Light-shielding film, solid-state imaging element, image display device, infrared sensor

Abstract

The first objective of this invention is to provide a light-shielding film with excellent light-shielding properties and low infrared light reflectivity. Furthermore, the second objective of this invention is to provide a solid-state imaging element, an image display device, and an infrared sensor incorporating the aforementioned light-shielding film. The light-shielding film of this invention contains a black pigment, and the light-shielding film has a phase-separated structure consisting of a first phase containing the aforementioned black pigment and a second phase substantially free of the aforementioned black pigment. The cross-section of the light-shielding film orthogonal to the surface measures 1 × 1 μm. When the range is 2, the total length of the boundary line between the first phase and the second phase is 2.50 to 15.00 μm.

Description

Technical Field

[0001] This invention relates to a light-shielding film, a solid-state camera element, an image display device, and an infrared sensor. Prior Art

[0002] Image display devices such as liquid crystal displays (LCDs) and solid-state imaging devices such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors often have light-shielding films placed at designated locations. For example, in LCDs, to improve contrast by blocking light between colored pixels, a light-shielding film, sometimes called a black matrix, is placed between the colored pixels on the color filter. Furthermore, in solid-state imaging devices, light-shielding films are sometimes used to prevent noise and improve image quality. The formation of these light-shielding films typically uses compositions containing black pigments.

[0003] For example, the main point disclosed in Patent Document 1 is that a pigment dispersion composition containing two dispersants with different SP values ​​is used. By the phase separation effect of the two dispersants, a light-shielding film having a concave-convex structure on the surface and a black pigment uniformly dispersed in the film can be formed.

[0004] [Patent Document 1] International Publication No. 2016 / 129342

[0005] Based on their research on the light-shielding film described in Patent Document 1, the inventors discovered that there is room for further improvement in the reflectivity of infrared light. Summary of the Invention

[0006] Therefore, the objective of this invention is to provide a light-shielding film with excellent light-shielding properties and low infrared light reflectivity. Furthermore, the present invention also provides a solid-state imaging element, an image display device, and an infrared sensor having the above-mentioned light-shielding film.

[0007] As a result of in-depth research conducted by the inventors in order to solve the above-mentioned problems, they discovered that the above-mentioned problems can be solved by the following configuration.

[0008] [1] A light-shielding film comprising a black pigment, wherein The light-shielding film has a phase-separated structure consisting of a first phase containing the black pigment and a second phase substantially not containing the black pigment. When observing the range of 1×1μm2 of the cross section orthogonal to the surface of the above-mentioned light-shielding film, the total length of the boundary line between the first phase and the second phase is 2.50~15.00μm. [2] The light-shielding film as described in [1], wherein The surface roughness Ra is 400~2000 Å. [3] The light-shielding film as described in [1] is formed using a composition comprising black pigment, resin and polymeric compound. [4] The light-shielding film as described in any one of [1] to [3], wherein The total length is 2.50~7.00μm. [5] The light-shielding film as described in any one of [1] to [4], wherein The first phase comprises a first resin having an acid value of 40 to 100 mgKOH / g, The aforementioned second phase includes a second resin with an acid value of 40~90 mgKOH / g. [6] The light-shielding film as described in [5], wherein The weight-average molecular weight of the first resin mentioned above is 20,000 to 40,000. The weight average molecular weight of the second resin mentioned above is 15,000 to 40,000. [7] The light-shielding film as described in [5] or [6], wherein The glass transfer temperature of the first resin mentioned above is -10~60℃. The glass transition temperature of the second resin is 0 to 70°C. [8] The light-shielding film according to any one of [1] to [7], wherein The aforementioned black pigment contains particles selected from the group consisting of metal nitride particles and metal oxide nitride particles. [9] The light-shielding film described in any one of [1] to [8] is patterned.

[10] A solid-state imaging element comprising the light-shielding film described in any one of [1] to [9].

[11] An image display device comprising the light-shielding film described in any one of [1] to [9].

[12] An infrared sensor comprising a light-shielding film as described in any one of [1] to [9]. [Effects of the Invention]

[0009] According to the present invention, a light-shielding film with excellent light-shielding properties and low infrared light reflectivity can be provided. Furthermore, according to the present invention, a solid-state imaging element, an image display device, and an infrared sensor including the light-shielding film can be provided. Simple diagram description

[0010] FIG1 is a schematic diagram schematically showing an example of a phase separation structure (sea-island structure) in a cross section T of a light-shielding film. Figure 2 is a schematic diagram of an example of a phase separation structure (co-continuous structure) of the cross section T of the light-shielding film. FIG3 is a schematic diagram showing an example of a SEM image of a cross section T after trimming. Figure 4 is a schematic diagram of the SEM image in Figure 3 after black and white binarization. Figure 5 is a schematic diagram illustrating the edge search method for the black-and-white binary image in Figure 4. Implementation Method

[0011] The present invention will now be described in detail. The description of the constituent elements described below may be completed based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. Furthermore, in this specification, the numerical range represented by "~" refers to the range including the values ​​recorded before and after "~" as the lower and upper limits.

[0012] Furthermore, in this specification, the term "group" (atomic group) not indicating "substituted" or "unsubstituted" includes not only groups without substituents but also 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).

[0013] Furthermore, in this specification, "active light" or "radiation" refers to, for example, far-ultraviolet light, extreme ultraviolet (EUV) lithography, X-rays, and electron beams. Also, in this specification, light refers to active light and radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure based on far-ultraviolet, X-ray, and EUV light, but also depiction based on particle beams such as electron beams and ion beams.

[0014] Furthermore, in this specification, "(meth)acrylate" refers to acrylate and methacrylate. Also, in this specification, "(meth)acrylic acid" refers to acrylic acid and methacrylic acid. Also, in this specification, "(meth)acrylyl" refers to acrylyl and methacrylyl. Also, in this specification, "(meth)acrylamine" refers to acrylamine and methacrylamine. Also, in this specification, "monomer" and "monomer" have the same meaning.

[0015] In this specification, the weight-average molecular weight (Mw) is a converted value for polystyrene based on GPC (Gel Permeation Chromatography). In this specification, the GPC method is based on the following approach: using an HLC-8020 GPC (manufactured by Tosoh Corporation), with TSKgel Super HZM-H, TSKgel Super HZ4000, or TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6mm ID × 15cm) as the column and THF (tetrahydrofuran) as the eluent.

[0016] In this specification, solid components in a composition refer to the composition layer formed using the composition. When the composition contains a solvent, it refers to all components other than the solvent. Furthermore, liquid components are also considered solid components as long as they form a composition layer.

[0017] [Light-shielding film] The light-shielding film of the present invention contains a black pigment and has a phase-separated structure consisting of a first phase containing the black pigment and a second phase that substantially does not contain the black pigment. When observing a 1×1μm² section of the light-shielding film orthogonal to the surface, the total length of the boundary lines of the first phase and the second phase (hereinafter also referred to as "boundary distance L") is 2.50~15.00μm.

[0018] As a first characteristic of the light-shielding film of the present invention, it can be cited that it has a phase separation structure consisting of a first phase containing black pigment and a second phase that substantially does not contain black pigment. Furthermore, as a second characteristic of the present invention, when observing a 1×1μm² section of the light-shielding film orthogonal to the surface, the boundary distance L between the first phase and the second phase is within a specified numerical range. Hereinafter, the configuration and the presumed mechanism of action of the present invention will be described. It is speculated that the light-shielding film of the present invention, as described above, has a fine uneven structure formed on its surface, resulting in excellent low reflectivity. That is, it is believed that the light-shielding film of the present invention has a phase-separated structure composed of a first phase and a second phase. By controlling the domain size and distribution of the first and second phases to adjust the boundary distance L to a predetermined length, an uneven structure originating from the phase-separated structure is formed on the surface of the light-shielding film, thereby achieving low reflectivity. Regarding the correlation between the boundary distance L and low reflectivity, it is shown in the embodiment section of this specification. When the boundary distance L is less than 2.50 μm, the region of the first phase is too large (the region of the first phase becomes larger than the wavelength of light), and the desired low reflectivity is not exhibited. Furthermore, when the boundary distance L exceeds 15.00 μm, the region of the first phase is too small (that is, the uneven structure on the surface of the light-shielding film is too small), and the desired low reflectivity is not exhibited. Furthermore, the method for measuring the boundary distance L will be described later. Furthermore, the light-shielding film of the present invention also has excellent light-shielding properties because it contains black pigment.

[0019] Hereinafter, the superior low-reflection characteristics of the light-shielding film of the present invention and / or the superior light-shielding performance of the light-shielding film of the present invention are sometimes referred to as "superior effects of the present invention".

[0020] Hereinafter, the structure of the light-shielding film of the present invention will be described in detail first, and then the components and formation method of the light-shielding film will be described in detail. The light-shielding film of the present invention is typically a resin film containing black pigment. The light-shielding film has a phase-separated structure consisting of a first phase containing black pigment and a second phase that does not substantially contain black pigment. Examples of phase-separated structures include island structures, co-continuous structures, and structures where island and co-continuous structures coexist. When the light-shielding film has an island structure, observing a section of the film orthogonal to its surface (in other words, the section exposed when the film is cut perpendicular to its surface; hereinafter referred to as "section T"), for example, as shown in Figure 1, reveals a structure where the first phase (dispersed phase (A in the figure)) is dispersed within the second phase (continuous phase (B in the figure)). Furthermore, when the light-shielding film has a co-continuous structure, observing section T, for example, as shown in Figure 2, reveals a complex three-dimensional network structure formed by the first phase (A in the figure) and the second phase (B in the figure). The surface structure of section T can be observed using a scanning electron microscope (SEM) (e.g., Hitachi High-Tech Corporation "S-4800"). As conditions for SEM observation, for example, it is preferable to observe the reflected electron image under the conditions of observation magnification: 5000 to 25000 times and acceleration voltage: 3.0 to 5.0 keV.

[0021] The first phase containing the black pigment is generally a phase containing the black pigment and a resin. Furthermore, the second phase that does not substantially contain a black pigment is usually a phase that does not substantially contain a black pigment but contains a resin. Furthermore, in this specification, the determination of whether the phase contains black pigment is performed by observing and analyzing the cross-section T of the light-shielding film using energy-dispersive X-ray spectroscopy (SEM-EDX). Specifically, the determination method is as follows. First, a surface structure image of the cross section T of the light-shielding film is obtained using SEM. When visually observing the obtained SEM image, a pattern of varying shades can be observed, consisting of two regions with varying shades (a dark image region and a light image region). (For example, a pattern of varying shades such as island structures, co-continuous structures, and structures where island structures and co-continuous structures coexist.) Next, an area of ​​0.1 μm × 0.1 μm (vertical × horizontal) is randomly selected from the light image region of the pattern within the field of view (hereinafter, also referred to as "Region A"). Elemental analysis (EDX) is performed on Region A to determine its atomic composition (atom%). Then, an area of ​​0.1 μm × 0.1 μm (vertical × horizontal) is randomly selected from the dark image region of the pattern within the field of view (hereinafter, also referred to as "Region B"). Elemental analysis is performed on Region B to determine its atomic composition (atom%). Finally, within each region of Region A and Region B, the content (atom%) of the atoms with the highest concentration in the black pigment is determined. Here, the atom with the highest content among the atoms contained in the black pigment refers to the atom with the highest content (mass %) among the atoms constituting the black pigment relative to the total mass of the black pigment. Furthermore, for example, if the black pigment is titanium black, the atom with the highest content among the atoms constituting the black pigment is titanium. Here, in Region A, when the content (atom%) of the atoms that account for the largest proportion of the atoms contained in the black pigment is 15 atom% or less, the entire light image region including Region A is considered to contain no black pigment. When the content (atom%) of the atoms that account for the largest proportion of the atoms contained in the black pigment exceeds 15 atom%, the entire light image region including Region A is considered to contain black pigment. Similarly to Region A, with respect to Region B, when the content (atom%) of the atoms that account for the largest proportion of the atoms contained in the black pigment is 15 atom% or less, the entire dark image region including Region B is considered to contain no black pigment. When the content (atom%) of the atoms that account for the largest proportion of the atoms contained in the black pigment exceeds 15 atom%, the entire dark image region including Region B is considered to contain black pigment. Furthermore, when regions A and B contain black pigment, it is preferable that the percentage of the most abundant atom in the black pigment is 40% or higher. In this invention, there are often cases where black pigment is contained in the light image region including region A, and black pigment is not contained in the dark image region including region B.

[0022] In the light-shielding film of the present invention, when observing a 1×1 μm² cross-section T, the total length of the boundary between the first and second phases (boundary distance L) is 2.50 to 15.00 μm. The method for measuring the boundary distance L is described below with reference to Figures 3 to 5.

[0023] [Method for determining boundary distance L] First, a surface structure image of the cross section T of the light-shielding film is obtained using SEM. As an apparatus, for example, "S-4800" manufactured by Hitachi High-Tech Corporation can be used. Furthermore, as observation conditions, for example, it is preferable to observe the reflected electron image under the conditions of observation magnification: 5.0k (5000 times) and acceleration voltage: 2.0 keV. Next, trim an arbitrary 6 μm × 15 μm area in the acquired SEM image of cross-section T. Figure 3 shows an example of an SEM image trimmed to a predetermined size. In the SEM image of Figure 3, the gray area corresponds to the first phase, and the black area corresponds to the second phase.

[0024] Next, the rectified SEM images were binarized using image processing software (ImageJ) (select the “Make Binary” option from the “Process” menu in ImageJ). Following the above sequence, if a pixel is below a specified tone, it is set to "black"; if a pixel exceeds a specified tone, it is set to "white," thus performing binarization. Figure 4 is a schematic diagram of the SEM image in Figure 3 after black-and-white binarization. In Figure 4, the areas displayed as "white" by binarization correspond to the first phase, and the areas displayed as "black" by binarization correspond to the second phase. Furthermore, when setting the threshold values ​​for the pixel tones in the above sequence, it is better to select the "Threshold" option from the "Adjust" menu in ImageJ and adjust the position of the two bars in the Threhold window so that the value displayed in the histogram of the Threhold window is in the range of 40-60%.

[0025] Next, using image processing software (ImageJ), search for and extract the boundary lines (also called "edges") between the first and second phases of the acquired binarized image. The boundary lines are equivalent to the contour lines of the boundary between the first and second phases. (Select the "Find Edges" option from the "Process" menu in ImageJ). Figure 5 is a schematic diagram showing the state of the boundary lines extracted from the black-and-white binary image of Figure 4. Following the above sequence, the boundary lines between the first phase (displayed as "white") and the second phase (displayed as "black") are extracted. Then, using image processing software (ImageJ), the number of pixels of the above boundary line is measured, and the obtained number of pixels is converted into distance (number of pixels × pixel spacing (μm)). The total length of the boundary line of the first phase and the second phase (total boundary distance L0) is calculated (select the "Histgram" option from the "Anarize" menu in ImageJ, and then select the "List" option from the "Histgram" menu).

