and equipment with personal authentication functions using facial image authentication or biometric authentication; vehicle-mounted camera equipment; medical camera equipment such as endoscopes, capsule endoscopes and catheters; and aerospace equipment such as living body sensors, biosensors, military reconnaissance cameras, stereo map cameras, meteorological and ocean observation cameras, land resource reconnaissance cameras, and astronomical and deep space target exploration cameras in the universe; etc.; and shading components and shading films of optical filters and modules used in the above-mentioned devices, and are therefore suitable for anti-reflection components and anti-reflection films.

[0830] The cured film can also be used for micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode) etc. In addition to optical filters and optical films used in micro LED and micro OLED, the cured film is also suitable for components that provide light shielding function or anti-reflection function.

[0831] Examples of micro LEDs and micro OLEDs include those described in Japanese Unexamined Patent Application Publication No. 2015-500562 and Japanese Unexamined Patent Application Publication No. 2014-533890.

[0832] The above-mentioned cured film is also preferably used as an optical film for quantum dot sensors and quantum dot solid-state imaging elements. In addition, it is suitable as a component that imparts light shielding function and anti-reflection function. As quantum dot sensors and quantum dot solid-state imaging elements, for example, examples described in the specification of U.S. Patent Application Publication No. 2012 / 37789 and the pamphlet of International Publication No. 2008 / 131313 can be cited.

[0833] [Light-shielding film, optical element, solid-state imaging element, and solid-state imaging device]

[0834] The cured film of the present invention is also preferably used as a so-called light-shielding film. Such a light-shielding film is also preferably used for a solid-state imaging element.

[0835] As described above, the cured film formed using the photosensitive composition of the present invention is excellent in light shielding property and low reflectivity.

[0836] In addition, a light-shielding film is one of the preferred uses of the cured film of the present invention, and the light-shielding film of the present invention can be produced by the method described as the method for producing the cured film. Specifically, the composition can be applied on a substrate to form a composition layer, and then exposed and developed to produce the light-shielding film.

[0837] The present invention also includes the invention of an optical element. The optical element of the present invention is an optical element having the above-mentioned cured film (light shielding film). As an optical element, for example, an optical element used in optical equipment such as a camera, binoculars, a microscope, and a semiconductor exposure device can be cited.

[0838] Among them, as the optical element, for example, a solid-state imaging element mounted on a camera or the like is preferable.

[0839] Furthermore, the solid-state imaging element of the present invention is a solid-state imaging element including the above-mentioned cured film (light shielding film) of the present invention.

[0840] As a method in which the solid-state imaging element of the present invention contains a cured film (light-shielding film), for example, a method in which a light-receiving element formed of a plurality of photodiodes and polycrystalline silicon, etc., which constitute a light-receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) is provided on a substrate, and a cured film is provided on the light-receiving element forming surface side of the support body (for example, a portion other than the light-receiving portion and / or pixels for adjusting color, etc.) or on the side opposite to the forming surface.

[0841] Furthermore, when the cured film is used as a light attenuation film, for example, if the light attenuation film is arranged so that a part of light enters a light receiving element after passing through the light attenuation film, the dynamic range of the solid-state imaging element can be improved.

[0842] A solid-state imaging device includes the above-mentioned solid-state imaging element.

[0843] refer to Figure 1-2 , a structural example of a solid-state imaging device and a solid-state imaging element is described. Figure 1-2 In order to make each part clear, the ratio of thickness and / or width to each other is ignored and a part is exaggeratedly displayed.

[0844] Figure 1 It is a schematic cross-sectional view showing a structural example of a solid-state imaging device including the solid-state imaging element of the present invention.

[0845] like Figure 1 As shown, the solid-state imaging device 100 includes a rectangular solid-state imaging element 101, and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Furthermore, a lens layer 111 is overlapped and provided on the cover glass 103 via a spacer 104. The lens layer 111 is composed of a support body 113 and a lens material 112. The lens layer 111 may be a structure in which the support body 113 and the lens material 112 are integrally formed. If stray light is incident on the peripheral region of the lens layer 111, the focusing effect of the lens material 112 is weakened due to the diffusion of light, and the light reaching the imaging unit 102 is reduced. In addition, the generation of noise caused by the stray light also occurs. Therefore, a light shielding film 114 is provided on the peripheral region of the lens layer 111 to shield light. The cured film of the present invention can also be used as the above-mentioned light shielding film 114.

[0846] The solid-state imaging element 101 performs photoelectric conversion on an optical image formed on an imaging unit 102 which is a light receiving surface thereof and outputs the image as an image signal. The solid-state imaging element 101 includes a stacked substrate 105 formed by stacking two substrates. The stacked substrate 105 is composed of a rectangular chip substrate 106 and a circuit substrate 107 of the same size, and the circuit substrate 107 is stacked on the back of the chip substrate 106.

[0847] As a material of a substrate used as the chip substrate 106 , for example, a known material can be used.

[0848] The imaging unit 102 is provided at the center of the surface of the chip substrate 106. In addition, a light shielding film 115 is provided in the peripheral region of the imaging unit 102. The light shielding film 115 shields stray light incident on the peripheral region, thereby preventing dark current (noise) from being generated from the circuit in the peripheral region. The cured film of the present invention is preferably used as the light shielding film 115.

[0849] A plurality of electrode pads 108 are provided on the edge of the surface of the chip substrate 106 . The electrode pads 108 are electrically connected to the imaging unit 102 via signal lines (which may be bonding wires) provided on the surface of the chip substrate 106 (not shown).

[0850] On the back surface of the circuit substrate 107, external connection terminals 109 are provided substantially below each electrode pad 108. Each external connection terminal 109 is connected to the electrode pad 108 via a through electrode 110 vertically penetrating the laminated substrate 105. Furthermore, each external connection terminal 109 is connected to a control circuit for controlling the driving of the solid-state imaging element 101 and an image processing circuit for performing image processing on an imaging signal output from the solid-state imaging element 101 via wiring (not shown).

[0851] Figure 2 1 is a schematic cross-sectional view of the imaging unit 102. Figure 2 As shown, the imaging unit 102 is composed of a light receiving element 201, a color filter 202, a micro lens 203 and other components provided on a substrate 204. The color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g and a black matrix 205bm. The cured film of the present invention can be used as the black matrix 205bm.

[0852] As the material of the substrate 204, for example, the same material as the aforementioned chip substrate 106 can be used. A p-well layer 206 is formed on the surface of the substrate 204. In the p-well layer 206, light receiving elements 201 composed of n-type layers and generating and accumulating signal charges by photoelectric conversion are arranged in a square lattice.

[0853] On one side of the light receiving element 201, a vertical transfer path 208 composed of an n-type layer is formed via a readout gate portion 207 of the surface layer of the p-well layer 206. On the other side of the light receiving element 201, a vertical transfer path 208 belonging to an adjacent pixel is formed via an element isolation region 209 composed of a p-type layer. The readout gate portion 207 is a channel region for reading the signal charge accumulated in the light receiving element 201 to the vertical transfer path 208.

[0854] A gate insulating film 210 formed of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204. A vertical transfer electrode 211 formed of polysilicon or amorphous silicon is formed on the gate insulating film 210 so as to cover the vertical transfer path 208, the readout gate portion 207, and substantially directly above the element isolation region 209. The vertical transfer electrode 211 functions as a driving electrode for driving the vertical transfer path 208 to transfer charges and a readout electrode for driving the readout gate portion 207 to read out signal charges. The signal charges are sequentially transferred from the vertical transfer path 208 to the horizontal transfer path and the output portion (floating diffusion amplifier) ​​not shown, and then output as a voltage signal.

[0855] A light shielding film 212 is formed on the vertical transfer electrode 211 to cover the surface thereof. The light shielding film 212 has an opening just above the light receiving element 201 and shields the other regions from light. The cured film of the present invention can also be used as the light shielding film 212.