[0026] Next, the calculated total boundary distance L0 is normalized by the observation area (6μm×15μm) of the modified SEM image to obtain the total interface distance L1 per 1μm×1μm (the total length of the boundary lines of the first and second phases within a 1×1μm 2 area of ​​section T (boundary distance L1)).

[0027] Following the above sequence, the boundary distance L1 is calculated for the three cross-sections of the light-shielding film, and the average value is taken as the boundary distance L.

[0028] In the light-shielding film of the present invention, the boundary distance L is 2.50~15.00 μm. From the perspective of further improving the effect of the present invention, 2.50~10.00 μm is preferred, and 2.50~7.00 μm is even more preferred. When the boundary distance L is less than 2.50 μm, the region of the first phase is too large (the region of the first phase becomes larger than the wavelength of light) and the desired low reflectivity characteristics are not exhibited. Furthermore, when the boundary distance L exceeds 15.00 μm, the region of the first phase is too small (that is, the surface unevenness of the light-shielding film is too small) and the desired low reflectivity characteristics are not exhibited.

[0029] Furthermore, there is no particular limitation on the surface roughness of the light-shielding film of the present invention. However, considering the superior effect of the present invention, a surface roughness Ra of 20 to 3000 Å is preferred, 200 to 2000 Å is even better, and 400 to 2000 Å is even more preferred. The above values ​​are equivalent to those obtained by measuring the surface roughness of the resin film over a distance of 1 mm using the DektakXT manufactured by BRUKER, with a resolution of 1 μm / point.

[0030] There is no particular limitation on the thickness of the light-shielding film of the present invention. However, considering the superior effect of the present invention, 0.2~10μm is preferred, and 0.5~3μm is even better.

[0031] [The various components of the light-blocking film] Next, the various components of the light-blocking film will be explained. <Black pigment> The light-blocking film contains black pigment. In this specification, black pigment refers to pigment that absorbs across the entire wavelength range of 400 to 700 nm. More specifically, for example, the black pigments described below are preferred for evaluation criterion Z. First, a composition containing a black pigment, a transparent resin matrix (such as an acrylic resin), and a solvent is prepared, with the black pigment content being 60% by mass relative to the total solids. The resulting composition is applied to a glass substrate until the cured film reaches a thickness of 1 μm after drying to form a cured film. The light-shielding properties of the cured film after drying are evaluated using a spectrophotometer (such as a UV-3600 manufactured by Hitachi, Ltd.). If the maximum transmittance of the cured film after drying at a wavelength of 400-700 nm is less than 10%, the colorant is considered to be a black pigment suitable for evaluation criterion Z. Under evaluation criterion Z, a maximum transmittance of the black pigment at a wavelength of 400-700 nm after drying is preferably less than 8%, and even more preferably less than 5%.

[0032] As a black pigment, it can be combined with multiple pigments that cannot be used as black pigments on their own, and adjusted to become black as a whole. For example, a combination of multiple pigments that have colors other than black when used alone can be used as a black pigment.

[0033] As the black pigment, a pigment that produces black alone is preferred. Alternatively, a black pigment that produces black alone and absorbs infrared light may be used. Here, the infrared absorbing black pigment has absorption in the infrared region (preferably a wavelength of 650 to 1300 nm). Black pigments having a maximum absorption wavelength in the wavelength range of 675 to 900 nm are also preferred.

[0034] As a black pigment, various well-known black pigments can be used. Black pigments can be inorganic or organic pigments. From the perspective of achieving better results in this invention, it is preferable that the black pigment is an inorganic pigment, and even more preferable that it is a metal nitride particle or a metal nitride particle.

[0035] (Inorganic pigments) As an inorganic pigment that can be used as a black pigment, there are no particular restrictions as long as it is an opaque particle containing an inorganic compound, and known inorganic pigments can be used. As inorganic pigments, examples include metal oxides, metal nitrides and metal oxynitrides, and metal nitrides or metal oxynitrides are preferred from the perspective of better performance of the present invention.

[0036] Examples of the inorganic pigment include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), yttrium (Y), aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag). Preferred are metal oxides, metal nitrides, or metal oxynitrides containing one or more metal elements selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V), yttrium (Y), aluminum (Al), and iron (Fe). In other words, the inorganic pigment may contain two or more metal atoms. The metal oxides, metal nitrides, and metal oxynitrides may be particles further mixed with other metal atoms. For example, metal nitride-containing particles further containing atoms selected from Groups 13 to 17 of the periodic table (preferably oxygen and / or sulfur atoms) may be used. Furthermore, the above-mentioned metal oxides, metal nitrides and metal oxynitrides may be coated with inorganic and / or organic substances. Examples of the inorganic substance include metal atoms contained in the inorganic pigments. Examples of the organic substance include organic substances having the above-mentioned hydrophobic group, and silane compounds are preferred.

[0037] The production method for the metal nitride, metal oxide, or metal oxynitride is not particularly limited as long as a black pigment having the desired physical properties can be obtained. Known production methods such as gas-phase reaction methods can be used. Examples of gas-phase reaction methods include electric furnace methods and thermal plasma methods. However, the thermal plasma method is preferred due to its low impurity content, ease of uniform particle size, and high productivity. The metal nitride, metal oxide, or metal oxynitride may be surface-modified. For example, surface modification can be performed using a surface treatment agent having both a silyl group and an alkyl group. Examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0038] Among them, from the perspective of being able to suppress undercutting when forming a light-shielding film, nitrides or oxynitrides of one or more metals selected from the group including titanium, vanadium, zirconium, niobium and iron are more preferred, and nitrides or oxynitrides of zirconium, or nitrides or oxynitrides of titanium (titanium black) are even more preferred.

[0039] Titanium black is a black particle containing titanium oxide. Titanium black can be surface-modified as needed to improve dispersibility and inhibit agglomeration. 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 as shown in Japanese Patent Application Publication No. 2007-302836.

[0040] Examples of methods for manufacturing titanium black include: a method of reducing a mixture of titanium dioxide and metallic titanium by heating in a reducing atmosphere (Japanese Patent Application Publication No. 49-05432); a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a hydrogen-containing reducing atmosphere (Japanese Patent Application Publication No. 57-205322); a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonium (Japanese Patent Application Publication No. 60-065069 and Japanese Patent Application Publication No. 61-201610); and a method of attaching vanadium compounds to titanium dioxide or titanium hydroxide and reducing them at high temperature in the presence of ammonium (Japanese Patent Application Publication No. 61-201610).

[0041] There are no particular limitations on the particle size of titanium black, but 10-45 nm is preferred, and 12-20 nm is even better. There are no particular limitations on the specific surface area of ​​titanium black. However, to ensure that the water repellency after surface treatment with a water-repellent agent meets specified performance requirements, a value of 5-150 m² / g, determined using the BET (Brunauer, Emmett, Teller) method, is preferred, and 20-100 m² / g is even better.

[0042] Examples of titanium blacks include 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilack D (trade name, manufactured by Ako Kasei Co., Ltd.), and MT-150A (trade name, manufactured by TAYCA CORPORATION).

[0043] It is also preferable that the light-shielding film includes titanium black as a dispersed component containing titanium black and Si atoms. In this configuration, titanium black is included as a dispersed component in the light-shielding film. The mass ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed component is preferably 0.05 to 0.5, and more preferably 0.07 to 0.4. Here, the dispersed component includes titanium black in both a primary particle state and an aggregate (secondary particle) state.

[0044] To adjust the Si / Ti ratio of the dispersed material (for example, to 0.05 or greater), the following method can be used. First, titanium oxide and silicon dioxide particles are dispersed in a disperser to obtain a dispersion. This mixture is then reduced at a high temperature (for example, 850-1000°C) to obtain a dispersed material containing Si and Ti, with titanium black particles as the main component. Titanium black with adjusted Si / Ti ratios can be produced, for example, by the method described in paragraphs

[0005] and

[0016] -

[0021] of Japanese Patent Application Laid-Open No. 2008-266045. Furthermore, the content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed body can be measured, for example, by method (2-1) or method (2-3) described in paragraphs

[0054] to

[0056] of International Publication No. 2011 / 049090.

[0045] In the dispersed body containing titanium black and Si atoms, the titanium black described above can be used. Furthermore, in order to adjust dispersibility and coloring properties, titanium black can be used in combination with one or more black pigments selected from composite oxides of multiple metals selected from Cu, Fe, Mn, V, and Ni, cobalt oxide, iron oxide, carbon black, and aniline black. In this case, the dispersed body composed of titanium black preferably accounts for 50% by mass or more of the total dispersed body.

[0046] Carbon black is another example of an inorganic pigment. Examples of carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black. As carbon black, carbon black manufactured by known methods such as the oil furnace method can be used, or commercially available products can be used. Specific examples of commercially available carbon black include inorganic pigments such as CI Pigment Black 7.

[0047] As carbon black, surface-treated carbon black is preferred. Examples of surface treatments include resin-based coating treatments, surface treatments that introduce acidic groups, and surface treatments based on silane coupling agents.

[0048] Carbon black that has undergone resin-based coating is preferred. By coating the surface of carbon black particles with insulating resin, the light-shielding and insulating properties of the light-shielding film can be improved. Furthermore, the reliability of image display devices can be improved by reducing leakage current. Therefore, it is preferable to use the light-shielding film for applications requiring insulation. Examples of coating resins include epoxy resins, polyamides, polyamide-imides, phenolic varnish resins, phenolic resins, urea resins, melamine resins, polyurethanes, diallyl phthalate resins, alkylbenzene resins, polystyrene, polycarbonate, polybutylene terephthalate, and modified polyphenylene ether. From the viewpoint of achieving superior light-shielding and insulating properties of the light-shielding film, the content of the coating resin is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, relative to the total amount of carbon black and the coating resin.

[0049] Zirconium, for example, can be cited as a black pigment in Japanese Patent Application Publication No. 2017-222559, International Publication No. 2019 / 130772, International Publication No. 2019 / 059359 and Japanese Patent Application Publication No. 2009-091205, the contents of which are incorporated herein by reference.

[0050] (Organic Pigments) The organic pigment that can be used as the black pigment is not particularly limited as long as it has light-shielding properties and contains particles of an organic compound, and known organic pigments can be used. In this invention, examples of organic pigments include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds or perylene compounds being preferred.

[0051] Examples of bisbenzofuranone compounds include those described in Japanese Patent Publication Nos. 2010-534726, 2012-515233, and 2012-515234. These bisbenzofuranone compounds are available as "Irgaphor Black" (trade name) manufactured by BASF. Examples of the perylene compound include compounds described in JP-A-62-001753 and JP-B-63-026784. The perylene compound can be obtained as CI Pigment Black 21, 30, 31, 32, 33, and 34.

[0052] From the viewpoint of achieving more excellent effects of the present invention, the content of the black pigment is preferably 20 to 90 mass %, more preferably 30 to 70 mass %, and even more preferably 30 to 60 mass % relative to the total mass of the light-shielding film. When two or more black pigments are used, their combined content is preferably within the above-mentioned range. Furthermore, the term "light-shielding" in the light-shielding film of the present invention encompasses the concept of attenuating light while passing through the light-shielding film. In light-shielding films having such light-attenuating functions, it is also preferred that the content of black pigments in the light-shielding film be less than the above-mentioned preferred range.

[0053] <Other Colorants> The light-shielding film may contain color materials other than the black pigment, that is, other color materials.

[0054] (Black dye) The light-blocking film may contain, for example, black dye. As a black dye, for example, dyes that produce black on their own can be used, such as pyrazole azo compounds, pyrrole methylene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzyl compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, anthocyanin compounds, phenanthrene compounds, and pyrrolopyrazole azomethylene compounds. Furthermore, as a black dye, for example, 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, US Patent No. 4808501, US Patent No. 5667920, US 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, etc., are incorporated herein by reference.

[0055] As examples of such black dyes, dyes specified in the Pigment Index (CI) of Solvent Black 27 to 47 can be cited, with dyes specified in the CI of Solvent Black 27, 29 or 34 being preferred. Commercially available products of these black dyes include, for example, Spilon Black MH and Black BH (all manufactured by Hodogaya Chemical Co., Ltd.), VALIFAST Black 3804, 3810, 3820, and 3830 (all manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Savinyl Black RLSN (all manufactured by Clariant Chemicals), and KAYASET Black KR and K-BL (all manufactured by Nippon Kayaku Co., Ltd.). Furthermore, polymerizable dyes having polymerizability within the molecule can also be used. Commercially available products include, for example, the RDW series manufactured by FUJIFILM Wako Pure Chemical Corporation.

[0056] Furthermore, a pigment multimer can 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. Furthermore, as mentioned above, a combination of multiple dyes that have colors other than black when used alone can be used as a black dye. As such coloring dyes, for example, in addition to using chromatic 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 can also be used.

[0057] (colorant) The light-shielding film may contain a colorant other than black. Using both a black colorant (including the aforementioned black pigment) and one or more colorants allows the light-shielding properties of the light-shielding film to be adjusted. Furthermore, for example, when the light-shielding film is used as a light-attenuating film, it is easier to evenly attenuate each wavelength of light containing a wide range of wavelength components. Examples of the colorant include pigments and dyes other than black colorants. Colorants may include chromatic colorants or white colorants. Examples of chromatic colorants include red, green, blue, yellow, violet, and orange. The chromatic colorants or white colorants may be pigments or dyes. Both pigments and dyes may be used. Furthermore, the pigments may be either inorganic or organic. Furthermore, the pigments may be those in which a portion of an inorganic or organic-inorganic pigment is replaced with an organic chromophore. Replacing an inorganic or organic-inorganic pigment with an organic chromophore facilitates color design. When the light-blocking film contains a colorant, the total content of the black pigment and the colorant relative to the total mass of the light-blocking film is preferably 10-90% by mass, more preferably 30-70% by mass, and further preferably 40-60% by mass. Furthermore, when using the light-shielding film as a light-attenuating film, it is also preferable that the total content of black pigment and colorant is less than the aforementioned preferred range. Furthermore, a mass ratio of colorant content to black pigment content (colorant content / black pigment content) of 0.1 to 9.0 is preferred.

[0058] (Infrared absorber) The light-shielding film may further contain an infrared absorber. Infrared absorbers refer to compounds that absorb in the infrared region (preferably with wavelengths of 650–1300 nm). Infrared absorbers are preferably compounds that have a maximum absorption wavelength in the 675–900 nm wavelength range. 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. Phthalocyanine compounds, naphthalocyanine compounds, iminium compounds, cyanine compounds, squarylium compounds, and crotonium compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750 can be used, the contents of which are incorporated herein. For cyanine compounds, reference can be made to "Functional Pigments, by Okawara Nobuyuki, Matsuoka Ken, Kitao Teijiro, and Hirashima Tsuneaki, Kodansha Scientific Ltd.", the contents of which are incorporated herein.

[0059] As a colorant with the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Publication No. 07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Application Publication No. 2002-146254, and near-infrared absorbing particles disclosed in paragraphs 0034 to 0067 of Japanese Patent Application Publication No. 2011-164583, which are composed of microcrystals containing Cu and / or P oxides and have an average aggregated particle size of 5 to 200 nm, can also be used.

[0060] The compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably selected from at least one of the group consisting of anthocyanin compounds, pyrrolopyrrole compounds, squaric acid cyanide compounds, phthalocyanine compounds and naphthalene phthalocyanine compounds. Furthermore, it is preferable for the infrared absorber to be a compound that dissolves in water at 25°C at a concentration of 1% or more by mass, and even more preferably a compound that dissolves in water at 25°C at a concentration of 10% or more by mass. By using such compounds, solvent resistance is improved. Pyrrolopyrrole compounds can be referenced to paragraphs 0049-0062 of Japanese Patent Application Publication No. 2010-222557, the contents of which are incorporated herein by reference. Anthocyanin compounds and squaricine compounds can be referenced to paragraphs 0022-0063 of International Publication No. 2014 / 088063, paragraphs 0053-0118 of International Publication No. 2014 / 030628, paragraphs 0028-0074 of Japanese Patent Application Publication No. 2014-59550, paragraphs 0013-0091 of International Publication No. 2012 / 169447, and Japanese Patent Application Publication No. 2... Paragraphs 0019 to 0033 of Japanese Patent Application Publication No. 015-176046, paragraphs 0053 to 0099 of Japanese Patent Application Publication No. 2014-63144, paragraphs 0085 to 0150 of Japanese Patent Application Publication No. 2014-52431, paragraphs 0076 to 0124 of Japanese Patent Application Publication No. 2014-44301, and paragraphs 0045 to 0078 of Japanese Patent Application Publication No. 2012-8532. Japanese Patent Application Publication No. 2015-172102, paragraphs 0027-0067; Japanese Patent Application Publication No. 2015-172004, paragraphs 0029-0067; Japanese Patent Application Publication No. 2015-40895, paragraphs 0029-0085; Japanese Patent Application Publication No. 2014-126642, paragraphs 0022-0036; Japanese Patent Application Publication No. 2014-148567, paragraph 00... Paragraphs 11 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., are included in this specification.

[0061] <Resin> Light-blocking films may contain resin. As resins, examples include the first resin and the second resin, which will be described later. Furthermore, the first resin and the second resin are different types of resins. In the light-shielding film, the content of the first resin relative to the total mass of the light-shielding film is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass. Furthermore, in the light-shielding film, the content of the second resin relative to the total mass of the light-shielding film is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 5 to 25% by mass. Furthermore, in the light-shielding film, the content ratio of the first resin to the second resin (first resin / second resin) is preferably 0.3 to 0.8, and even more preferably 0.3 to 0.6.

[0062] In the light-shielding film, it is preferable that both the first phase and the second phase contain resin, the first phase preferably contains the first resin (described later), and the second phase preferably contains the second resin (described later). The first resin and the second resin will be described separately below.

[0063] (First Resin) There are no particular restrictions on the types of resins used as dispersants. Examples include polyaminoamines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylate copolymers, and naphthalenesulfonic acid formaldehyde condensates, as well as polyoxyethylene alkyl phosphates, polyoxyethylene alkylamines, and pigment derivatives.

[0064] As shown in the description of the manufacturing sequence of the light-shielding film in the rear section, the first resin is usually the dispersant itself introduced into the dispersion composition in which black pigment is dispersed in the light-shielding film forming composition, or a resin equivalent to the above-mentioned dispersant (a resin polymerized from a dispersant having polymerizable groups). The first resin may contain structural units containing grafted chains that may be contained in the dispersant described later. When the first resin contains structural units containing grafted chains (especially structural units represented by formulas (1) to (4) described later), the content of structural units containing grafted chains relative to the total mass of the first resin is preferably 2 to 90% by mass, and more preferably 5 to 30% by mass. The first resin may contain hydrophobic structural units that may be contained in the dispersant described later. When the first resin contains hydrophobic structural units, the content of the hydrophobic structural units relative to the total mass of the first resin is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. The first resin may contain a structural unit comprising a functional group capable of interacting with a pigment, etc., which may be included in the dispersant described below. When the first resin contains a structural unit comprising a functional group capable of interacting with a pigment, etc., the content of the structural unit comprising a functional group capable of interacting with a pigment, etc., relative to the total mass of the first resin, is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and even more preferably 10 to 70% by mass. The first resin can be of only one type, or it can be of two or more types.

[0065] For the first resin, an acid value of 10~200 mgKOH / g is preferred, 20~150 mgKOH / g is even better, 40~100 mgKOH / g is further preferred, and 40 mgKOH / g or higher but less than 60 mgKOH / g is especially preferred. Furthermore, in this specification, "acid value" can be calculated, for example, from the average content of acid groups in the compound. Also, by changing the composition of the resin, that is, the content of structural units containing acid groups, a resin with the desired acid value can be obtained. The weight average molecular weight of the first resin is preferably 5,000 to 100,000, more preferably 6,000 to 80,000, further preferably 15,000 to 40,000, particularly preferably 20,000 to 40,000, and most preferably 25,000 to 40,000. The glass transition temperature of the first resin is preferably -20~100℃, more preferably -20~80℃, and even more preferably -10~60℃. Glass transition temperature can be measured using a DSC 3500 Sirius (manufactured by Netzsch).

[0066] (Second Resin) There are no particular restrictions on the type of resin used as a second type; alkali-soluble resins are an example. Alkali-soluble resins are generally resins containing acid groups. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, and phenolic hydroxyl groups. The second resin may contain only one type of acid group or more than two types. It is preferred that the second resin contains repeating units having acid groups in their side chains. As a repeating unit having an acid group in the side chain, for example, the repeating unit represented by the formula (2RB) that may be contained in the composition for forming a light-shielding film as shown in the following section can be cited. When the second resin contains repeating units with acid groups on the side chains, its content relative to all repeating units of the resin is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 30% by mass.

[0067] Furthermore, it is preferable that the second resin contains repeating units derived from compounds with a ClogP value of 1.0 or higher. As repeating units derived from compounds with a ClogP value of 1.0 or higher, repeating units derived from (meth)acrylates are preferred. Moreover, the definition of ClogP value will be explained later. As a repeating unit derived from (meth)acrylate, for example, the alkali-soluble resin contained in the composition for forming a light-shielding film shown later in this section may have a repeating unit represented by the formula (2RA) described later. Furthermore, it is preferable that the repeating unit derived from (meth)acrylate has a hydroxyl group as a substituent. When the second resin contains repeating units derived from (meth)acrylate, its content, relative to all repeating units of the resin, is preferably 30% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and especially preferably 80% by mass or more. Furthermore, as an upper limit, for example, 99% by mass or less is preferred, and 95% by mass or less is even more preferred.

[0068] As a sample of the second resin, the following resin can be cited: a resin comprising repeating units having acid groups on the side chains and repeating units derived from (meth)acrylates, wherein the repeating units derived from (meth)acrylates account for 60% or more by mass relative to all repeating units of the resin.

[0069] As shown in the description of the manufacturing sequence of the light-shielding film in the rear section, the second resin is usually an alkali-soluble resin itself or a resin equivalent to the alkali-soluble resin introduced into the composition for forming the light-shielding film as an adhesive component. The second resin can be of only one type, or it can be of two or more types.

[0070] For the acid value of the second resin, 0~150mgKOH / g is preferred, 20~100mgKOH / g is even better, 40~90mgKOH / g is further preferred, and 60~90mgKOH / g is optimal. The weight average molecular weight of the second resin is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, further preferably 15,000 to 40,000, and especially preferably 18,000 to 25,000. The glass transition temperature of the second resin is preferably -20~120℃, preferably -20~110℃, even better -5~80℃, and further preferably 0~70℃. Glass transition temperature can be measured using a DSC 3500 Sirius (manufactured by Netzsch).

[0071] <Other arbitrary ingredients> The light-blocking film may further contain any other components besides those mentioned above. For example, it may include colorants other than black pigments (which may be pigments or dyes), ultraviolet absorbers, surfactants, plasticizers, adhesion promoters for the substrate surface, and other known additives such as conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, antioxidants, fragrances, surface tension modifiers, and chain transfer agents, as needed.

[0072] [Manufacturing method of light-blocking film] The method for producing the light-shielding film of the present invention is not particularly limited, and examples thereof include methods using a light-shielding film-forming composition containing a black pigment. More specifically, an embodiment preferably includes a composition layer forming step of coating a light-shielding film-forming composition containing a black pigment on a support to form a composition layer, and an exposure step of exposing the composition layer to light. Furthermore, when producing a light-shielding film having a predetermined pattern shape, it is more preferred to further include an exposure step of exposing the composition layer in a predetermined pattern through a predetermined mask, and a development step of developing the exposed composition layer to form a light-shielding film, after the composition layer forming step. Furthermore, the development process can be either solvent development or alkali development, with alkali development being preferred. The following describes the components used to form the light-shielding film.

[0073] [Composition for forming a light-shielding film] The composition for forming the light-shielding film (hereinafter also referred to as the "composition") preferably includes black pigment, resin and polymeric compound. The following is a description of each component.

[0074] <Black pigment> The composition used to form the light-shielding film includes a black pigment. Examples of the black pigment include the same ones as those contained in the light-shielding film. From the perspective of achieving better results with respect to the present invention, the content of black pigment relative to the total solid content of the light-shielding film is preferably 20-90% by mass, more preferably 30-70% by mass, and even more preferably 30-60% by mass. When using two or more types of black pigments, it is preferable that their total content is within the above-mentioned range. Furthermore, in a light-shielding film used as a light-attenuating film, it is also preferable that the content of black pigments in the light-shielding film is less than the above-mentioned preferred range.

[0075] <Polymerizable Compound> It is preferable that the composition contains polymeric compounds. In this specification, "polymerizable compound" refers to an organic compound (e.g., an organic compound containing an ethylene unsaturated group) that can be polymerized under the action of polymerization initiators or the like described later. When the composition contains a solvent, it is preferable that the polymeric compound is dissolved in the solvent.

[0076] The polymerizable compound is a low molecular weight polymerizable compound and is a component different from the resin described below. The content of polymeric compounds in the composition relative to the total solid content of the composition is preferably 5-60% by mass, preferably 7-30% by mass, and even more preferably 10-30% by mass. The composition may contain only one polymeric compound, or it may contain two or more. When it contains two or more compounds, it is preferable that the total amount of these compounds is within the range described above. There are no particular restrictions on the molecular weight (weight average molecular weight when molecular weight distribution is available) of polymerizable compounds, but below 2500 is preferred. A lower limit of 100 or above is also preferred.

[0077] Polymerizable compounds containing vinyl unsaturated groups (groups containing vinyl unsaturated bonds) are preferred. In other words, it is preferable that the composition contains low molecular weight compounds with vinyl unsaturated groups as polymerizable compounds. As polymerizable compounds, compounds containing one or more vinyl unsaturated bonds are preferred, compounds containing two or more are even more preferred, compounds containing three or more are further preferred, and compounds containing four or more are particularly preferred. The upper limit is, for example, 15 or less. Examples of vinyl unsaturated groups include vinyl, (methyl)allyl, and (meth)acrylyl.

[0078] As polymerizable compounds, for example, compounds described in paragraph

[0050] of Japanese Patent Application Publication No. 2008-260927 and paragraph

[0040] of Japanese Patent Application Publication No. 2015-068893 can be used, and such contents are incorporated into this specification.

[0079] Polymerizable compounds can be, for example, any of the chemical forms such as monomers, prepolymers, oligomers, mixtures thereof, and polymers thereof. Polymerizable (meth)acrylate compounds with 3 to 15 functionalities are preferred, and (meth)acrylate compounds with 3 to 6 functionalities are even more preferred.

[0080] The polymerizable compound is preferably a compound containing one or more vinyl unsaturated groups and having a boiling point of 100°C or higher at normal pressure. For example, compounds described in paragraph

[0227] of Japanese Patent Application Publication No. 2013-029760 and paragraphs

[0254] to

[0257] of Japanese Patent Application Publication No. 2008-292970 are included in this specification.

[0081] Preferred polymerizable compounds include dipentatriol triacrylate (commercially available products include KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetraacrylate (commercially available products include KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available products include KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available products include KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd. and A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and structures in which these (meth)acryloyl groups mediate ethylene glycol residues or propylene glycol residues (for example, commercial products SR454 and SR499 from Sartomer Company Inc.). These oligomer types can also be used. Also, 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, and KAYARAD DPEA-12 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) can be used. Furthermore, as the polymerizable compound, a (meth)acrylate urethane compound having both a (meth)acrylic group and a urethane bond can be used. For example, KAYARAD DPHA-40H (trade name, manufactured by Nippon Kayaku Co., Ltd.) can be used. The following shows the morphology of preferred polymerizable compounds.

[0082] The polymerizable compound may have acid groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups. Preferred polymerizable compounds containing acid groups are esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids. More preferred are polymerizable compounds containing acid groups obtained by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Among these esters, the aliphatic polyhydroxy compound is preferably a compound that is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include ARONIX TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

[0083] The acid value of polymerizable compounds containing acid groups is preferably 0.1~40 mgKOH / g, and more preferably 5~30 mgKOH / g. If the acid value of the polymerizable compound is above 0.1 mgKOH / g, the developing and dissolving properties are good; if it is below 40 mgKOH / g, it is advantageous in manufacturing and / or processing. Furthermore, it exhibits good photopolymerization performance and excellent curing properties.

[0084] Regarding polymerizable compounds, those containing caprolactone structures are also considered to be of better quality. Compounds containing a caprolactone structure are not particularly limited as long as they contain a caprolactone structure in the molecule. Examples include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying polyols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

[0085] [Chemical Formula 1]

[0086] In formula (Z-1), all 6 Rs are groups represented by formula (Z-2) below, or 1 to 5 of the 6 Rs are groups represented by formula (Z-2) below, and the rest are groups represented by formula (Z-3) below.

[0087] [Chemical Formula 2]

[0088] In formula (Z-2), R1 represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and * represents the bond position.

[0089] [Chemical Formula 3]

[0090] In formula (Z-3), R1 represents a hydrogen atom or a methyl group, and "*" represents the bond position.