[0856] A transparent intermediate layer is provided on the light shielding film 212. The intermediate layer is formed of an insulating film 213 formed of BPSG (borophospho silicate glass), an insulating film (passivation film) 214 formed of P-SiN, and a planarizing film 215 formed of a transparent resin or the like. The color filter 202 is formed on the intermediate layer.

[0857] 〔Image display device〕

[0858] The image display device of the present invention includes the cured film of the present invention.

[0859] As an embodiment in which the image display device has a cured film, for example, there can be mentioned an embodiment in which the cured film is contained in a black matrix and a color filter including such a black matrix is ​​used for the image display device.

[0860] Next, a black matrix and a color filter including the black matrix will be described, and further, a liquid crystal display device including such a color filter will be described as a specific example of an image display device.

[0861] <Black Matrix>

[0862] The cured film of the present invention is also preferably included in a black matrix. A black matrix may be included in an image display device such as a color filter, a solid-state imaging element, and a liquid crystal display device.

[0863] As examples of the black matrix, there can be cited the black matrix described above; a black edge provided at the periphery of an image display device such as a liquid crystal display device; a black grid-shaped and / or striped portion between red, blue, and green pixels; a dot-shaped and / or linear black pattern used for light shielding of a TFT (thin film transistor); etc. The definition of the black matrix is ​​described, for example, in "Dictionary of Terms for Liquid Crystal Display Manufacturing Equipment", 2nd edition, NIKKAN KOGYO SHIMBUN, LTD., 1996, p. 64.

[0864] In order to improve display contrast and prevent image quality degradation caused by light leakage current in the case of an active matrix driven liquid crystal display device using a thin film field effect transistor (TFT), the black matrix preferably has a high light shielding property (optical density OD of 3 or more).

[0865] As a method for manufacturing a black matrix, for example, it can be manufactured using the same method as the method for manufacturing the above-mentioned cured film. Specifically, the composition can be applied on a substrate to form a composition layer, and a patterned cured film (black matrix) is manufactured by exposure and development. In addition, the film thickness of the cured film used as the black matrix is ​​preferably 0.1 to 4.0 μm.

[0866] The material of the substrate preferably has a transmittance of 80% or more for visible light (wavelength 400 to 800 nm). Examples of such materials include glasses such as soda-lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; and the like. From the viewpoint of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferred.

[0867] <Color filter>

[0868] The cured film of the present invention is also preferably included in a color filter.

[0869] As an embodiment of a color filter including a cured film, for example, a color filter including a substrate and the above-mentioned black matrix can be cited. That is, a color filter including red, green and blue colored pixels formed in the openings of the above-mentioned black matrix formed on the substrate can be exemplified.

[0870] A color filter including a black matrix (cured film) can be produced by, for example, the following method.

[0871] First, a coating film (composition layer) containing a composition of a pigment corresponding to each color pixel of the color filter is formed in the opening of the patterned black matrix formed on the substrate. In addition, as the composition for each color, for example, a known composition can be used, and among the compositions described in this specification, a composition in which the black color material is replaced with a colorant corresponding to each pixel is preferably used.

[0872] Next, the composition layer is exposed via a photomask having a pattern corresponding to the opening of the black matrix. Next, after the unexposed portion can be removed by development, baking is performed to form colored pixels at the opening of the black matrix. For example, a color filter having red, green, and blue pixels can be manufactured by performing a series of operations using compositions of each color containing red, green, and blue pigments.

[0873] <Liquid crystal display device>

[0874] The cured film of the present invention is also preferably included in a liquid crystal display device. As an embodiment in which a liquid crystal display device includes a cured film, an embodiment including a color filter including the black matrix (cured film) described above can be given.

[0875] The liquid crystal display device of this embodiment may include, for example, a pair of substrates disposed opposite to each other and a liquid crystal compound sealed between the substrates. The substrates may be, for example, the substrates described above as black matrix substrates.

[0876] As a specific form of the above-mentioned liquid crystal display device, for example, there can be cited a stacked body containing, in order from the user side, polarizer / substrate / color filter / transparent electrode layer / orientation film / liquid crystal layer / orientation film / transparent electrode layer / TFT (Thin Film Transistor: thin film field effect transistor) element / substrate / polarizer / backlight unit.

[0877] In addition, as a liquid crystal display device, for example, a liquid crystal display device described in "Electronic Display Device (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)", "Display Device (written by Junsho Ibuki, published by Sangyo Tosho Publishing Co., Ltd. in 1989)", etc. can be cited. In addition, for example, a liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (written by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. in 1994)" can be cited.

[0878] 〔Infrared sensor〕

[0879] The cured film of the present invention is also preferably included in an infrared sensor.

[0880] use Figure 3 The infrared sensor of the above-mentioned embodiment will be described. Figure 3 It is a schematic cross-sectional view showing a structural example of an infrared sensor including the cured film of the present invention. Figure 3 The infrared sensor 300 shown includes a solid-state imaging element 310 .

[0881] The imaging region provided in the solid-state imaging element 310 is constituted by combining an infrared absorption filter 311 and a color filter 312 according to an embodiment of the present invention.

[0882] The infrared absorption filter 311 is a film that transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm, and more preferably light with a wavelength of 900 to 1000 nm). As a colorant, a cured film containing an infrared absorber (the method of the infrared absorber is as described above) can be used.

[0883] The color filter 312 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light region, for example, a color filter formed with pixels of red (R), green (G), and blue (B) is used, and the method is as described above.

[0884] A resin film 314 (for example, a transparent resin film) that can transmit light having a wavelength of the infrared transmission filter 313 is disposed between the infrared transmission filter 313 and the solid-state imaging element 310 .

[0885] The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light of a specific wavelength, and can use the cured film of the present invention containing a colorant that absorbs light in the visible light region (e.g., perylene compounds and / or bisbenzofuranone compounds, etc.) and an infrared absorber (e.g., pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, and polymethine compounds, etc.). For example, the infrared transmission filter 313 preferably shields light of a wavelength of 400 to 830 nm and transmits light of a wavelength of 900 to 1300 nm.

[0886] A microlens 315 is disposed on the incident light hv side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed so as to cover the microlens 315.

[0887] exist Figure 3 In the illustrated embodiment, the resin film 314 is provided, but the infrared transmission filter 313 may be formed instead of the resin film 314 . That is, the infrared transmission filter 313 may be formed on the solid-state imaging element 310 .

[0888] And, in Figure 3 In the illustrated embodiment, the film thickness of the color filter 312 is the same as the film thickness of the infrared transmission filter 313, but the film thicknesses of the two may be different.

[0889] And, in Figure 3 In the manner shown, the color filter 312 is arranged at a position closer to the incident light hν side than the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 can also be swapped, and the infrared absorption filter 311 can be arranged at a position closer to the incident light hν side than the color filter 312.

[0890] And, in Figure 3In the embodiment shown, the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other, but the two filters do not necessarily need to be adjacent to each other, and another layer may be provided between the two filters. In addition to being used as a light shielding film on the end and / or side of the surface of the infrared absorption filter 311, the cured film of the present invention can also be used as an inner wall of an infrared sensor device to prevent internal reflection and / or unexpected light from entering the light receiving part, thereby improving sensitivity.

[0891] Since the infrared sensor can read image information at the same time, it is possible to perform motion sensing such as identifying and detecting an object in motion. Furthermore, since the infrared sensor can acquire distance information, it is possible to perform photography of images including 3D information. Furthermore, the infrared sensor can also be used as a biometric authentication sensor.

[0892] Next, a solid-state imaging device to which the above-mentioned infrared sensor is applied will be described.

[0893] The solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light emitting diode, etc. For each structure of the solid-state imaging device, reference can be made to paragraphs 0032 to 0036 of Japanese Patent Application Laid-Open No. 2011-233983, and the contents are incorporated into this specification.