[0091] Examples of polymeric compounds containing caprolactone structures include, for instance, Nippon Kayaku Co., Ltd.'s commercially available KAYARAD DPCA series: DPCA-20 (in formulas (Z-1) to (Z-3) above, m=1, the number of groups represented by formula (Z-2)=2, and R1 is a compound consisting entirely of hydrogen atoms), DPCA-30 (same formula, m=1, the number of groups represented by formula (Z-2)=3, and R1 is a compound consisting entirely of hydrogen atoms), DPCA-60 (same formula, m=1, the number of groups represented by formula (Z-2)=6, and R1 is a compound consisting entirely of hydrogen atoms), and DPCA-120 (same formula, m=2, the number of groups represented by formula (Z-2)=6, and R1 is a compound consisting entirely of hydrogen atoms). Furthermore, as a commercially available polymeric compound containing a caprolactone structure, TOAGOSEI CO.,LTD.'s M-350 (trade name) (trimethylolpropane triacrylate) can also be cited.

[0092] As the polymerizable compound, a compound represented by the following formula (Z-4) or formula (Z-5) can also be used.

[0093] [Chemical Formula 4]

[0094] In formulas (Z-4) and (Z-5), E represents -((CH 2) yCH 2O)- or -((CH 2) yCH(CH 3)O)-, y represents an integer from 0 to 10, and X represents (meth)acrylic acid, hydrogen atom, or carboxylic acid group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m represents an integer of 0 to 10, and the total number of each m is an integer of 0 to 40. In formula (Z-5), the total number of (meth)acrylic acid groups is 5 or 6, n represents an integer from 0 to 10, and the total number of each n is an integer from 0 to 60.

[0095] In formula (Z-4), it is preferable for m to be an integer from 0 to 6, and even better if it is an integer from 0 to 4. Furthermore, it is preferable for the sum of each m to be an integer between 2 and 40, even better for an integer between 2 and 16, and even better for an integer between 4 and 8. In formula (Z-5), it is better for n to be an integer from 0 to 6, and even better for n to be an integer from 0 to 4. Furthermore, the total of n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12. Furthermore, in formula (Z-4) or formula (Z-5), the form in which -((CH 2) yCH 2O)- or -((CH 2) yCH(CH 3)O)- is the terminal bond of the oxygen atom to X is preferred.

[0096] The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, preferred embodiments include those in which all six X's in formula (Z-5) are acryloyl groups, and those in which all six X's in formula (Z-5) are acryloyl groups, and mixtures of compounds in which at least one of the six X's is a hydrogen atom. These structures can further improve developability.

[0097] Furthermore, it is preferable that the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is 20% by mass or more, and even more preferable that it is 50% by mass or more. Among the compounds represented by formula (Z-4) or formula (Z-5), neopentyl tetrol derivatives and / or dinepentyl tetrol derivatives are preferred.

[0098] Furthermore, polymeric compounds can contain a Cardo skeleton. Polymers containing a caloric skeleton, particularly those containing a 9,9-diaryl fumarate skeleton, are preferred. Examples of polymeric compounds containing a caloric skeleton include, for example, the Oncoat EX series (manufactured by NAGASE & CO.,LTD) and Ogsol (manufactured by Osaka Gas Chemicals Co.,Ltd.). The polymerizable compound is preferably a compound containing an isocyanuric acid skeleton as a central core. Examples of such polymerizable compounds include NK Ester A-9300 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.). The ethylenically unsaturated group content of 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, and the upper limit is preferably 20.0 mmol / g or less.

[0099] <Resin> The composition includes resin. Examples of resins include dispersants and alkali-soluble resins. The light-shielding film of the present invention is preferably formed by phase separation of the dispersant and the alkali-soluble resin. When the light-shielding film of the present invention is formed using this composition and the manufacturing sequence described later, a domain portion (corresponding to the first phase) composed of black pigment and the dispersant itself or a resin derived from the dispersant (a resin polymerized from a dispersant having polymerizable groups) and a matrix portion (corresponding to the second phase) composed of the alkali-soluble resin itself or a resin derived from the aforementioned alkali-soluble resin (a resin polymerized from an alkali-soluble resin having polymerizable groups) are formed in the light-shielding film. When the light-shielding film of the present invention is formed using this composition and the manufacturing sequence described later, the phase separation structure of the first and second phases is more often an island structure or a co-continuous structure.

[0100] The molecular weight of the resin is preferably greater than 2,000. Furthermore, when the molecular weight of the resin is polydisperse, the weight average molecular weight is preferably greater than 2,000. Hereinafter, the dispersant and the alkali-soluble resin will be described. In this specification, the dispersant refers to a compound different from the alkali-soluble resin described later.

[0101] (Dispersant) The content of the dispersant in the composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass relative to the total solid content of the composition. 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.

[0102] As the dispersant, for example, a known dispersant can be appropriately selected, among which a polymer compound is preferred. Examples of dispersants include, for example, polyaminoamines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylate copolymers and naphthalene sulfonic acid formaldehyde condensates, etc., which are commonly used as dispersing resins; polyoxyethylene alkyl phosphates, polyoxyethylene alkylamines; pigment derivatives, etc.

[0103] The following describes polymeric compounds that can function as dispersants.

[0104] Polymer compounds The polymeric compound adsorbs onto the surface of the dispersed body, such as black pigment and various pigments that can be arbitrarily included in the composition (hereinafter, these pigments are also simply referred to as "pigments"), and plays a role in preventing the re-aggregation of the dispersed body. Therefore, end-modified polymers, grafted (containing polymer chains) polymers, or block polymers containing anchor sites on the pigment surface are preferred.

[0105] The above-mentioned polymer compound may contain a curable group. Examples of the curable group include ethylenically unsaturated groups (such as a (meth)acryl group, a vinyl group, and a styryl group) and cyclic ether groups (such as an epoxy group and an oxetane group). Among them, as a curing group, an ethylenically unsaturated group is preferred from the viewpoint of being able to control polymerization in a radical reaction. As an ethylenically unsaturated group, a (meth)acryloyl group is preferred.

[0106] It is preferable that the polymeric compound containing the curing group comprises one or more structures selected from the group including polyester structures and polyether structures. In this case, the main chain may contain polyester structures and / or polyether structures. As described later, when the polymeric compound contains structural units containing grafted chains, the grafted chains may contain polyester structures and / or polyether structures. As the polymer compound, it is more preferred that the graft chain comprises a polyester structure.

[0107] It is preferred that the polymer compound contains a structural unit comprising a graft chain. In addition, in this specification, "structural unit" and "repeating unit" have the same meaning. Polymer compounds containing structural units with such grafted chains exhibit excellent dispersibility and long-term dispersion stability of pigments and the like due to the affinity of these grafted chains for solvents. Furthermore, the presence of grafted chains enhances the affinity of polymeric compounds and other resins that can be used simultaneously with these structures. Consequently, residue formation is less likely during alkaline development. As the graft chain becomes longer, the steric repulsion effect increases, improving the dispersibility of pigments, etc. On the other hand, if the graft chain is too long, the adsorption capacity for pigments, etc. decreases, tending to reduce the dispersibility of pigments, etc. Therefore, the number of atoms in the graft chain, excluding hydrogen atoms, is preferably 40 to 10,000, more preferably 50 to 2,000, and even more preferably 60 to 500. Here, the graft chain refers to the root of the main chain of the copolymer (the atom bonded to the main chain in the group branching from the main chain) to the terminal of the group branching from the main chain.

[0108] The graft chain preferably comprises a polymer structure. Examples of such polymer structures include poly(meth)acrylate structures (e.g., poly(meth)acrylic acid structures), polyester structures, polyurethane structures, polyurea structures, polyamide structures, and polyether structures. In order to enhance the interaction between the graft chain and the solvent and thereby improve the dispersibility of the pigment, etc., the graft chain preferably comprises one or more types selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure, and more preferably comprises at least one type of graft chain selected from the group consisting of a polyester structure and a polyether structure.

[0109] There is no particular limitation on the macromonomer containing such a graft chain (a monomer having a polymer structure and bonded to the main chain of the copolymer to form a graft chain), and a macromonomer containing a reactive double bond group can be preferably used.

[0110] As commercially available macromonomers that correspond to the structural units containing graft chains contained in the polymer compound and are preferably used for synthesizing the polymer compound, AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS-6 (trade name, manufactured by Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), AW-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-714 (trade name, manufactured by Toagosei Co., Ltd.), AY-707 (trade name, manufactured by Toagosei Co., Ltd.), AY-714 (trade name, manufactured by Toagosei Co., Ltd.), AK-5 (trade name, manufactured by Toagosei Co., Ltd.), Co., Ltd.), AK-30 (trade name, manufactured by Toagosei Co., Ltd.), AK-32 (trade name, manufactured by Toagosei Co., Ltd.), Blemmer PP-100 (trade name, manufactured by No. 5 Corporation), Blemmer PP-500 (trade name, manufactured by No. 5 Corporation), Blemmer PP-800 (trade name, manufactured by No. 5 Corporation), Blemmer PP-1000 (trade name, manufactured by No. 5 Corporation), Blemmer 55-PET-800 (trade name, manufactured by No. 5 Corporation), Blemmer PME-4000 (trade name, manufactured by No. 5 Corporation), Blemmer PSE-400 (trade name, manufactured by No. 5 Corporation), Blemmer PSE-1300 (trade name, manufactured by No. 5 Corporation), or Blemmer 43PAPE-600B (trade name, manufactured by NOF CORPORATION.), etc. Among them, AA-6 (trade name, manufactured by TOAGOSEI CO.,LTD.), AA-10 (trade name, manufactured by TOAGOSEI CO.,LTD.), AB-6 (trade name, manufactured by TOAGOSEI CO.,LTD.), AS-6 (trade name, manufactured by TOAGOSEI CO.,LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO.,LTD.), or BLEMMER PME-4000 (trade name, manufactured by NOF CORPORATION.) are preferred.

[0111] The dispersant described above preferably contains one or more structures selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyesters; more preferably, it contains one or more structures selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyesters; and even more preferably, it contains one or more structures selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, polycaprolactone, and polyvalerol structures. The dispersant can be a dispersant that contains only one of the above structures, or it can be a dispersant that contains a plurality of such structures. Here, the polycaprolactone structure represents a structure containing a repeating unit formed by ring-opening of ε-caprolactone. The polyvalerol structure represents a structure containing a repeating unit formed by ring-opening of δ-valerol. As a specific example of a dispersant containing a polycaprolactone structure, a dispersant in formula (1) and formula (2) below, where j and k are 5, can be given. Furthermore, as a specific example of a dispersant containing a polyvalerone structure, a dispersant in formula (1) and formula (2) below, where j and k are 4, can be given. As a specific example of a dispersant containing a polymethyl acrylate structure, a dispersant in formula (4) below where X5 is a hydrogen atom and R4 is a methyl group can be given. Also, as a specific example of a dispersant containing a polymethyl methacrylate structure, a dispersant in formula (4) below where X5 is a methyl group and R4 is a methyl group can be given.

[0112] • Structural units containing graft chains As the structural unit containing the graft chain, a structural unit represented by any one of the following formulas (1) to (4) is preferred.

[0113] [Chemical Formula 5]

[0114] In formulas (1) to (4), W1, W2, W3, and W4 each independently represent an oxygen atom or NH. As W1, W2, W3, and W4, an oxygen atom is preferred. In formulas (1) to (4), X1, X2, X3, X4 and X5 independently represent a hydrogen atom or a monovalent organic group. From the point of view of synthetic constraints, it is preferable that X1, X2, X3, X4 and X5 are independently hydrogen atoms or alkyl groups with 1 to 12 carbon atoms, and even more preferable that they are independently hydrogen atoms or methyl groups, with methyl groups being even more preferable.

[0115] In equations (1) to (4), Y1, Y2, Y3, and Y4 independently represent divalent linking groups, and the linking groups are not structurally restricted. Specifically, examples of divalent linking groups represented by Y1, Y2, Y3, and Y4 include the linking groups (Y-1) to (Y-21) below. In the structures shown below, A and B refer to the bonding sites with the left-hand and right-hand end groups in equations (1) to (4), respectively. In the structures shown below, (Y-2) or (Y-13) is preferred for ease of synthesis.

[0116] [Chemical Formula 6]

[0117] In formulas (1) to (4), Z1, Z2, Z3 and Z4 independently represent hydroxyl, amino or monovalent organic groups. There are no particular restrictions on the structure of the organic group. Specifically, alkyl, alkoxy, aryloxy, heteroaryloxy, alkylthioether, arylthioether and heteroarylthioether groups can be cited. As for the organic groups represented by Z1, Z2, Z3 and Z4, groups with stereorepulsion effects are preferred, especially from the viewpoint of improving dispersibility. Alkyl or alkoxy groups with 5 to 24 carbon atoms are more preferred, and branched alkyl, cyclic alkyl or alkoxy groups with 5 to 24 carbon atoms are even more preferred. Furthermore, the alkyl group contained in the alkoxy group can be any of the following: straight-chain, branched, or cyclic. Also, the methylene group in the alkoxy group can be substituted with -O-. Furthermore, the aforementioned groups may have substituents (e.g., hydroxyl and (meth)acryloxy, etc., vinyl unsaturated groups).

[0118] Furthermore, in formula (1), when Z 1 is a hydroxyl group, the site represented by -COZ 1 in the formula can be anionized (-COO -). In this case, as a relative cation, a quaternary ammonium salt can be cited, among which the structure represented by formula (TY) is preferred.

[0119] [Chemical Formula 7]

[0120] In formula (TY), R 1f and R 1g independently represent a hydrogen atom or an alkyl group, respectively. As for the alkyl group represented by R 1f and R 1g, a straight-chain or branched form is preferred. Furthermore, as for the number of carbon atoms, 1 to 10 is preferred, 1 to 4 is more preferred, and 1 or 2 is even more preferred. In formula (TY), R 1e represents an alkyl group. A straight-chain alkyl group represented by R 1e is preferred. Furthermore, 10 to 24 carbon atoms are preferred, and 10 to 20 carbon atoms are even more preferred. In formula (TY), L2 represents an alkyl group. As an alkyl group represented by L2, a straight-chain or branched form is preferred, with a straight-chain form being more preferred. As for the number of carbon atoms, 1 to 20 is preferred, with 1 to 12 being more preferred. Furthermore, the alkyl group may have substituents (e.g., hydroxyl groups). Also, the methylene group in the alkyl group may be substituted with -O-. In formula (TY), R 1h represents a hydrogen atom or an vinyl unsaturated group such as (meth)acryloxy.

[0121] In equations (1) to (4), n, m, p and q represent integers from 1 to 500 independently. Furthermore, in equations (1) and (2), j and k independently represent integers from 2 to 8. From the viewpoint of the viscosity stability and developability of the composition over time, integers from 4 to 6 are preferred for j and k in equations (1) and (2), and 5 is even better. Furthermore, in equations (1) and (2), integers of 5 or more as n and m are preferred, integers of 8 or more are even more preferred, and integers of 10 or more are even more preferred. Furthermore, when the dispersant contains polycaprolactone structure and polyvalerolactone structure, integers of 10 or more as the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of the polyvalerolactone structure are preferred, and integers of 20 or more are even more preferred.