[0894] 〔Headlight unit〕

[0895] The cured film of the present invention is also preferably included as a light shielding film in a headlamp unit for a vehicle such as an automobile. The cured film of the present invention included as a light shielding film in a headlamp unit is preferably formed in a pattern to shield at least a part of light emitted from a light source.

[0896] use Figure 4 and Figure 5 The headlamp unit of the above-mentioned embodiment will be described. Figure 4 is a schematic diagram showing a structural example of a headlamp unit, Figure 5 It is a schematic perspective view showing a structural example of a light shielding portion of a headlight unit.

[0897] like Figure 4 As shown, the headlamp unit 10 includes a light source 12, a light shielding portion 14, and a lens 16. The light source 12, the light shielding portion 14, and the lens 16 are arranged in this order.

[0898] like Figure 5 As shown, the light shielding portion 14 includes a base 20 and a light shielding film 22 .

[0899] The light shielding film 22 is provided with a patterned opening 23 for irradiating the light emitted from the light source 12 in a specific shape. The light distribution pattern irradiated from the lens 16 is determined by the shape of the opening 23 of the light shielding film 22. The lens 16 projects the light L from the light source 12 that has passed through the light shielding portion 14. As long as a specific light distribution pattern can be irradiated from the light source 12, the lens 16 is not necessarily required. The lens 16 is appropriately determined according to the irradiation distance and irradiation range of the light L.

[0900] The structure of the base 20 is not particularly limited as long as it can hold the light shielding film 22 , but is preferably not deformed by heat from the light source 12 , and is, for example, made of glass.

[0901] Figure 5 An example of a light distribution pattern is shown in FIG. , but the present invention is not limited to this.

[0902] Furthermore, the light source 12 is not limited to one, and can be arranged in a row or in a matrix. When multiple light sources are provided, for example, one light shielding portion 14 can be provided for one light source 12. In this case, the light shielding films 22 of the multiple light shielding portions 14 can all have the same pattern or different patterns.

[0903] The light distribution pattern based on the pattern of the light shielding film 22 will be described.

[0904] Figure 6 is a schematic diagram showing an example of a light distribution pattern based on a headlamp unit, Figure 7 is a schematic diagram showing another example of a light distribution pattern based on a headlamp unit. Figure 6 The light distribution pattern 30 and Figure 7 The light distribution patterns 32 shown all represent areas where light is irradiated. Figure 6 The area 31 and Figure 7 The areas 31 shown in the figure all represent the case where the light shielding film 22 is not provided, and the light source 12 (reference Figure 4 ) irradiated area.

[0905] For example, Figure 6 In the light distribution pattern 30 shown, the light intensity drops sharply at the edge 30a due to the pattern of the light shielding film 22. For example, Figure 6 The light distribution pattern 30 shown is a pattern that does not irradiate light toward an oncoming vehicle when the vehicle is traveling to the left.

[0906] And, if Figure 7 The light distribution pattern 32 shown can also be set to Figure 6 The light distribution pattern 30 shown in FIG. Figure 6Similar to the light distribution pattern 30 shown in FIG. 1 , the light intensity drops sharply at the edge 32a, for example, a pattern in which the light is not irradiated to the oncoming vehicle when driving to the left. Furthermore, the light intensity also drops sharply at the notch 33. Therefore, in the area 34 corresponding to the notch 33, for example, a sign indicating that the road is curved, uphill, downhill, etc. can be displayed. Thus, safety during nighttime driving can be improved.

[0907] The light shielding portion 14 is not limited to being fixed and arranged between the light source 12 and the lens 16 , and may be provided between the light source 12 and the lens 16 as necessary by a driving mechanism (not shown) to obtain a specific light distribution pattern.

[0908] Furthermore, the light shielding portion 14 may constitute a light shielding member capable of shielding light from the light source 12. In this case, the light shielding portion 14 may be provided between the light source 12 and the lens 16 as required by a driving mechanism (not shown) to obtain a specific light distribution pattern.

[0909] Example

[0910] Below, the present invention is further described in detail based on embodiment.The materials, usage, ratio, processing content and processing steps etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention.Thus, the scope of the present invention should not be interpreted restrictively by the embodiments shown below.

[0911] <<Test X>>

[0912] [Manufacturing of Composition]

[0913] Hereinafter, each component used for preparation of the composition will be described.

[0914] 〔Black Pigment〕

[0915] Particles produced by the method described below were used as a black pigment in the preparation of the composition.

[0916] In addition, Zr-2 to Zr-9 among the particles shown below are coated particles.

[0917] <Production of Zr-1 (uncoated zirconium nitride)>

[0918] To 7.4 g of monoclinic zirconium dioxide powder having an average primary particle size of 50 nm calculated from the specific surface area measured by the BET method, 7.3 g of metal magnesium powder having an average primary particle size of 150 μm and 9.0 g of magnesium nitride powder having an average primary particle size of 200 nm were added, and the mixture was uniformly mixed by a reaction device equipped with a graphite boat in a quartz glass tube. At this time, the amount of metal magnesium added was 5.0 times the mole of zirconium dioxide, and the amount of magnesium nitride added was 0.5 times the mole of zirconium dioxide. The mixture was calcined at 700° C. for 60 minutes under a nitrogen atmosphere to obtain a calcined product. The calcined product was dispersed in 1 liter of water, and 10% hydrochloric acid was slowly added. After washing while maintaining the pH at above 1 and the temperature at below 100° C., the pH was adjusted to 7-8 using 25% ammonia water and filtered. The filtered solid content was dispersed in water again at 400 g / L, and acid washing and pH adjustment with ammonia water were performed again in the same manner as above, and then filtered. After repeating the acid washing-ammonia water pH adjustment twice, the residue was dispersed in ion exchange water at 500 g / L in terms of solid content, heated and stirred at 60°C and adjusted to pH 7, filtered using a suction filtration device, further washed with an equal amount of ion exchange water, and dried using a hot air dryer set at a temperature of 120°C, thereby obtaining zirconium nitride powder Zr-1.

[0919] <Production of Zr-2 (zirconium nitride coated with silicon dioxide)>

[0920] 12 mol of ethanol as alcohol was added to 0.1 mol of the above Zr-1, and Zr-1 was dispersed in the ethanol, and wet-pulverized by a bead mill to obtain a Zr-1 dispersion. Next, 6 mol of ethanol was added to the Zr-1 dispersion for concentration adjustment, and 1×10 -2 Then, 1×10 mol of tetramethyl silicate was added to the Zr-1 dispersion to which the tetramethyl silicate was added. -3 The dispersion was washed and dried, and then calcined to obtain zirconium nitride powder Zr-1 coated with a silicon dioxide film and powder Zr-2.

[0921] The dispersion was washed by passing the dispersion through a centrifugal separator and then through an ion exchange resin filter to remove impurities from the dispersion. The calcination was performed by maintaining the dispersion at 350° C. for 5 hours in a nitrogen atmosphere.

[0922] The content of the metal oxide in Zr-2 (the metal oxide coating layer formed of silicon dioxide) was 5% by mass based on the total mass of the coated particles.

[0923] The presence or absence of coating was confirmed by FE-STEM / EDS, and the above content was confirmed by ESCA.

[0924] <Production of Zr-3 to Zr-9 (zirconium nitride coated with alumina)>

[0925] The Zr-1 was mixed with water and adjusted to an aqueous slurry with a powder weight of 100 g / L using a sand mill, thereby obtaining an aqueous dispersion with a powder concentration of 100 g / L. The slurry was heated to 60° C. while stirring, and while maintaining the temperature, a sodium aluminate aqueous solution and a dilute sulfuric acid solution were simultaneously added for 30 minutes while maintaining the pH of the aqueous slurry at 7.0, and aging was continued for 30 minutes.

[0926] Thereafter, the obtained neutralization reaction product was filtered, washed, and dried at 120° C. for 5 hours to obtain a powder in which a powder matrix of zirconium nitride was coated with an alumina film (alumina-coated zirconium nitride).

[0927] The amount of the sodium aluminate aqueous solution added is set within the range of 0.1 to 25 parts by mass of the amount corresponding to Al 2 O 3 relative to 100 parts by mass of Zr-1.

[0928] By adjusting the amount of sodium aluminate aqueous solution added, zirconium nitrides Zr-3 to Zr-9 coated with a metal oxide coating layer (alumina) in the following coating amounts were obtained.

[0929]

[0930] The above-mentioned coating amount indicates the amount of the metal oxide (metal oxide coating layer formed of aluminum oxide) content relative to the total mass of the coated particles.

[0931] The presence or absence of coating was confirmed by FE-STEM / EDS, and the coating amount was confirmed by ESCA.

[0932] <Manufacturing of Ti-1>

[0933] 100 g of titanium oxide MT-150A (product name: TAYCA CORPORATION) with an average primary particle size of 15 nm and 25 g of a BET surface area of ​​300 m 2 / g of silica particles AEROPERL (registered trademark) 300 / 30 (manufactured by EVONIK) and 100 g of a dispersant Disperbyk 190 (product name: manufactured by BYK-Chemie GmbH) were added to 71 g of ion-exchanged water to obtain a mixture.

[0934] Afterwards, the mixture was treated for 20 minutes at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm using KURABO MAZERUSTAR KK-400W to obtain a mixed solution. The mixed solution was filled in a quartz container and heated to 920°C in an oxygen atmosphere using a small rotary kiln (produced by Motoyama Co., Ltd.). Afterwards, the atmosphere in the small rotary kiln was replaced with nitrogen, and ammonia was allowed to flow in the small rotary kiln at 100 mL / min for 5 hours at the same temperature to perform a nitriding reduction treatment. The powder recovered after the completion was crushed in a mortar to obtain a powdered titanium black Ti-1 containing Si atoms. The dispersed body containing titanium black (titanium oxynitride) particles and Si atoms was obtained. Specific surface area: 73m 2 / g〕.

[0935] <Manufacturing of V-1>

[0936] In a nitrogen atmosphere, vanadium oxide powder (specific surface area 1-10m 2 / g) was heated to 800°C at a heating rate of 7°C / min, and then ammonia gas was flowed to perform nitriding reduction, so that the blackness (L value) of the finally obtained black particles was 14.9, the oxygen content was 6.4% by mass, and the nitrogen content was 19% by mass. The product obtained by nitriding reduction was crushed by a hammer mill to obtain single-particle black particles V-1 (vanadium oxynitride).

[0937] <Production of Vc-1>

[0938] In the production of Zr-2, Vc-1, an oxynitride of vanadium coated with silica, was obtained in the same manner except that the raw material was changed from Zr-1 to V-1.

[0939] The content of the metal oxide (metal oxide coating layer formed of silicon dioxide) in Vc-1 was 5% by mass based on the total mass of the coated particles.

[0940] The presence or absence of coating was confirmed by FE-STEM / EDS, and the above content was confirmed by ESCA.

[0941] <Manufacturing of Nb-1>

[0942] In a nitrogen atmosphere, niobium oxide powder (specific surface area 1-10 m 2 After the temperature was raised to 800°C at a heating rate of 7°C / min, ammonia gas was flowed to perform nitriding reduction, so that the blackness (L value) of the finally obtained black particles was 14.9, the oxygen content was 6.4% by mass, and the nitrogen content was 19% by mass. The product obtained by the nitriding reduction was crushed by a hammer mill to obtain single-particle black particles Nb-1 (niobium oxynitride).

[0943] <Manufacturing of Nbc-1>

[0944] In the production of Zr-2, except that the raw material was changed from Zr-1 to Nb-1, niobium oxynitride Nbc-1 coated with silica was obtained in the same manner.

[0945] The content of the metal oxide (metal oxide coating layer formed of silicon dioxide) in Nbc-1 was 5% by mass based on the total mass of the coated particles.

[0946] The presence or absence of coating was confirmed by FE-STEM / EDS, and the above content was confirmed by ESCA.

[0947] 〔Dispersant〕

[0948] The following dispersants were used.

[0949] Dispersant A

[0950] Dispersant A is a dispersant produced by the production method shown below.

[0951] ··Synthesis Example A1: Synthesis of Macromonomer A-1

[0952] ε-caprolactone (1044.2 g), δ-valerolactone (184.3 g) and 2-ethyl-1-hexanol (71.6 g) were introduced into a 3000 mL three-necked flask to obtain a mixture. Then, the mixture was stirred while blowing nitrogen gas. Then, Disperbyk111 (12.5 g, manufactured by BYK-Chemie GmbH, phosphoric acid resin) was added to the mixture, and the obtained mixture was heated to 90°C. After 6 hours, the mixture was heated to 100°C using a flask having a capacity of 1000 mL. 1 After confirming the disappearance of the signal derived from 2-ethyl-1-hexanol in the mixture by H-NMR (nuclear magnetic resonance), the mixture was heated to 110° C. The polymerization reaction was continued at 110° C. for 12 hours under nitrogen. 1H-NMR confirmed the disappearance of the signals from ε-caprolactone and δ-valerolactone, and the molecular weight of the obtained compound was measured by GPC (Gel permeation chromatography). After confirming that the molecular weight of the compound reached the desired value, 2,6-di-tert-butyl-4-methylphenol (0.35 g) was added to the mixture containing the above compounds, and 2-methacryloyloxyethyl isocyanate (87.0 g) was further added to the obtained mixture over 30 minutes. Six hours after the addition was completed, the molecular weight of the obtained compound was measured by using the method of HPLC. 1 After H-NMR confirmed that the signal from 2-methacryloyloxyethyl isocyanate (MOI) disappeared, propylene glycol monomethyl ether acetate (PGMEA) (1387.0 g) was added to the mixture to obtain a macromonomer A-1 solution (2770 g) with a concentration of 50% by mass. The obtained macromonomer A-1 had a weight average molecular weight of 6,000.

[0953] ··Synthesis Example P-1: Synthesis of Dispersant A

[0954] A mixture was obtained by introducing macromonomer A-1 (200.0 g), methacrylic acid (hereinafter also referred to as "MAA", 60.0 g), benzyl methacrylate (hereinafter also referred to as "BzMA", 40.0 g), and PGMEA (propylene glycol 1-monomethyl ether 2-acetate, 366.7 g) into a three-necked flask with a capacity of 1000 mL. The above mixture was stirred while blowing nitrogen. Then, the mixture was heated to 75°C while nitrogen was flowing in the flask. Next, dodecyl mercaptan (5.85 g) was added to the mixture, followed by 2,2'-azobis(methyl 2-methylpropionate) (1.48 g, hereinafter also referred to as "V-601"), and a polymerization reaction was started. After heating the mixture at 75°C for 2 hours, V-601 (1.48 g) was further added to the mixture. After 2 hours, V-601 (1.48 g) was further added to the mixture. After further reacting for 2 hours, the mixture was heated to 90° C. and stirred for 3 hours. The polymerization reaction was completed through the above operation, and a dispersant A was obtained.

[0955] Dispersant B

[0956] Dispersant B is a dispersant produced by the production method shown below.

[0957] Under air, tetrabutylammonium bromide (TBAB, 7.5 g) and p-methoxyphenol (MEHQ, 0.13 g) were added to the solution of dispersant A obtained in Synthesis Example P-1, and then glycidyl methacrylate (GMA, 66.1 g) was added dropwise. After the addition was completed, the reaction was continued for 7 hours under air, and the completion of the reaction was confirmed by acid value measurement. PGMEA (643.6 g) was added to the obtained mixture to obtain a 20% solution of dispersant B. The weight average molecular weight of the obtained dispersant B was 35,000, and the acid value was 50 mgKOH / mg.

[0958] The structures of dispersants C to H are shown below.

[0959] In the structural formulas of dispersants C to F, the numerical values ​​indicated in the respective repeating units represent the mass ratios.