[0122] In formula (3), R3 represents a branched or straight-chain alkyl group, preferably an alkyl group with 1 to 10 carbon atoms, and even more preferably an alkyl group with 2 or 3 carbon atoms. When p is 2 to 500, there may be multiple R3s that are the same or different from each other. In formula (4), R4 represents a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited in structure. As R4, a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferred, and a hydrogen atom or an alkyl group is more preferred. When R4 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. A linear alkyl group having 1 to 20 carbon atoms is more preferred, and a linear alkyl group having 1 to 6 carbon atoms is even more preferred. In formula (4), when q is 2 to 500, the plurality of X5 and R4 present in the graft copolymer may be the same or different.

[0123] Furthermore, a polymer compound can contain two or more structural units with different structures, including grafted chains. That is, the molecule of a polymer compound can contain structural units with different structures represented by equations (1) to (4). Also, in equations (1) to (4), when n, m, p and q represent integers of 2 or more, in equations (1) and (2), the side chains can contain structures with different j and k. In equations (3) and (4), the molecule contains a plurality of R3, R4 and X5 that can be the same or different.

[0124] In polymer compounds, the content of structural units with grafted chains (especially structural units represented by formulas (1) to (4) above) relative to the total mass of the polymer compound is preferably 2 to 90% by mass, and more preferably 5 to 30% by mass. When the content of structural units with grafted chains (especially structural units represented by formulas (1) to (4) above) is 5% by mass or more, the pigment dispersibility is high and the effect of the present invention is even better.

[0125] Hydrophobic structural unit Furthermore, it is preferable that the polymer compound contains hydrophobic structural units that are different from those containing grafted chains (i.e., do not belong to structural units containing grafted chains). In this specification, the hydrophobic structural unit is a structural unit that does not have an acid group (e.g., carboxylic acid group, sulfonic acid group, phosphate group, phenolic hydroxyl group, etc.).

[0126] The hydrophobic structural unit is preferably derived from the corresponding structural unit of a compound (monomer) with a ClogP value of 1.2 or higher, and is more preferably derived from the structural unit of a compound with a ClogP value of 1.2 to 8. This allows the effects of the present invention to be demonstrated more reliably.

[0127] In this specification, the ClogP value is calculated using the program "CLOGP," available from Daylight Chemical Information System, Inc. This program provides "calculated logP" values ​​calculated using Hansch, Leo's fragment approach (see references below). The fragment approach divides the chemical structure of a compound into segments and calculates the logP contribution allocated to each segment. Details are described in the references below. In this specification, the ClogP value is calculated using the program CLOGP v4.82. AJ Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, PG Sammnens,JB Taylor and CA Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & AJ Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. AJ Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

[0128] logP refers to the commonly used logarithm of the partition coefficient P, which is a quantitative value representing how an organic compound is distributed in a two-phase equilibrium system of oil (usually 1-octanol) and water, and is expressed by the following formula. logP = log(Coil / Cwater) In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase. The value of logP is based on 0. If it increases positively (plus), it indicates an increase in oil solubility. If the absolute value increases negatively (minus), it indicates an increase in water solubility. It is negatively correlated with the water solubility of organic compounds and is widely used as a parameter to predict the hydrophilicity and hydrophobicity of organic compounds.

[0129] In polymer compounds, it is preferable that the hydrophobic structural units, on a mass conversion basis, comprise 10% to 90% of the total mass of the polymer compound, and even more preferably 20% to 80%. When the content is within the above range, sufficient patterning can be formed.

[0130] • Functional groups capable of interacting with pigments, etc. The polymer compound can incorporate functional groups that can interact with pigments (e.g., opaque pigments). Preferably, the polymer compound further contains structural units that include functional groups capable of interacting with pigments. Examples of functional groups that can interact with pigments include acid groups, base groups, ligands, and reactive functional groups. When a polymeric compound contains acid groups, base groups, ligands, or reactive functional groups, it is preferable that it contains structural units containing acid groups, structural units containing base groups, structural units containing ligands, or structural units containing reactive functional groups, respectively. In particular, if the polymer compound further contains alkali-soluble groups such as carboxylic acid groups as acid groups, it can endow the polymer compound with developability for forming patterns by alkali development. In other words, if an alkali-soluble group is introduced into the polymer compound, the polymer compound in the above composition, which serves as a dispersant to aid in the dispersion of pigments, etc., becomes alkali-soluble. Regarding compositions containing such polymer compounds, the light-shielding film formed after exposure exhibits excellent light-shielding properties, and the alkali developability of the unexposed portion is improved. Furthermore, if a polymer contains structural units that include acid groups, the polymer is more miscible with solvents, and its coatability is often improved. This is presumably because the acid groups in the structural units containing acid groups readily interact with pigments, etc., allowing the polymer to stably disperse the pigments, etc., and the viscosity of the polymer that disperses the pigments, etc., becomes lower, making the polymer itself easier to disperse stably.

[0131] The structural unit containing the base-soluble group as an acid group can be the same as the structural unit containing the grafted chain, or it can be a different structural unit. However, the structural unit containing the base-soluble group as an acid group is a structural unit that is different from the hydrophobic structural unit (that is, it does not belong to the hydrophobic structural unit).

[0132] As functional groups, i.e. acid groups, that can interact with pigments, such as carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups, it is preferable to select at least one from the group including carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups, with carboxylic acid groups being more preferred. Carboxylic acid groups have good adsorption capacity for pigments and the like, and high dispersibility. That is, it is preferable that the polymer contains one or more structural units selected from the group including carboxylic acid groups, sulfonic acid groups and phosphate groups.

[0133] Polymers can have one or more structural units containing acid groups. The polymer may not contain structural units containing acid groups, but when it does, the content of structural units containing acid groups, in terms of mass conversion, is preferably 5 to 80% by mass relative to the total mass of the polymer. From the viewpoint of suppressing damage to image intensity based on alkali development, 10 to 60% by mass is even better.

[0134] Functional groups, or bases, that can interact with pigments, include primary amine groups, secondary amine groups, tertiary amine groups, heterocycles containing nitrogen atoms, and amide groups. From the viewpoint of good adsorption and high dispersibility for pigments, tertiary amine groups are preferred. Polymer compounds may contain one or more of these bases. Polymer compounds may not contain structural units containing bases, but when they do, the content of structural units containing bases, in terms of mass conversion, is preferably 0.01 to 50% by mass relative to the total mass of the polymer compound. From the viewpoint of suppressing and hindering development, 0.01 to 30% by mass is even better.

[0135] Examples of functional groups capable of interacting with pigments, i.e., ligands and reactive functional groups, include acetylacetoxy, trialkoxysilyl, isocyanate, acid anhydrides, and acetyl chloride. From the viewpoint of good adsorption to pigments and high dispersibility, acetylacetoxy is a preferred functional group. Polymers may possess one or more of these groups. The polymer may not contain structural units containing ligands or structural units containing reactive functional groups, but when it does contain such structural units, the content of such structural units, in terms of mass conversion, is preferably 10 to 80% by mass relative to the total mass of the polymer, and from the viewpoint of suppressing and hindering development, 20 to 60% by mass is even better.

[0136] From the viewpoints of interaction with pigments, viscosity stability over time, and permeability to developer, the content of structural units containing functional groups that can form interactions with pigments is preferably 0.05 to 90% by mass relative to the total mass of the polymer compound, more preferably 1.0 to 80% by mass, and further preferably 10 to 70% by mass.

[0137] Other structural units Furthermore, for the purpose of improving various properties such as image strength, the polymer compound may further have other structural units (for example, structural units containing functional groups having affinity for the solvent described below) within the scope that does not impair the effects of the present invention: structural units having various functions different from those of structural units containing graft chains, hydrophobic structural units, and structural units containing functional groups capable of interacting with pigments, etc. Other structural units of this kind can be exemplified by structural units derived from free radical polymerizable compounds selected from acrylonitrile and methacrylonitrile.

[0138] The polymer compound can use one or more of these other structural units, and their content, on a mass conversion basis, is preferably 0 to 80% by mass relative to the total mass of the polymer compound, and more preferably 10 to 60% by mass. Sufficient pattern-forming properties can be maintained within the above range.

[0139] Physical properties of polymer compounds The preferred acid value for polymeric compounds is 0~200mgKOH / g, the better is 20~150mgKOH / g, the further better is 40~100mgKOH / g, and the best is 40mgKOH / g or higher but less than 60mgKOH / g. If the acid value of the polymer compound is below 200 mg KOH / g, it can more effectively suppress pattern stripping during the development of the exposed composition layer. Furthermore, if the acid value of the polymer compound is above 10 mg KOH / g, its alkaline developability is even better. For the weight average molecular weight of the polymer compound, 5,000 to 100,000 is preferred, 6,000 to 80,000 is even better, 15,000 to 40,000 is further preferred, 20,000 to 40,000 is particularly preferred, and 25,000 to 40,000 is optimal. For glass transition temperatures of polymer compounds, -20~100℃ is preferred, -20~80℃ is even better, and -10~60℃ is further preferred. Glass transition temperature can be measured using a DSC 3500 Sirius (manufactured by Netzsch). Polymer compounds can be synthesized using known methods.

[0140] As a polymer compound, examples include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., and BYK Chemie. GmbH's "Disperbyk-101 (polyamide phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid groups), 111 (phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 167, 170, 190 (high molecular weight copolymers)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", EFKA's "EFKA4047, 4050~4010~4165 (polyurethane), EFKA4330~4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyamide), 5765 (high molecular weight polycarboxylic acid), 6220 (fatty acid polyester), 6750 (azo pigment derivative)", Ajinomoto Fine-Techno Co., Inc. manufactures "AJISPER PB821, PB822, PB880, PB881"; Kyoeisha Chemical Co., Ltd. manufactures "FLOREN TG-710 (carbamate oligomer)" and "Polyflow No.50E, No.300 (acrylic copolymer)"; Kusumoto Chemicals, Ltd. manufactures "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725"; Kao Corporation manufactures "DEMOL RN, N (naphthalenesulfonic acid formaldehyde condensate), MS, C, SN-B (aromatic sulfonic acid formaldehyde condensate)"; "HOMOGENOL L-18 (high molecular weight polycarboxylic acid)"; "EMULGEN" 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether), ACETAMIN 86 (stearylamine acetate), The Lubrizol Corporation's 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymers containing functional parts at the ends), 24000, 28000, 32000, 38500 (graft copolymers), Nikko Chemicals Co., Ltd.'s NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Kawaken Fine Chemicals Co., Ltd.Manufacturers include: HINOAKUTO T-8000E, Shin-Etsu Chemical Co., Ltd. (organosiloxane polymer KP341), Yusho Co Ltd ("W001: cationic surfactant"), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, 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. High molecular weight dispersants such as Disperse Aid 15 and Disperse Aid 9100; ADEKA CORPORATION's "Adeka Pluronic (registered trademark) L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123"; and Sanyo Chemical Industries, Ltd.'s "Ionet (trade name) S-20," etc. Acrybase FFS-6752 and Acrybase FFS-187 can also be used.

[0141] Furthermore, amphoteric resins containing both acid and base groups are preferred. As amphoteric resins, those with an acid value of 5 mg KOH / g or higher and an amine value of 5 mg KOH / g or higher are preferred. Commercially available amphoteric resins include, for example, those manufactured by BYK-Chemie GmbH such as 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, and those manufactured by Ajinomoto Fine-Techno Co., Inc. such as AJISPER PB821, AJISPER PB822, and AJISPER PB881. These polymeric compounds can be used alone or in combination with two or more.

[0142] In addition, as a polymer compound, for example, the polymer compound described in paragraphs 0127 to 0129 of Japanese Patent Application Laid-Open No. 2013-249417 can be referred to, and the contents thereof are incorporated into this specification.

[0143] Furthermore, in addition to the aforementioned polymeric compounds, graft copolymers of segments 0037 to 0115 (corresponding to segments 0075 to 0133 of US2011 / 0124824) can be cited as dispersants, and their contents are incorporated into this specification. Furthermore, in addition to the above, examples can be cited of polymeric compounds containing side-chain structures with acid groups bonded by linking groups, as described in Japanese Patent Application Publication No. 2011-153283, paragraphs 0028 to 0084 (corresponding to paragraphs 0075 to 0133 of US2011 / 0279759), and these contents can be incorporated into this specification.

[0144] Furthermore, as a dispersant, the resin described in paragraphs 0033 to 0049 of Japanese Patent Application Publication No. 2016-109763, the contents of which are included in this specification, can also be cited.

[0145] (Alkali-soluble resin) In this specification, alkali-soluble resin refers to a resin containing groups that promote alkali solubility (hereinafter also simply referred to as "alkali-soluble groups." For example, acid groups such as carboxylic acid groups can be mentioned), and refers to a resin different from the dispersants already described. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, and phenolic hydroxyl groups. It is preferred that the alkali-soluble resin comprises repeating units having acid groups in their side chains. Examples of the repeating unit having an acid group in its side chain include a repeating unit represented by the formula (2RB) described below. When the second resin contains repeating units with acid groups on the side chains, its content relative to all repeating units of the resin is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 30% by mass.

[0146] Examples of alkali-soluble resins include polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic acid / (meth)acrylamide copolymer resins, epoxy resins, and polyimide resins.

[0147] Examples of alkali-soluble resins include copolymers of unsaturated carboxylic acids and ethylene-unsaturated compounds. As unsaturated carboxylic acids, there are no particular limitations. Examples include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acids or their anhydrides such as itaconic acid, maleic acid, and fumaric acid; and mono(2-(meth)acrylic acid oxyethyl) phthalate and other polycarboxylic acid monoesters.

[0148] Examples of vinyl unsaturated compounds capable of copolymerization include methyl methacrylate. Furthermore, compounds described in paragraph 0027 of Japanese Patent Application Publication No. 2010-097210 and paragraphs 0036-0037 of Japanese Patent Application Publication No. 2015-068893 can also be used; the above information is incorporated herein by reference.

[0149] From the perspective of further improving the effects of the present invention, alkali-soluble resins containing curing groups are also preferred as alkali-soluble resins. As for the aforementioned curing groups, other curing groups that may be contained in the aforementioned polymer compounds can also be cited, and the preferred range is also the same. Examples of alkali-soluble resins containing curing groups include acrylic resins containing vinyl unsaturated groups in their side chains. Acrylic resins containing vinyl unsaturated groups in their side chains can be obtained, for example, by adding the carboxylic acid group of an acrylic resin containing a carboxylic acid group to a vinyl unsaturated compound containing an epoxypropyl or alicyclic epoxy group. As an alkali-soluble resin containing a curing group, an alkali-soluble resin having a curing group in its side chain is preferred.