[0960] [Chemical formula 39]

[0961]

[0962] Dispersant I: A resin containing the structural units (1a) to (3a) shown below, having an amine value of 75 mgKOH / g and an acid value of 0 mgKOH / g

[0963] [Chemical formula 40]

[0964]

[0965] In addition, among the dispersants A to I, the dispersants A to G and I correspond to dispersants having a graft structure.

[0966] Dispersant H corresponds to a dispersant having a radial structure.

[0967] Among the dispersants A to I, the dispersants A to H correspond to dispersants containing an acid group.

[0968] The acid value (unit: mgKOH / g), amine value (unit: mgKOH / g), and molecular weight (weight average molecular weight) of the solid content of Dispersants A to I are as follows.

[0969]

[0970] 〔Resin (alkali soluble resin)〕

[0971] The following resins (alkali-soluble resins) were used.

[0972] A-1: Resin with the following structure (solid content 40%, solvent: propylene glycol monomethyl ether, the structure of the solid content (resin) refers to the following structure, and the composition ratio shown in the structure is a molar ratio, and the weight average molecular weight of the resin: 11000, the acid value of the resin: 70 mgKOH / g)

[0973] [Chemical formula 41]

[0974]

[0975] A-2: copolymer of benzyl methacrylate and methacrylic acid in a ratio of 7:3 (molar ratio) (weight average molecular weight: 30,000, acid value: 112.8 mgKOH / g, PGMEA 40 mass % solution)

[0976] 〔Polymerizable compounds〕

[0977] The following polymerizable compounds were used.

[0978] M1: A mixture of compounds having the following structures (the composition ratios shown in the structures are mass ratios):

[0979] [Chemical formula 42]

[0980]

[0981] M2: A mixture of compounds having the following structures (the composition ratios shown in the structures are in mass %)

[0982] [Chemical formula 43]

[0983]

[0984] M3: Compounds with the following structures

[0985] [Chemical formula 44]

[0986]

[0987] M4: A mixture of compounds of the following structures

[0988] [Chemical formula 45]

[0989]

[0990] 〔Polymerization initiator〕

[0991] The following polymerization initiators (photopolymerization initiators) were used. Among the following polymerization initiators, I-1 to I-8 are photopolymerization initiators of oxime compounds. I-9 is a photopolymerization initiator other than an oxime compound.

[0992] I-1: A polymerization initiator of the following formula (I-1)

[0993] I-2: Irgacure OXE01 (product name, manufactured by BASF Japan Ltd.)

[0994] I-3: Irgacure OXE02 (product name, manufactured by BASF Japan Ltd.)

[0995] I-4: A polymerization initiator of the following formula (I-4)

[0996] I-5: A polymerization initiator of the following formula (I-5)

[0997] I-6: A polymerization initiator of the following formula (I-6)

[0998] ·I-7: Adeka Arkls NCI-831 (made by ADEKA CORPORATION)

[0999] ·I-8: N-1919 (made by ADEKA CORPORATION)

[1000] I-9: Omnirad 907 (manufactured by IGM Resins BV)

[1001] [Chemical formula 46]

[1002]

[1003] 〔Surfactant〕

[1004] The surfactants shown below were used.

[1005] F-1: Surfactant represented by the following formula (weight average molecular weight (Mw) = 15311)

[1006] In the following formula, the structural unit represented by (A) accounts for 62 mol%, and the structural unit represented by (B) accounts for 38 mol%. In the structural unit represented by (B), a, b, and c satisfy the relationship of a+c=14 and b=17, respectively.

[1007] [Chemical formula 47]

[1008]

[1009] 〔Inhibitor〕

[1010] The following polymerization inhibitors were used.

[1011] PI-1: p-Methoxyphenol

[1012] 〔Organic solvent〕

[1013] The following organic solvents were used.

[1014] ·PGMEA: Propylene glycol monomethyl ether acetate

[1015] Cyclopentanone

[1016] 〔Silica particles〕

[1017] Silica particles produced by the method described below were used to prepare the composition.

[1018] <Preparation of Silica Particle Dispersion>

[1019] (Synthesis Example 1: Preparation of Silica Particle Dispersion Liquid PS-1)

[1020] 100 g of THRULYA4110 (manufactured by JGC Catalysts and Chemicals Ltd., solid content 20%, isopropanol solvent, hollow silica sol, average primary particle size 60 nm) was mixed with 4 g of KBM-503 (manufactured by Shin-Etsu Chemical Co., LTD., 3-methacryloxypropyltrimethoxysilane), 0.5 g of a 10% by mass aqueous solution of formic acid, and 1 g of water to obtain a mixed solution. The obtained mixed solution was stirred at 60° C. for 3 hours. Furthermore, using a rotary evaporator, the solvent in the mixed solution was replaced with 1-methoxy-2-propanol. The solid content concentration of the mixed solution was confirmed, and it was further diluted with the required amount of 1-methoxy-2-propanol to obtain a silica particle dispersion PS-1 (a dispersion of silica as hollow particles surface-modified with methacryloyl groups) having a solid content of 20% by mass.

[1021] (Synthesis Example 2: Production of Silica Particles S-1)

[1022] Silica particle dispersion PS-1 (dispersion with a solid content of 20% by mass prepared in the previous paragraph) (30.0 g), X-22-2404 (manufactured by Shin-Etsu Chemical Co., LTD., single-end methacrylic acid modified silicone oil, 1.8 g) and PGMEA (propylene glycol monomethyl ether acetate, 28.2 g) were added to a 3-necked flask, and the contents of the flask were heated to 80° C. under a nitrogen atmosphere. Initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation., 0.01 g) was added to the flask and stirred for 3 hours. Furthermore, V-601 (0.02 g) was added to the flask and stirred for 2 hours. Afterwards, the contents of the flask were finely filtered, and the filtrate obtained was set as silica particles S-1.

[1023] (Synthesis Example 3: Production of Silica Particles S-2)

[1024] Silica particles S-2 were obtained in the same manner as in Synthesis Example 2 except that the silica particle dispersion PS-1 in Synthesis Example 2 was changed to a PGM-AC-4130Y dispersion.

[1025] The PGM-AC-4130Y dispersion was obtained by adding 1-methoxy-2-propanol to PGM-AC-4130Y (manufactured by Nissan Chemical Corporation, solid content 32% by mass, 1-methoxy-2-propanol solvent, a dispersion of solid particles of silica surface-modified with methacrylic acid groups) so that the solid content became 20% by mass.

[1026] [Preparation of Composition (Photosensitive Composition)]

[1027] A composition (photosensitive composition) was prepared by the method shown below.

[1028] <Preparation of Pigment Dispersion Liquid 1 (Dispersion Liquid 1)>

[1029] First, a pigment dispersion (dispersion liquid) was prepared.

[1030] The following components were mixed according to the following formulation to prepare a dispersion 1.

[1031] · Any one of black pigment Zr-2 to Zr-9, Vc-1, and Nbc-1: 25 parts by mass

[1032] · PGMEA 30 mass % solution of any one of dispersants A to I (a solution in which any one of dispersants A to I is dissolved in PGMEA at a content of 30 mass % relative to the total mass of the solution): 25 parts by mass

[1033] Cyclopentanone: 50 parts by mass

[1034] · Silica particles S-1 or S-2 as needed: 2.08 parts by mass

[1035] In addition, silica particles S-1 or S-2 are added to dispersion 1 only when the composition to be finally prepared contains silica particles.

[1036] (Dispersion conditions)

[1037] The mixture of the above components was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Corporation. This was used as a dispersion liquid 1.

[1038] · Microbead diameter: φ0.05mm, (zirconia beads made by NIKKATO CORPORATION, YTZ)

[1039] Microsphere filling rate: 65% by volume

[1040] ·Grinding circumferential speed: 10m / sec

[1041] ·Separator circumferential speed: 13m / s

[1042] ·Amount of mixed liquid for dispersion treatment: 15kg

[1043] ·Circulation flow rate (pump supply): 90kg / hour

[1044] ·Processing liquid temperature: 45℃

[1045] Cooling water: water

[1046] Processing time: 22 hours

[1047] <Preparation of Pigment Dispersion Liquid 2 (Dispersion Liquid 2)>

[1048] The following components were mixed according to the following formulation to prepare a dispersion 2. The mixing conditions were the same as those for the dispersion 1.

[1049] Black pigment: any one of Zr-1, Ti-1, V-1 and Nb-1: 25 parts by mass

[1050] · PGMEA 30 mass % solution of any one of dispersants A to I: 25 parts by mass

[1051] Cyclopentanone: 50 parts by mass

[1052] <Preparation of Composition>

[1053] The compositions of each example were prepared by mixing the dispersion 1, the dispersion 2 added as needed, the resin (alkali-soluble resin), the polymerizable compound, the polymerization initiator, the surfactant, the polymerization inhibitor, the PGMEA for solid content adjustment added as needed, and the pure water for water content adjustment. The mixing ratio of each component in each composition was adjusted so that the composition finally obtained satisfied the type and mass ratio of the solid component, the solid content concentration, and the water content described in the table shown in the latter section.

[1054] In addition, before preparing the composition, the organic solvent to be used (including the organic solvent for preparing the dispersion etc.) is subjected to a drying treatment using distillation and a desiccant, and the organic solvent from which the water is removed is used in the preparation of the composition. After mixing the components, it is confirmed that the water content of the obtained composition (the composition in the state where the pure water shown below is not added) is 0.001% by mass or less, and then the required amount of pure water is added to the above composition, thereby adjusting the composition having the water content (mass %) shown in the table.

[1055] In the table, "particle 1" and "particle 2" respectively represent the amount or type of black pigment introduced from dispersion 1 and dispersion 2. "dispersant 1" and "dispersant 2" respectively represent the amount or type of dispersant introduced from dispersion 1 and dispersion 2.

[1056] The water content was measured by the Karl Fischer method according to a known method. Specifically, the water content of the sample was measured using a Karl Fischer titrator (KF-06 manufactured by Mitsubishi Chemical Holdings Corporation), and the water content was determined as water content / mass of the sample×100.

[1057] [evaluate]

[1058] The composition of each example was subjected to the following evaluations.

[1059] [Moisture resistance]

[1060] The composition was applied to an 8-inch glass substrate by a spin coating method at a rotation speed capable of forming a cured film having an OD (optical density) of 3 with respect to light of a wavelength of 940 nm, thereby forming a coating film. The coating film was heat-treated at 100° C. for 2 minutes on a hot plate to obtain a dried film. Next, an i-ray stepper exposure device FPA-5510iZa (manufactured by CANON ELECTRONICS INC.) was used, and a photomask of an area of ​​20 μm×20 μm was exposed at a wavelength of 365 nm at a rate of 500 mJ / cm 2 The dried film was exposed to an exposure amount of . After that, the glass substrate formed with the exposed dried film was placed on a horizontal rotating table of a rotary spray developer (DW-30 model, manufactured by Chemitronics Co., Ltd.), and a rotary immersion development was performed at 23°C for 60 seconds using CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd., organic alkaline solution developer). Next, the glass substrate after the rotary immersion development was fixed on the above-mentioned horizontal rotating table in a vacuum chuck manner, and the glass substrate was rotated at a rotation speed of 50 rpm by a rotating device, and pure water was supplied from a spray nozzle from above the rotation center in a spray state for rinsing treatment, thereby producing a glass substrate with a 20μm×20μm pattern formed on the substrate. The obtained pattern-forming substrate was heat-treated at 220° C. for 1 hour using a clean oven (high-temperature clean oven CLH-300S, manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured film (glass substrate with a cured film).

[1061] The obtained cured film (cured film-attached glass substrate) was stored at 85% humidity and 85°C for 2000 hours, and the OD (optical density) at 400 to 700 nm was measured by UV-3600 (manufactured by Hitachi, Ltd.) before and after the storage. Moisture resistance was evaluated according to the following criteria.

[1062] A: The maximum value of the change in light shielding (OD) before and after the exposure under a humid environment is less than 2% at a wavelength of 400 to 700 nm.

[1063] B: The maximum value of the change in light shielding property (OD) before and after the humidity environment is 2% or more and less than 5% at a wavelength of 400 to 700 nm.

[1064] C: The maximum value of the change in light shielding (OD) before and after the humidity environment is 5% or more at a wavelength of 400 to 700 nm.

[1065] 〔Dispersibility (dispersion stability)〕

[1066] 50 g of the composition just prepared was placed in a 100 mL glass container, which was sealed and left to stand at 45° C. for 7 days. After standing, the viscosity change before and after standing was measured, and the dispersibility (dispersion stability) was evaluated according to the following criteria.

[1067] The viscosity change was determined based on the viscosity before standing as a standard (100%).

[1068] The viscosity was measured at 25° C. using a cone-plate viscometer (manufactured by Toki Sangyo Co., Ltd., model number RE-85L).

[1069] A: The change in viscosity is less than 5%.

[1070] B: The amount of change in viscosity is 5% or more and less than 10%.

[1071] C: The change in viscosity is 10% or more.

[1072] 〔Light-blocking property (visible)〕

[1073] The composition was applied to a glass plate (EagleXG, Corning) with a thickness of 0.7 mm and a square of 10 cm by a spin coating method at a rotation speed of 1.5 μm to form a coating film, and the coating film was heat-treated at 100° C. for 2 minutes on a hot plate to obtain a dry film. The OD (optical density) of the obtained dry film was measured for light with a wavelength of 400 to 700 nm using UV-3600 (manufactured by Hitachi, LTD.). The minimum OD of 400 to 700 nm was confirmed, and the spectral (light-shielding) evaluation was performed using the following criteria.

[1074] A: OD>3.0

[1075] B: 3.0≥OD>2.0

[1076] C: 2.0 ≥ OD

[1077] 〔Light blocking properties (940nm)〕

[1078] The composition was applied to a glass plate (EagleXG, Corning) with a thickness of 0.7 mm and a square of 10 cm by a spin coating method at a rotation speed such that the film thickness of the dry film became 1.5 μm to form a coating film, and the coating film was heat-treated at 100° C. for 2 minutes on a hot plate to obtain a dry film. The OD (optical density) of the obtained dry film was measured by UV-3600 (manufactured by Hitachi, LTD.) for light with a wavelength of 940 nm. The spectral (light-shielding) evaluation was performed according to the following criteria.

[1079] A: OD>3.0

[1080] B: 3.0≥OD>2.0

[1081] C: 2.0 ≥ OD

[1082] 〔Patternization〕

[1083] The composition was applied to an 8-inch silicon wafer substrate by a spin coating method at a rotation speed capable of forming a cured film having an OD (optical density) of 3 relative to light of a wavelength of 940 nm, thereby forming a coating film. The coating film was heat treated at 100° C. for 2 minutes on a hot plate to obtain a dried film. Next, an i-ray stepper exposure device FPA-5510iZa (manufactured by CANON ELECTRONICS INC.) was used, and a photomask of an area of ​​20 μm×20 μm was exposed at a wavelength of 365 nm at a rate of 500 mJ / cm 2 The dry film was exposed to an exposure amount of . After that, the silicon wafer substrate formed with the exposed dry film was placed on the horizontal rotating table of a rotary spray developer (DW-30 model, manufactured by Chemitronics Co., Ltd.), and was subjected to 60 seconds of spin-up immersion development at 23°C using CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd., organic alkaline solution developer). Next, the silicon wafer substrate after the spin-up immersion development was fixed on the above-mentioned horizontal rotating table in a vacuum chuck manner, and the silicon wafer substrate was rotated at a rotation speed of 50 rpm by a rotating device, while pure water was supplied from a spray nozzle from above the rotation center in a spray state for rinsing treatment, thereby producing a silicon wafer substrate with a 20μm×20μm pattern formed on the substrate. The obtained pattern-forming substrate was heat-treated at 220° C. for 1 hour using a clean oven (High-temperature clean oven CLH-300S, manufactured by Koyo ThermoSystems Co., Ltd.) to obtain a cured film (cured film-attached substrate).