[0150] Alkali-soluble resins containing repeating units derived from compounds with a ClogP value of 1.0 or higher are also preferred. Of the aforementioned ClogP values, 1.0 to 8.0 are preferred. The definition of the ClogP value is as described above.

[0151] As repeating units derived from compounds with a ClogP value of 1.0 or higher, repeating units derived from (meth)acrylates are preferred. As a repeating unit derived from (meth)acrylate, for example, a repeating unit represented by the formula (2RA) described later can be cited. Furthermore, it is preferable that the repeating unit derived from (meth)acrylate has a hydroxyl group as a substituent. When an alkali-soluble resin contains repeating units derived from (meth)acrylates, its content, relative to all repeating units of the resin, is preferably 30% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and especially preferably 80% by mass or more. Furthermore, as an upper limit, for example, 99% by mass or less is preferred, and 95% by mass or less is even more preferred.

[0152] As an alkali-soluble resin, from the viewpoint of easily forming the light-shielding film of the present invention, a resin comprising repeating units represented by the following formula (2RA) and repeating units represented by the following formula (2RB), and wherein the content of repeating units represented by formula (2RA) is 30% by mass or more (preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more) relative to all repeating units of the resin is preferred.

[0153] [Chemical Formula 8]

[0154] In formula (2RA), R 1a represents a hydrogen atom or a methyl group. R 2a represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms that may have substituents, or an aralkyl group having 7 to 18 carbon atoms that may have substituents. The number of carbon atoms in the alkyl group represented by R 2a is preferably 1 to 8, more preferably 2 to 6, and even more preferably 3 to 4. Furthermore, a linear alkyl group is preferred. For the number of carbon atoms in the aralkyl group represented by R 2a, 7 to 18 is preferred, 7 to 12 is even more preferred, and 7 to 10 is even more preferred. Furthermore, the substituent that the alkyl group and the aralkyl group represented by R 2a may have is not particularly limited, and examples thereof include a hydroxyl group.

[0155] In formula (2RB), R 1b represents a hydrogen atom or a methyl group. L b represents a single bond or a divalent linking group. The type of divalent linking group is not particularly limited. Examples include divalent hydrocarbon groups (which may be divalent saturated hydrocarbon groups or divalent aromatic hydrocarbon groups. The divalent saturated hydrocarbon group may be linear, branched, or cyclic, and preferably has 1 to 10 carbon atoms. For example, an alkylene group may be mentioned. The divalent aromatic hydrocarbon group preferably has 5 to 10 carbon atoms. For example, a phenylene group may be mentioned. In addition, alkenylene and alkynylene groups may also be mentioned.), divalent heterocyclic groups, -O-, -S-, -SO2-, -NR A-, -CO-(-C(=O)-), -COO-(-C(=O)O-), -NR A-CO-, -SO3-, -SO2NR A-, and groups formed by combining two or more of these. Here, RA represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).

[0156] The content of the repeating unit, expressed by formula (2RA), relative to all repeating units in the resin, is preferably 30% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and especially preferably 80% by mass or more. There is no particular upper limit, but 99% by mass or less is preferred, and 90% by mass or less is even more preferred. The content of repeating units represented by formula (2RB) relative to all repeating units of the resin is preferably 1~40% by mass, more preferably 1~30% by mass, further preferably 5~30% by mass, and especially preferably 5~25% by mass.

[0157] An alkali-soluble resin containing repeating units represented by formula (2RA) and repeating units represented by formula (2RB) may contain other repeating units besides those mentioned above. Other repeating units include repeating units with hardening bases. As for the aforementioned curing groups, other curing groups that may be contained in the aforementioned polymer compounds can also be cited, and the preferred range is also the same. When an alkali-soluble resin contains repeating units with curable groups, its content relative to all repeating units of the resin is preferably 3 to 40% by mass, and more preferably 5 to 30% by mass.

[0158] Furthermore, the structure of the alkali-soluble resin comprising repeating units represented by formula (2RA-1) and repeating units represented by formula (2RA-2) is also preferred as a repeating unit represented by formula (2RA). The repeating unit represented by formula (2RA-1) refers to the following state: in the repeating unit represented by the above formula (2RA), R 2a is an unsubstituted straight-chain or branched alkyl group having 1 to 12 carbon atoms. Furthermore, the repeating unit represented by formula (2RA-2) refers to the following state: in the repeating unit represented by the above formula (2RA), R 2a represents a straight-chain or branched alkyl group having 1 to 12 carbons with a substituent containing a hydroxyl group, or represents an aralkyl group having 7 to 18 carbons with a substituent. When the structure of the alkali-soluble resin comprises repeating units represented by formula (2RA-1) and repeating units represented by formula (2RA-2), the content of repeating units represented by formula (2RA-1) is preferably 60 to 90% by mass relative to all repeating units of the resin, and the content of repeating units represented by formula (2RA-2) is preferably 2 to 15% by mass relative to all repeating units of the resin.

[0159] Specific examples of alkali-soluble resins include, for example, the resins shown below, but are not limited thereto. In Table 1 below, “Copolymer Types” indicates the types of repeating units contained in the polymer. “Copolymer Ratio (mass %)” indicates the content (mass %) of each unit relative to all repeating units in the polymer.

[0160] [Table 1] Table 1 polymer Types of copolymer components Copolymer composition ratio [mass %] Mv Acid value [mgKOH / g] Repeating unit 1 Repeating Unit 2 Repeating Unit 3 Repeating unit 4 Repeating Unit 1 Repeating Unit 2 Repeating unit 3 Repeating Unit 4 1 A-1 B-1 A-7 - 86.85 10 3.15 - 18400 61.2 2 A-1 B-1 - - 87.5 12.5 - - 19500 75.9 3 A-1 B-1 A-3 A-7 80.05 10 6.8 3.15 19900 61.3 4 A-2 B-1 A-6 - 78.00 10:00 12:00 - 21900 64.9 5 A-3 B-1 A-6 - 80.75 7.5 11.75 - 24100 48.9 6 A-3 B-1 A-7 - 86.85 10 3.15 - 24600 65.3 7 A4 B-3 - - 82.8 17.2 - - 28700 63.9 8 A-5 B-2 A-8 - 78.6 10 11.4 - 27900 78.2 9 A-10 B-2 A-9 - 82.5 6.35 11.15 - 12600 49.3 10 A-11 B-4 A-6 - 40.5 50 9.5 - 23300 85.2 11 A-1 B-1 C-1 - 61.3 12.5 26.2 - 16340 72.4 12 A-1 B-1 C-5 - 74.7 12.5 12.8 - 19514 73.0 13 A-2 B-4 C-2 C-3 35 46.5 12.5 6 17300 80.4 14 A-3 B-3 C-4 - 78.5 12 9.5 - 23600 45.8

[0161] The following table shows the raw material monomers that constitute the repeating units of each polymer.

[0162] [Chemical Formula 9]

[0163] For alkali-soluble resins, an acid value of 0~150mgKOH / g is preferred, 20~100mgKOH / g is even better, 40~90mgKOH / g is further preferred, and 60~90mgKOH / g is optimal. The weight average molecular weight of the alkali-soluble resin is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, further preferably 15,000 to 40,000, and particularly preferably 18,000 to 25,000. For alkali-soluble resins, the glass transition temperature is preferably -20~120℃, preferably -20~110℃, even better -5~80℃, and further better 0~70℃. Glass transition temperature can be measured using a DSC 3500 Sirius (manufactured by Netzsch).

[0164] There is no particular limitation on the content of alkali-soluble resin in the composition. 1 to 40% by mass is preferred, 2 to 30% by mass is more preferred, and 5 to 25% by mass is even more preferred relative to the total solid content of the composition. Alkali-soluble resins can be used alone or in combination with two or more. When using two or more alkali-soluble resins simultaneously, it is preferable that the total content be within the range mentioned above.

[0165] The content of the resin (including the alkali-soluble resin and the dispersant) in the composition is not particularly limited, but is preferably 3 to 70% by mass, more preferably 9 to 50% by mass, and even more preferably 10 to 40% by mass.

[0166] <Polymerization Initiator> The composition may contain a polymerization initiator. There are no particular limitations on the polymerization initiator; any known polymerization initiator can be used. Examples of polymerization initiators include photopolymerization initiators and thermal polymerization initiators, with photopolymerization initiators being preferred. Furthermore, free radical polymerization initiators are preferred.

[0167] Examples of thermal polymerization initiators include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalonitrile and dimethyl-(2,2')-azobis(2-propionate)[V-601], as well as organic peroxides such as benzoyl peroxide, lauryl peroxide and potassium persulfate. Specific examples of thermal polymerization initiators include the polymerization initiators described on pages 65-148 of Kiyoshi Kato's "Ultraviolet Curing System" (published by Comprehensive Technology Center Co., Ltd., Heisei 1).

[0168] There are no particular limitations on the photopolymerization initiator, as long as it can initiate the polymerization of the polymerizable compound, and known photopolymerization initiators can be used. For example, photopolymerization initiators that are photosensitizing from the ultraviolet region to the visible light region are preferred. Furthermore, it can be an activator that interacts with the photoexcited sensitizer to generate active free radicals, or it can be an initiator that initiates cationic polymerization depending on the type of polymerizable compound.

[0169] Examples of photopolymerization initiators include, for example, halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing a diazole skeleton, etc.), acetylenol compounds such as acetylenol oxide, hexaaryl diimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone, etc. As specific examples of the photopolymerization initiator, for example, reference can be made to paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-029760, the contents of which are incorporated herein.

[0170] Examples of the photopolymerization initiator include aminoacetophenone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine-based initiators described in Japanese Patent No. 4225898. Examples of the hydroxyacetophenone compound include Omnirad-184, Omnirad-1173, Omnirad-500, Omnirad-2959, and Omnirad-127 (trade names: all manufactured by IGM RESINS BV). Examples of aminoacetophenone compounds include commercially available products such as Omnirad-907, Omnirad-369, or Omnirad-379EG (all manufactured by IGM RESINS BV). Also examples of aminoacetophenone compounds include those described in Japanese Patent Application Publication No. 2009-191179, whose absorption wavelength matches that of long-wavelength light sources such as 365 nm or 405 nm. Examples of the acylphosphine compound include commercially available products Omnirad-819 and Omnirad-TPO (trade names: both manufactured by IGM RESINS BV).

[0171] (oxime compounds) Oxime ester-based polymerization initiators (oxime compounds) are preferred as photopolymerization initiators. Oxime compounds are particularly advantageous due to their high sensitivity and polymerization efficiency, and the ease with which the content of opaque pigments in the composition can be set high. Examples of oxime compounds include, for example, compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, or Japanese Patent Application Publication No. 2006-342166. Examples of oxime compounds include, for example, 3-benzyloxyiminobut-2-one, 3-acetyloxyiminobut-2-one, 3-acetyloxyiminobut-2-one, 2-acetyloxyiminopentan-3-one, 2-acetyloxyimino-1-phenylprop-1-one, 2-benzyloxyimino-1-phenylprop-1-one, 3-(4-toluenesulfonyloxy)iminobut-2-one, and 2-ethoxycarbonyloxyimino-1-phenylprop-1-one. Furthermore, examples can be found in JCS Perkin II (1979), pages 1653-1660 and 156-162; Journal of Photopolymer Science and Technology (1995), pages 202-232; compounds described in Japanese Patent Application Publication No. 2000-066385; Japanese Patent Application Publication No. 2000-080068; Japanese Patent Publication No. 2004-534797; and Japanese Patent Application Publication No. 2006-342166. Commercially available products include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), and IRGACURE-OXE04 (manufactured by BASF). Also mentioned are TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), Adeka Arkls NCI-730, Adeka Arkls NCI-831, Adeka Arkls NCI-930 (manufactured by ADEKA CORPORATION), and N-1919 (a photopolymerization initiator containing a carbazole / oxime ester backbone (manufactured by ADEKA CORPORATION)). Omnirad1316 (IGM RESINS BV) is also an example.

[0172] Furthermore, examples of oxime compounds other than those mentioned above include compounds described in Japanese Patent Application Publication No. 2009-519904, which has an oxime linked to the N-position of a carbazole; compounds described in US Patent No. 7626957, which has a hetero substituent introduced into the benzophenone site; compounds described in Japanese Patent Application Publication No. 2010-015025 and US Patent Publication No. 2009-292039, which have a nitro group introduced into the pigment site; ketoxime compounds described in International Publication No. 2009-131189; and compounds described in US Patent No. 7556910, which contains a trisodium skeleton and an oxime skeleton within the same molecule; and compounds described in Japanese Patent Application Publication No. 2009-221114, which has a maximum absorption at 405 nm and good sensitivity to gamma-ray sources; etc. For example, reference can be made to paragraphs 0274-0275 of Japanese Patent Application Publication No. 2013-029760, the contents of which are incorporated into this specification. Specifically, as an oxime compound, a compound represented by the following formula (OX-1) is preferred. Furthermore, the NO bond of the oxime compound can be an (E) type oxime compound, a (Z) type oxime compound, or a mixture of (E) and (Z) types.

[0173] [Chemical Formula 10]

[0174] In formula (OX-1), R and B independently represent monovalent substituents, A represents divalent organogroups, and Ar represents aryl groups. In formula (OX-1), a monovalent nonmetallic group is preferred as a monovalent substituent represented by R. Examples of monovalent nonmetallic radicals include alkyl, aryl, acetyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic, alkylthiocarbonyl, and arylthiocarbonyl. Furthermore, these groups may have one or more substituents. Moreover, the aforementioned substituents may be further replaced by other substituents. Examples of substituents include halogen atoms, aryloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acetoxy groups, acetyl groups, alkyl groups, and aryl groups. In formula (OX-1), aryl, heterocyclic, arylcarbonyl, or heterocyclic carbonyl groups are preferred as the monovalent substituent represented by B, with aryl or heterocyclic groups being more preferred. These groups may have one or more substituents. Examples of the aforementioned substituents can be cited. 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.

[0175] Fluorine-containing oxime compounds can also be used as photopolymerization initiators. Examples of fluorine-containing oxime compounds include compounds described in JP-A-2010-262028; compounds 24, 36, and 40 described in JP-A-2014-500852; and compound (C-3) described in JP-A-2013-164471. These details are incorporated into this specification.

[0176] Examples of the polymerization initiator include compounds represented by the following formulas (1) to (4).

[0177] [Chemical Formula 11]

[0178] [Chemical Formula 12]

[0179] In formula (1), R1 and R2 each independently represent 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; when R1 and R2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorenyl group; R3 and R4 each independently represent 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.