[1084] The obtained cured film (cured film-attached substrate) was observed by cross-sectional SEM (scanning electron microscope), and patterning properties were evaluated based on the following criteria.

[1085] A: The width of the space between the cured film and the substrate (the width at which the cured film peels off) is less than 5 μm from the pattern edge.

[1086] B: The width of the space between the cured film and the substrate (the width at which the cured film peels off) is 5 μm or more from the pattern edge.

[1087] C: 20μm×20μm pattern peeled off and could not be measured

[1088] [Alignment mark visibility]

[1089] The composition was applied to an 8-inch silicon substrate having an alignment mark by a spin coating method at a rotation speed capable of forming a dry film having an OD (optical density) of 3 relative to light of a wavelength of 940 nm, thereby forming a coating film. The coating film was heat-treated at 100° C. for 2 minutes on a hot plate to obtain a dry film (silicon substrate with a dry film). Three such silicon substrates with dry films were prepared using each composition. Next, the visibility of the alignment mark was evaluated from the following viewpoints using an i-ray stepper exposure device FPA-5510iZa (manufactured by CANON ELECTRONICS INC.).

[1090] A: Among the 3 pieces, the alignment marks of all 3 pieces are visible

[1091] B: Among the three pieces, the alignment marks of 1 to 2 pieces are visible (1 or 2 pieces are not visible)

[1092] C: Among the 3 pieces, the alignment marks of all 3 pieces are not visible

[1093] [result]

[1094] The following table shows the solid content formulation and characteristics of the composition used in each test example and the test results.

[1095] In the table, the amount of each component recorded in the column "Solid content" represents the content (mass %) of each component relative to the total solid content of the composition. In addition, the content of each component recorded in the column "Solid content" is the content of the solid content of each component itself. For example, a resin (alkali-soluble resin) is used in the preparation of a composition in the form of a dispersed solution in which the resin (solid content) is dissolved in an organic solvent, and the value of the content of the resin recorded in the table represents the content (mass %) of the resin (solid content) itself relative to the total solid content of the composition.

[1096] In the table, the column "Type" indicates more specific types of each component used in the preparation of the composition. In addition, the record "M2 / M4=83 / 17" in the column "Polymerizable compound" under the column "Type" indicates that M2 and M4 are used simultaneously at a ratio of M2 / M4=83 / 17 (mass ratio).

[1097] In the table, "Particle 1" and "Particle 2" respectively represent the amount or type of black pigment added from dispersion 1 and dispersion 2. "Dispersant 1" and "Dispersant 2" respectively represent the amount or type of dispersant added from dispersion 1 and dispersion 2.

[1098] In the table, the column "Polymerizable compound not containing an acid group" indicates whether the polymerizable compound used is a polymerizable compound not having an acid group. If this requirement is satisfied, it is designated as "A", and if not, it is designated as "B".

[1099] In the table, the column "Oxime-based polymerization initiator" indicates whether the polymerization initiator used is a photopolymerization initiator of an oxime compound. If this requirement is satisfied, it is designated as "A", and if not, it is designated as "B".

[1100] In the table, the column "Pigment concentration (mass %)" shows the content (mass %) of the black pigment relative to the total solid content of the composition.

[1101] In the table, the column “Coating type of particle 1 ” indicates the type of coating layer in particle 1 .

[1102] In the table, the column “Coating type of particle 1 (mass %)” shows the content (coating amount, mass %) of the coating layer (metal oxide) relative to the total mass of the particle 1 .

[1103] In the table, the column "Polymerizable Dispersant" indicates whether the dispersant used has a polymerizable group (curable group). If this requirement is met, it is designated as "A", and if it is not met, it is designated as "B".

[1104] In the table, the columns “Ratio of Particle 1 (mass %)” and “Ratio of Particle 2 (mass %)” indicate the content (mass %) of Particle 1 or Particle 2 relative to the total content of Particle 1 and Particle 2 .

[1105] In the table, the column "Water content (mass %)" shows the water content (mass %) of each composition.

[1106] [Table 1]

[1107]

[1108] [Table 2]

[1109]

[1110] [Table 3]

[1111]

[1112] [Table 4]

[1113]

[1114] [Table 5]

[1115]

[1116] [Table 6]

[1117]

[1118] It was confirmed that the light-shielding film (cured film) formed using the composition of the present invention has excellent moisture resistance. In addition, it was confirmed that the dispersibility and patterning properties of the composition of the present invention are also good. Furthermore, it was confirmed that the light-shielding film (cured film) formed using the composition of the present invention has good light-shielding properties for visible light and infrared light, and the alignment mark visibility is also good.

[1119] From the viewpoint of more excellent dispersibility of the composition, it was confirmed that the metal oxide in the metal oxide coating layer preferably contains aluminum oxide (see comparison of Example 1 and Example 5, etc.).

[1120] From the viewpoint of better moisture resistance and / or visible light shielding properties of the cured film, it was confirmed that the content of the metal oxide coating layer is preferably 3 to 7% by mass relative to the total mass of the coated particles (see comparison of Examples 2 to 8, etc.).

[1121] From the viewpoint of more excellent dispersibility of the composition, it was confirmed that the content of water is preferably 0.01 to 3.0% by mass relative to the total mass of the composition (see comparison of Examples 11 to 14, etc.).

[1122] From the viewpoint of better infrared light shielding properties of the cured film, it is confirmed that the black pigment preferably contains a black pigment that is different from the coated particles and is a nitride or oxynitride of one or more metals selected from titanium, vanadium and niobium (see comparison of Example 1, Examples 15 to 23, Example 36, Example 37, Example 38, etc.).

[1123] Furthermore, it was confirmed that the content of the coated particles is preferably 50 to 90% by mass relative to the total mass of the black pigment from the viewpoint of more excellent patterning properties (see comparison of Examples 15 to 23, etc.).

[1124] From the viewpoint of better shading properties against visible light, shading properties against infrared light, patterning properties and / or visibility of alignment marks, it is confirmed that the content of black pigment is preferably 40 to 70 mass % (more preferably more than 40 mass % and less than 70 mass %) relative to the total solid content of the composition (refer to comparison of Example 15, Examples 24 to 26, etc.).

[1125] From the viewpoint of more excellent patterning properties, it was confirmed that it is preferable to contain an oxime compound as a photopolymerization initiator (see Example 15, and comparison of Examples 28 to 35, etc.).

[1126] From the viewpoint of more excellent patterning properties, it was confirmed that the dispersant preferably contains a polymerizable group (curable group) (see Example 15, and comparison of Examples 39 to 46, etc.).

[1127] From the viewpoint of more excellent dispersibility, it was confirmed that the dispersant preferably contains an acid group (see Example 15, and comparison of Examples 39 to 46, etc.).

[1128] From the viewpoint of better patterning properties, it was confirmed that the content of the polymerizable compound not containing an acid group is preferably 50 to 100% by mass relative to the total mass of the polymerizable compound (see Example 15, and comparison of Examples 47 to 50, etc.).

[1129] In Example 13, the evaluation was performed in the same manner without adding a surfactant, and the same results were obtained. In Example 13, the evaluation was performed in the same manner without adding a polymerization inhibitor, and the same results were obtained.

[1130] <<Test Y>>

[1131] [Application in various uses]

[1132] The applicability of the compositions of Examples (Examples 1 to 11 and 13 to 49) used in the above-mentioned <<Test X>> to various applications was confirmed by the method shown below.

[1133] 〔Fabrication and evaluation of light-shielding films for wafer-level lenses〕

[1134] The lens film was formed by the following operation.