[0180] In formula (2), R1, R2, R3 and R4 have the same meaning as R1, R2, R3 and R4 in formula (1). R5 represents -R6, -OR6, -SR6, -COR6, -CONR6R6, -NR6COR6, -OCOR6, -COOR6, -SCOR6, -OCSR6, -COSR6, -CSOR6, -CN, halogen atom or hydroxyl group. R6 represents alkyl with 1 to 20 carbon atoms, aryl with 6 to 30 carbon atoms, aralkyl with 7 to 30 carbon atoms or heterocyclic group with 4 to 20 carbon atoms. X represents direct bonding or carbonyl group. a represents an integer from 0 to 4.

[0181] In formula (3), R1 represents an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 4 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an aralkyl group with 7 to 30 carbon atoms, R3 and R4 represent hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms, or heterocyclic groups with 4 to 20 carbon atoms, respectively, and X represents a direct bond or a carbonyl group.

[0182] In formula (4), R1, R3 and R4 have the same meaning as R1, R3 and R4 in formula (3). R5 represents -R6, -OR6, -SR6, -COR6, -CONR6R6, -NR6COR6, -OCOR6, -COOR6, -SCOR6, -OCSR6, -COSR6, -CSOR6, -CN, halogen atom or hydroxyl group. R6 represents alkyl with 1 to 20 carbon atoms, aryl with 6 to 30 carbon atoms, aralkyl with 7 to 30 carbon atoms or heterocyclic group with 4 to 20 carbon atoms. X represents direct bonding or carbonyl group. a represents an integer from 0 to 4.

[0183] Examples of the compounds represented by formula (1) and formula (2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466, the contents of which are incorporated herein.

[0184] Furthermore, as the polymerization initiator, a compound represented by the following formula (1) is also preferred.

[0185] [Chemical Formula 13]

[0186] In formula (1), R represents a group represented by the following formula (1a),

[0187] [Chemical Formula 14]

[0188] In formula (1a), n represents an integer of 1 to 5. m represents an integer of 1 to 6. * represents a bonding position.

[0189] For m, 3 or 4 are preferred. The compound represented by formula (1) can be synthesized according to the synthesis method described in, for example, JP-A-2012-519191.

[0190] The following are specific examples of oxime compounds that are preferably used in the above-mentioned compositions. Furthermore, as oxime compounds, the compounds described in Table 1 of International Publication No. 2015-036910 can also be cited, and the above information is incorporated into this specification.

[0191] [Chemical Formula 15] [Chemical Formula 16]

[0192] [Chemical Formula 17]

[0193] Oxidime compounds are preferably those with maximum absorption wavelengths in the 350–500 nm wavelength region, even more preferably those with maximum absorption wavelengths in the 360–480 nm wavelength region, and even more preferably those with high absorbance at wavelengths of 365 nm and 405 nm. From a sensitivity point of view, a molar absorptivity of 1,000 to 300,000 at 365 nm or 405 nm for the oxime compound is preferred, 2,000 to 300,000 is more preferred, and 5,000 to 200,000 is even more preferred. The molar absorptivity of a compound can be determined using known methods, such as by a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer), preferably using ethyl acetate at a concentration of 0.01 g / L. Two or more photopolymerization initiators can be used in combination as needed.

[0194] Furthermore, as photopolymerization initiators, compounds described in Japanese Patent Application Publication No. 2008-260927, paragraph 0052, Japanese Patent Application Publication No. 2010-097210, paragraphs 0033 to 0037, and Japanese Patent Application Publication No. 2015-068893, paragraph 0044, can also be used, and the above information is incorporated herein by reference.

[0195] As a polymerization initiator, oxime ester-based polymerization initiators are preferred from the perspective of better performance of the present invention, and compounds represented by the above formula (1) are even more preferred.

[0196] The content of the polymerization initiator in the composition is not particularly limited. From the perspective of achieving better effects of the present invention, it 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 relative to the total solid content of the composition. A polymerization initiator can be used alone or in combination with two or more. When using two or more polymerization initiators, it is preferable that the total content be within the range mentioned above.

[0197] <surfactants> The composition may contain surfactants. Surfactants help improve the coatability of the composition. Examples of surfactants include polysiloxane surfactants, fluorinated surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants. Among these considerations, polysiloxane surfactants are preferred for achieving better results in this invention.

[0198] Examples of polysiloxane surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains and / or ends.

[0199] Examples of polysiloxane surfactants include, for instance, the DOWSIL (registered trademark) series of DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6000, KF-6004, KP-323, KP-341, KF-6001, and KF-6002 (all manufactured by Shin-Etsu Chemical). (Manufactured by Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by omentive performance materials Inc.); BYK307, BYK323 and BYK330 (manufactured by BYK-Chemie GmbH). As a preferred form of polysiloxane surfactant, considering the superior effects of the present invention, aromatic-modified polysiloxane surfactant (polysiloxane surfactant having aromatic groups) is preferred, and phenyl-modified polysiloxane surfactant (polysiloxane surfactant having phenyl groups) is even more preferred.

[0200] Examples of fluorinated surfactants include, for example, 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, and MEGAFACE F780 (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, and Surflon... SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393 and Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.); and PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, a block polymer can also be used, and examples thereof include the compounds described in JP-A-2011-089090.

[0201] When the composition contains a surfactant, there is no particular limitation on the content of the surfactant in the composition. However, from the perspective of better performance of the present invention, 0.001 to 2.0% by mass is preferred, 0.005 to 0.5% by mass is more preferred, and 0.01 to 0.1% by mass is even more preferred relative to the total solid content of the composition. 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.

[0202] <Solvent> The composition may contain solvents. The solvent is not particularly limited, and a known solvent can be used, and examples thereof include organic solvents and water. The content of solid components in the composition relative to the total mass of the composition is preferably 10-90% by mass, more preferably 10-50% by mass, and further preferably 15-50% by mass. That is, there is no particular limitation on the content of solvent in the composition, but it is preferable to adjust the solid components of the composition to the above-mentioned content. The solvent may be used alone or in combination of two or more. When two or more solvents are used in combination, it is preferred to adjust the total solid content of the composition to be within the above range.

[0203] Examples of organic solvents include, but are not limited to, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, 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.

[0204] <Compounds containing epoxy groups (adhesives)> The composition may contain a compound containing an epoxy group. Compounds containing epoxy groups include those having one or more epoxy groups, with those having two or more epoxy groups being preferred. The number of epoxy groups is preferably between 1 and 100. The upper limit can be, for example, 10 or less, or 5 or less. The lower limit is 2 or more, which is preferred. The epoxy group-containing compound refers to a component different from the above-mentioned dispersant, alkali-soluble resin, and polymerizable compound.

[0205] The epoxy equivalent weight (= molecular weight of the epoxy group-containing compound / number of epoxy groups) of the epoxy group-containing compound is preferably 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and even more preferably 100 to 300 g / equivalent.

[0206] Compounds containing epoxy groups can be low molecular weight compounds (e.g., molecular weight less than 2000) or macromolecules (e.g., molecular weight 2000 or more; in the case of polymers, the weight average molecular weight is 2000 or more). A weight average molecular weight of 200 to 100,000 is preferred, and 500 to 50,000 is more preferred. An upper limit of 10,000 or less is preferred, less than 5,000 is further preferred, and less than 3,000 is especially preferred.

[0207] Compounds containing epoxy groups may be commercially available. Examples include EHPE3150 (manufactured by Daicel Corporation) and EPICLON N-695 (manufactured by DIC CORPORATION). Furthermore, compounds containing epoxy groups may include those described in paragraphs 0034-0036 of Japanese Patent Application Publication No. 2013-011869, paragraphs 0147-0156 of Japanese Patent Application Publication No. 2014-043556, and paragraphs 0085-0092 of Japanese Patent Application Publication No. 2014-089408. These contents are incorporated herein by reference.

[0208] When the composition contains a compound containing an epoxy group, the content of the compound containing an epoxy group in the composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 8% by mass, and even more preferably 0.01 to 6% by mass relative to the total solid content in the composition. The epoxy-containing compound may be used alone or in combination with two or more compounds. When the above composition contains two or more epoxy-containing compounds, it is preferable that their total content is within the range described above.

[0209] <Silane coupling agent (adhesive)> The composition may contain silane coupling agents. When a light-shielding film is formed on a substrate, the silane coupling agent functions as a bonding agent to improve the adhesion between the substrate and the light-shielding film. Silane coupling agents are compounds containing hydrolyzable groups and other functional groups in their molecules. Furthermore, hydrolyzable groups such as alkoxy groups are bonded to silicon atoms. A hydrolyzable group refers to a substituent that directly bonds to a silicon atom and can form a siloxane bond through a hydrolysis reaction and / or a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, and alkenyloxy groups. When a hydrolyzable group contains carbon atoms, it is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms are preferred. Furthermore, when forming a light-shielding film on a substrate, in order to improve the adhesion between the substrate and the light-shielding film, it is preferred that the silane coupling agent does not contain fluorine atoms and silicon atoms (except for silicon atoms bonded to hydrolyzable groups). It is also preferred that the silane coupling agent does not contain fluorine atoms, silicon atoms (except for silicon atoms bonded to hydrolyzable groups), alkylene groups substituted with silicon atoms, linear alkyl groups with 8 or more carbon atoms, and branched alkyl groups with 3 or more carbon atoms. Silane coupling agents may contain ethylenically unsaturated groups such as (meth)acryloyl groups. When containing ethylenically unsaturated groups, the number is preferably 1 to 10, and more preferably 4 to 8. Furthermore, silane coupling agents containing ethylenically unsaturated groups (e.g., compounds containing hydrolyzable groups and ethylenically unsaturated groups and having a molecular weight of 2000 or less) are not considered polymerizable compounds.

[0210] Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0211] When the composition contains a silane coupling agent, the content of the silane coupling agent in the composition relative to the total solid content in the composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and further preferably 1.0 to 6% by mass. The composition may contain one silane coupling agent alone or two or more. When the composition contains two or more silane coupling agents, the total amount thereof may be within the above range.

[0212] <Ultraviolet absorber> The composition may contain an ultraviolet absorber. This allows the pattern shape of the light-shielding film formed by exposure to be more excellent (fine). Examples of UV absorbers include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and tris(III)-based UV absorbers. Furthermore, examples include the compounds described in paragraphs 0137 to 0142 of JP-A-2012-068418 (corresponding to paragraphs 0251 to 0254 of US 2012 / 0068292), the contents of which are incorporated herein by reference. In addition, diethylamino-phenylsulfonyl ultraviolet absorbers (manufactured by DAITO CHEMICAL CO.,LTD., trade name: UV-503) can also be cited. As ultraviolet absorbers, compounds illustrated in paragraphs 0134 to 0148 of Japanese Patent Application Publication No. 2012-032556 can also be cited. When the composition contains an ultraviolet absorber, the content of the ultraviolet absorber relative to the total solid content of the composition is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.1 to 5% by mass.

[0213] <Other colorants> The composition can contain any colorant, selected from pigments, dyes, or infrared absorbers, etc. However, it must be a colorant other than carbon black, barium sulfate, and those containing metal particles, as mentioned above.

[0214] <Other arbitrary ingredients> The composition may further include any other components besides those mentioned above. For example, polymerization inhibitors, sensitizers, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and sensitizers may be added as needed. Furthermore, known additives such as adhesion promoters and other auxiliaries (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peel accelerators, antioxidants, fragrances, surface tension modifiers, and chain transfer agents) may also be added as needed. For example, the components described in paragraphs 0183 to 0228 of Japanese Patent Application Publication No. 2012-003225 (paragraphs 0237 to 0309 of the corresponding 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 are incorporated herein by reference.

[0215] [Method for producing the composition] Regarding the composition, it is preferable to first prepare a dispersed composition in which the black pigment is dispersed, and then further mix the obtained dispersed composition with other components to form the composition. The dispersion composition is preferably prepared by mixing a black pigment, a resin (dispersion resin), and a solvent. Furthermore, it is also preferred to introduce a polymerization inhibitor into the dispersion composition. The dispersed 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, or a wet disperser). After preparing the dispersion composition, it is possible to mix the above dispersion composition, resin (alkali-soluble resin), polymerizable compound, polymerization initiator and solvent to prepare the product. When preparing the composition, all components can be combined at once, or each component can be dissolved or dispersed in a solvent separately and then combined sequentially. Furthermore, there are no particular restrictions on the order of addition or the operating conditions during the combination process.

[0216] The composition is designed to remove foreign matter and reduce defects, and filtration using a filter is preferable. As a filter, for example, any filter that has been used for filtration purposes can be used without particular restrictions. Examples include filters based on fluoropolymers such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight resins). Among these, polypropylene (including high-density polypropylene) or nylon is preferred. The filter pore size is preferably 0.1-7.0 μm, more preferably 0.2-2.5 μm, even more preferably 0.2-1.5 μm, and particularly preferably 0.3-0.7 μm. This range prevents clogging of the filter by pigments (including black pigments) and reliably removes fine foreign matter such as impurities and aggregates contained in the pigment. The composition preferably contains no impurities such as metals, halogen-containing metal salts, acids, and bases. The content of impurities in these materials is preferably 1 ppm by mass or less, more preferably 1 ppb by mass or less, even more preferably 100 ppt by mass or less, and particularly preferably 10 ppt by mass or less. Most preferably, the content is substantially free (below the detection limit of the measuring device). Furthermore, the aforementioned impurities can be determined using an inductively coupled plasma mass spectrometer (Yokogawa Electric Corporation, Agilent 7500cs model).

[0217] [Manufacturing method of light-blocking film] Hardened films are preferred for light-shielding films. In this specification, "cured film" refers to a film formed by subjecting a composition layer formed using the composition to a curing process such as exposure treatment. The following describes the manufacturing method of a light-shielding film (hardened film) when the light-shielding film is a hardened film. A preferred method for manufacturing a light-shielding film includes the following steps. Through these steps, for example, a patterned light-shielding film can be formed. Furthermore, if the light-shielding film is not patterned, a developing step may be omitted. The following is a description of each step.

[0218] [Steps for the formation of constituent layers] In the composition layer formation step, a composition layer (composition layer) is formed by applying a composition onto a support or the like before exposure. For example, a solid-state imaging substrate can be used where an imaging element (light-receiving element) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) is disposed on a substrate (e.g., a silicon substrate). Furthermore, as needed, a lower coating layer can be provided on the support to improve adhesion to the upper layer, prevent material diffusion, and planarize the substrate surface.

[0219] Various coating methods can be used to coat the composition onto the support, including slot coating, inkjet coating, spin coating, cast coating, roller coating, and screen printing. A film thickness of 0.1–10 μm is preferred, 0.2–5 μm is more preferred, and 0.2–3 μm is further preferred. Drying (pre-baking) of the composition layer coated on the support can be performed using a heated plate or oven at a temperature of 50–140°C for 10–300 seconds.