[1135] 1. Formation of thermosetting cured film

[1136] A curable composition for a lens (a composition obtained by adding 1% by mass of an aryl sulfonium salt derivative (SP-172 manufactured by ADEKA CORPORATION) to an alicyclic epoxy resin (EHPE-3150 manufactured by Daicel Corporation) (2 mL) was applied on a 5×5 cm glass substrate (1 mm thick, manufactured by SCHOTT, BK7), and the coating was heated at 200°C for 1 minute and cured to form a film capable of evaluating residues on the lens.

[1137] 2. Evaluation on the lens

[1138] The composition of the example used in the above-mentioned <<Test X>> was applied to the glass wafer (support) on which the above-mentioned lens film was formed, and the support coated with the composition was heated for 120 seconds by a hot plate having a surface temperature of 120° C. In this way, a coating film (composition layer) having a film thickness of 2.0 μm was obtained.

[1139] <Exposure process>

[1140] Next, a high-pressure mercury lamp was used to expose the light at an exposure dose of 500 mJ / cm 2 The obtained composition layer was exposed to light.

[1141] <Development process>

[1142] The exposed composition layer was subjected to spin immersion development for 60 seconds at 23° C. using a 0.3% aqueous solution of tetramethylammonium hydroxide. Thereafter, the developed composition layer was rinsed by spin spraying, and the rinsed composition layer was further washed with pure water, thereby obtaining a patterned light-shielding film (cured film).

[1143] 〔Fabrication and evaluation of solid-state imaging devices〕

[1144] A curable resin layer was formed on the substrate having the patterned light-shielding film prepared above using a curable composition for a lens (a composition obtained by adding 1% by mass of an arylsulfonium salt derivative (SP-172 manufactured by ADEKA CORPORATION) to an alicyclic epoxy resin (EHPE-3150 manufactured by Daicel Corporation) and the shape was transferred using a quartz mold having a lens shape and irradiated with a high-pressure mercury lamp at 400 mJ / cm 2 The exposure amount is set to cure it, thereby producing a wafer-level lens array having multiple wafer-level lenses.

[1145] The manufactured wafer-level lens array is cut and a lens module is manufactured using the obtained wafer-level lens. Then, an imaging element and a sensor substrate are mounted to manufacture an imaging unit.

[1146] The obtained wafer-level lens has good transmittance without any residue in the lens opening, and the light-shielding layer has high uniformity on the coating surface and high light-shielding property.

[1147] [Manufacturing of color filter with black matrix]

[1148] <Formation of black matrix>

[1149] The composition of the example used in the above-mentioned <<Test X>> was applied onto a glass wafer by spin coating, and then the glass wafer was heated on a hot plate at 120° C. for 2 minutes to obtain a coating film (composition layer). The rotation speed by the spin coating method was adjusted so that the film thickness of the coating film was 2.0 μm.

[1150] Next, an i-ray stepper was used to irradiate the laser beam at 500 mJ / cm through a photomask having an island pattern of 0.1 mm. 2 The obtained composition layer was exposed to light at an exposure amount of .

[1151] The exposed composition layer was subjected to spin immersion development for 60 seconds at 23° C. using a 0.3% aqueous solution of tetramethylammonium hydroxide. Thereafter, the developed composition layer was rinsed by spin spraying, and the rinsed composition layer was further washed with pure water, thereby obtaining a patterned light-shielding film (black matrix).

[1152] <Preparation of Color Curable Composition>

[1153] In the composition of Example 1 in the above-mentioned "Test X", except that Zr-2 in the dispersion 1 was replaced with the following color pigment, a colored curable composition R-1 for red (R), a colored curable composition G-1 for green (G), and a colored curable composition B-1 for blue (B) were prepared in the same manner.

[1154] ·Color pigments for forming RGB color pixels

[1155] ··Red (R) pigment

[1156] CI Pigment Red 254

[1157] ··Green (G) pigment

[1158] A 30 / 70 (mass ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 219

[1159] ··Blue (B) pigment

[1160] A 30 / 70 mixture of CI Pigment Blue 15:6 and CI Pigment Violet 23 (mass ratio)

[1161] <Color filter production>

[1162] The same method as the method for preparing the black matrix prepared above was used, and a 80×80 μm red (R) coloring pattern was formed in the black matrix prepared above using the red (R) colored curable composition R-1. Furthermore, in the same manner, a green (G) coloring pattern was formed using the green (G) colored curable composition G-1, and a blue (B) coloring pattern was formed using the blue (B) colored curable composition B-1, thereby preparing a color filter having a black matrix for a liquid crystal display device.

[1163] It was confirmed that the composition of the present invention can also be suitably used for a black matrix for color filters.

[1164] Explanation of symbols

[1165] 10-headlamp unit, 12-light source, 14-light shielding portion, 16-lens, 20-base, 22-light shielding film, 23-opening portion, 30-light distribution pattern, 30a-edge, 31-region, 32-light distribution pattern, 32a-edge, 33-notch portion, 34-region, 100-solid-state imaging device, 101-solid-state imaging element, 102-imaging portion, 103-cover glass, 104-spacer, 105-laminated substrate, 106-chip substrate, 107-circuit substrate, 108-electrode pad, 109-external connection terminal, 110-through electrode, 111-lens layer, 112-lens material, 113-support body, 114, 115-light shielding film, 201 -light receiving element, 202-color filter, 203-microlens, 204-substrate, 205b-blue pixel, 205r-red pixel, 205g-green pixel, 205bm-black matrix, 206-p well layer, 207-readout gate portion, 208-vertical transfer path, 209-element separation region, 210-gate insulating film, 211-vertical transfer electrode, 212-light shielding film, 213, 214-insulating film, 215-planarization film, 300-infrared sensor, 310-solid-state imaging element, 311-infrared absorption filter, 312-color filter, 313-infrared transmission filter, 314-resin film, 315-microlens, 316-planarization film.

Claims

1. A photosensitive composition comprising a black pigment, a resin, a polymerizable compound and a photopolymerization initiator, The black pigment contains coated particles, The coated particles include metal-containing particles and a metal oxide coating layer formed of a metal oxide coating the metal-containing particles, the metal-containing particles are formed of a nitride or oxynitride of one or more metals selected from zirconium, vanadium and niobium, and the metal oxide includes aluminum oxide.

2. The photosensitive composition according to claim 1, wherein The metal oxide contains silicon dioxide.

3. The photosensitive composition according to claim 1 or 2, wherein The black pigment further includes a black pigment which is different from the coated particles and is a nitride or oxynitride of one or more metals selected from the group consisting of titanium, zirconium, vanadium, and niobium.

4. The photosensitive composition according to claim 1 or 2, wherein The photopolymerization initiator contains an oxime compound.

5. The photosensitive composition according to claim 1 or 2, wherein The content of the black pigment is 40% by mass to 70% by mass based on the total solid content of the photosensitive composition.

6. The photosensitive composition according to claim 1 or 2, wherein The resin includes at least one of a resin containing a structural unit having a graft chain and containing an acid group, and a resin containing a radial structure and containing an acid group.

7. The photosensitive composition according to claim 1 or 2, wherein The content of the metal oxide coating layer is 3% to 7% by mass relative to the total mass of the coated particles.

8. The photosensitive composition according to claim 1 or 2, further comprising water, The content of the water is 0.01% by mass to 3.0% by mass based on the total mass of the photosensitive composition. 9 . The photosensitive composition according to claim 1 , further comprising silica particles. 10 . A cured film formed using the photosensitive composition according to claim 1 . A light-shielding film, which is the cured film according to claim 10. 12 . A color filter comprising the cured film according to claim 10 . 13 . An optical element comprising the cured film according to claim 10 . 14 . A solid-state imaging element comprising the cured film according to claim 10 . 15 . An infrared sensor comprising the cured film according to claim 10 .

16. A headlamp unit, which is a vehicle headlamp unit, comprising: light source; and a light shielding portion that shields at least a portion of the light emitted from the light source, The light-shielding portion includes the cured film according to claim 10 .

Images