[0220] [Exposure Step] The exposure step is a step of exposing the composition layer formed in the composition layer formation step to active light or radiation. Specifically, the exposure step is as follows: exposing the composition layer formed in the composition layer formation step to active light or radiation to harden the light-exposed area of ​​the composition layer. There are no particular restrictions on the method of light irradiation, but it is better to irradiate the light through a light mask with patterned openings. Exposure is preferably performed by irradiation with radiation. Ultraviolet radiation, especially gamma rays, h-rays, and i-rays, is preferred for exposure. High-pressure mercury lamps are preferred as the light source. An irradiation intensity of 5–1500 mJ / cm² is preferred, and 10–1000 mJ / cm² is even better. Furthermore, when the composition contains a thermal polymerization initiator, heating the composition layer during the aforementioned exposure step is also preferable. There are no particular limitations on the heating temperature, but 80–250°C is preferred. Also, there are no particular limitations on the heating time, but 30–300 seconds is preferred. Furthermore, the heating of the constituent layer during the exposure step can also serve as the post-heating step described later. In other words, the method for manufacturing the light-shielding film may not include the post-heating step when heating the constituent layer during the exposure step.

[0221] [Developing steps] The development step is a process of developing the exposed constituent layer. Through this step, the constituent layer in the photoexposed area of ​​the exposure step dissolves, leaving only the photocured portion. For example, when light is applied through a photomask with patterned openings during the exposure step, a patterned light-shielding film can be obtained. There are no particular restrictions on the type of developer used in the developing step, but an alkaline developer that will not damage the imaging elements and circuitry of the substrate is preferred. The developing temperature is, for example, 20~30℃. The development time is, for example, 20 to 90 seconds. In recent years, 120 to 180 seconds has sometimes been used to further remove residue. Furthermore, in order to further improve the removal of residue, the following steps are sometimes repeated several times: the developer is shaken off every 60 seconds and then the developer is replenished.

[0222] The alkaline 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). Examples of basic compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diacrylbicyclo[5.4.0]-7-undecene (of which, organic bases are preferred). Furthermore, when used as an alkaline developer, washing with water is usually performed after development.

[0223] [Post-baking] After the exposure step, a heat treatment (post-baking) is preferable. Post-baking is a heat treatment used after development for complete curing. The heating temperature is preferably below 240°C, and even better below 220°C. There is no particular lower limit, but for efficient and effective processing, temperatures above 50°C are preferred, and above 100°C are even better. Post-baking can be carried out continuously or intermittently using heating mechanisms such as hot plates, convection ovens (hot air circulation dryers) and high-frequency heaters.

[0224] The above-mentioned post-baking is preferably carried out in a low-oxygen atmosphere. An oxygen concentration of 19% by volume or less is preferred, 15% by volume or less is even better, 10% by volume or less is further preferred, 7% by volume or less is particularly preferred, and 3% by volume or less is optimal. There is no specific lower limit, but in practice it is above 10 ppm by volume.

[0225] Alternatively, it can be modified to bake after heating as described above, and then harden completely by UV (ultraviolet) irradiation. At this point, it is preferable that the above-mentioned composition further includes a UV curing agent. The UV curing agent is preferably one capable of curing at a wavelength shorter than 365 nm, i.e., the exposure wavelength of the polymerization initiator added by the lithography step using conventional i-ray exposure. Ciba IRGACURE 2959 (trade name) is an example of a UV curing agent. It is preferable that the composition layer is cured at a wavelength below 340 nm during UV irradiation. There is no particular limitation on the lower limit of the wavelength, but it is typically 220 nm or higher. Furthermore, the exposure dose of the UV irradiation is preferably 100-5000 mJ, more preferably 300-4000 mJ, and further preferably 800-3500 mJ. For more effective low-temperature curing, it is preferable that the UV curing step is performed after the lithography step. An ozone-free mercury lamp is preferably used as the exposure light source.

[0226] [Physical properties and applications of light-blocking film] [Physical properties of light-shielding film] From the perspective of excellent light-shielding performance, it is preferable for the light-shielding film to have an optical density (OD) of 3.0 or higher per 5.0 μm of film thickness in the wavelength region of 400~1100nm, and even better if it is 3.5 or higher. Furthermore, there is no particular upper limit, and it is generally preferred to be below 10. In this specification, the optical density of 3.0 or more per 5.0 μm film thickness in the wavelength region of 400 to 1100 nm means that the optical density per 5.0 μm film thickness is 3.0 or more in the entire wavelength region of 400 to 1100 nm. In this specification, as a method for measuring the optical density of a light-shielding film, first, a light-shielding film is formed on a glass substrate and measured using a spectrophotometer (eg, U-4100 manufactured by Hitachi High-Tech Corporation). The thickness of the light-shielding film is preferably 0.1~6.0μm, more preferably 1.0~5.0μm, and even more preferably 1.0~2.5μm. Furthermore, the light-shielding film can be configured as a thin film smaller than this range, or as a thick film larger than this range, depending on the application. Furthermore, considering excellent low reflectivity, it is preferable for the maximum reflectivity of the light-shielding film per 5.0 μm film thickness (at an incident angle of 5°) to be less than 5% in the wavelength region of 350~1200nm, and even better if it is less than 3%. Moreover, there is no particular limitation on the lower limit value, which is usually above 0%. Furthermore, in this specification, as a method for determining the maximum reflectivity of the light-shielding film, firstly, a light-shielding film is formed on a glass substrate, and then a reflectivity spectrum relative to an incident angle of 5° is obtained using a spectrometer (e.g., the VAR unit of a JASCO Corporation V7200 spectrometer), and the reflectivity of light at the wavelength exhibiting the maximum reflectivity in the wavelength region of 350~1200nm is determined.

[0227] Furthermore, the aforementioned light-shielding film is suitable for portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) equipment such as multifunction printers and scanners; industrial equipment such as surveillance cameras, barcode readers, and automated teller machines (ATMs), high-speed cameras, and devices with facial recognition authentication functions; vehicle-mounted camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters; space equipment such as biosensors, biological sensors, military reconnaissance cameras, stereoscopic map cameras, meteorological and oceanographic observation cameras, land resource reconnaissance cameras, and space exploration cameras for astronomy and deep space targets; and light-shielding components and films used in optical filters and modules, and are further suitable for anti-reflective components and anti-reflective films.

[0228] The aforementioned light-shielding film can also be used in applications such as micro-LEDs (Light Emitting Diodes) and micro-OLEDs (Organic Light Emitting Diodes). Besides being suitable for optical filters and films used in micro-LEDs and micro-OLEDs, the aforementioned light-shielding film is also suitable for components that impart light-shielding or anti-reflective functions. Examples of micro LEDs and micro OLEDs include those described in Japanese Patent Application Publication No. 2015-500562 and Japanese Patent Application Publication No. 2014-533890.

[0229] Light-shielding films are also suitable as optical filters and films used in quantum dot sensors and quantum dot solid-state imaging devices. They are also suitable as components that impart light-shielding and anti-reflection functions. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in U.S. Patent Application Publication No. 2012 / 37789 and International Publication No. 2008 / 131313.

[0230] [Solid-state imaging element and solid-state imaging device] The light-shielding film is also preferably used for a solid-state imaging element. In other words, the solid-state imaging element of the present invention is a solid-state imaging element having the light-shielding film of the present invention. There are no particular limitations on the form in which a light-shielding film is included in a solid-state imaging element. For example, the following form can be given: a light-receiving element is provided on a substrate, which is composed of a plurality of photodiodes and polysilicon, etc., constituting the light-receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.), and a light-shielding film is provided on the side of the light-receiving element forming surface of the support (e.g., the part other than the light-receiving part and / or the pixel for color adjustment, etc.) or on the side opposite to the forming surface. Furthermore, when a light-shielding film is used as a light-attenuating film, for example, if the light-attenuating film is configured such that a portion of the light is incident on the light-receiving element after passing through the light-attenuating film, the dynamic range of the solid-state imaging element can be improved. The solid-state imaging device includes the aforementioned solid-state imaging element.

[0231] [Image display device] The light-shielding film is also preferably applicable to image display devices. In other words, the image display device of the present invention is an image display device having the light-shielding film of the present invention. As an image display device, it may have the form of a light-shielding film. For example, a color filter with a black matrix containing a light-shielding film may be applied to an image display device. Next, the black matrix and the color filter containing the black matrix will be explained, and then, as a specific example of an image display device, a liquid crystal display device containing such a color filter will be explained.

[0232] <Black Matrix> It is also preferable to include the light-shielding film within the black matrix. Black matrices are sometimes included in image display devices such as color filters, solid-state imaging elements, and liquid crystal displays. Examples of a black matrix include those described above; black edges set at the periphery of image display devices such as liquid crystal displays; grid-like and / or linear black portions between red, blue, and green pixels; dot-like and / or linear black patterns used for light shielding in TFTs (thin film transistors); etc. A definition of this black matrix can be found, for example, in Taihei Sugano's "Dictionary of Terms for Liquid Crystal Display Manufacturing Equipment," 2nd edition, NIKKAN KOGYO SHIMBUN, LTD., 1996, page 64. In order to improve the display contrast and prevent the degradation of image quality caused by light leakage current when using an active matrix drive liquid crystal display device using a thin film transistor (TFT), it is preferred that the black matrix has high light shielding properties (measured in optical density OD of 3 or more).

[0233] The method for producing the black matrix is ​​not particularly limited and can be produced using the same method as the aforementioned method for producing the light-shielding film. Specifically, a composition can be applied to a substrate to form a composition layer, which is then exposed and developed to produce a patterned light-shielding film (black matrix). The thickness of the light-shielding film (black matrix) is preferably 0.1 to 4.0 μm.

[0234] The substrate is not particularly limited, but preferably has a transmittance of 80% or greater for visible light (wavelength 400-800 nm). Examples of materials for this substrate include glasses such as soda-lime glass, alkali-free glass, quartz glass, and borosilicate glass; and plastics such as polyester resins and polyolefin resins. From the perspective of chemical resistance and heat resistance, alkali-free glass and quartz glass are preferred.

[0235] <Color Filter> It is also preferred that a light-shielding film be included in the color filter. The form of the color filter including the light-shielding film is not particularly limited, and examples thereof include a color filter comprising a substrate and the aforementioned black matrix. Specifically, an example of a color filter comprising red, green, and blue colored pixels formed in the openings of the aforementioned black matrix formed on the substrate can be exemplified.

[0236] Color filters containing a black matrix can be manufactured, for example, by the following methods. First, a coating film (composition layer) containing a pigment corresponding to each colored pixel of the color filter is formed in the openings of a patterned black matrix formed on a substrate. The composition for each color is not particularly limited, and known compositions can be used. Among the compositions described in this specification, it is preferred to use a composition that replaces the black pigment with a colorant corresponding to each pixel. Next, the composition layer is exposed through a photomask with a pattern corresponding to the openings of the black matrix. Then, after removing the unexposed areas by development, a baking process is performed to form colored pixels at the openings of the black matrix. For example, by performing a series of operations using a composition containing red, green, and blue pigments, a color filter with red, green, and blue pixels can be manufactured.

[0237] Liquid crystal display device It is also preferable that a light-shielding film is included in the liquid crystal display device. There are no particular limitations on the form in which the light-shielding film is included in the liquid crystal display device, and a form that includes a color filter containing the black matrix (light-shielding film) described above can be cited as an example.

[0238] As a liquid crystal display device, for example, there can be mentioned a form including a pair of substrates arranged opposite to each other and a liquid crystal compound sealed between the substrates. As the substrate, the black matrix substrate has been described.

[0239] As a specific form of the aforementioned liquid crystal display device, for example, a multilayer assembly comprising, in sequence from the user side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) element / substrate / polarizing plate / backlight unit.

[0240] Furthermore, liquid crystal display devices are not limited to those mentioned above. Examples include those described in works such as "Electronic Display Devices" (by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd., 1990) and "Display Devices" (by Junsho Ibuki, published by Sangyo Tosho Publishing Co., Ltd., 1994). Also, examples include those described in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd., 1994).

[0241] [Infrared sensor] It is also preferred that a light-shielding film be included in the infrared sensor. Next, a solid-state imaging device to which the above-mentioned infrared sensor is applied will be described. The aforementioned solid-state imaging device includes a lens optical system, a solid-state imaging element, and an infrared light-emitting diode, etc. Furthermore, regarding the various structures of the solid-state imaging device, please refer to paragraphs 0032 to 0036 of Japanese Patent Application Publication No. 2011-233983, the contents of which are incorporated herein by reference. [Example]

[0242] The present invention will now be described in further detail with reference to the embodiments. The materials, amounts, proportions, processing contents, and processing order shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be limited by the embodiments shown below.

[0243] [Various components used in the preparation of compositions for forming light-shielding films] The following is a detailed description of the components used to prepare the light-shielding film.

[0244] [Adhesive resin] The following resins were used as adhesive resins (resins B-1 to B-12) as shown in Table 3.

[0245] <Resin B-1~B-10> The structures of resins B-1 to B-10 are shown in Table 2. Synthetic resins were used as resins B-1 to B-10. Hereinafter, an example of the synthesis of resin B-1 will be shown. Furthermore, resins B-2 to B-10 were synthesized in the same order as in the example of resin B-1, except that the types and proportions of the raw material monomers were changed.

[0246] (Synthesis example of resin B-1) A monomer solution was prepared by mixing 173.7 g of butyl methacrylate, 20.0 g of methacrylic acid, and 6.3 g of 2-hydroxyethyl methacrylate. A mixture A was then prepared, which contained 2 mol% of a thermal polymerization initiator (FUJIFILM Wako Pure Chemical Corporation V-601) relative to the total mass of the monomers, and 111% by mass of 1-methoxy-2-propanol relative to the total mass of the monomers. Next, a mixture B consisting of the monomer mixture and 74% by mass of 1-methoxy-2-propanol relative to the total mass of the monomers was prepared and heated to 80°C. Mixture A was then added dropwise to mixture B over 2 hours (droplet polymerization). Following the droplet addition, the mixture was heated at 80°C for 2 hours, and then further heated at 90°C for 3 hours, thereby synthesizing resin B-1.

[0247] [Table 2] Table 2 Composition of adhesive resin Ingredient types Component ratio (mass%) Repeating Unit 1 Repeating Unit 2 Repeating unit 3 Repeating Unit 1 Repeating Unit 2 Repeating unit 3 B-1 X-1 Y-1 Z-1 86.85 10 3.15 B-2 X-2 Y-1 Z-1 86.85 10 3.15 B-3 X-1 Y-1 Z-1 86.85 10 3.15 B-4 X-1 Y-1 Z-1 86.85 10 3.15 B-5 X-2 Y-1 - 87.5 12.5 - B-6 X-2 Y-1 - 87.5 12.5 - B-7 X-2 Y-1 - 87.5 12.5 - B-8 X-2 Y-1 - 87.5 12.5 - B-9 X-2 Y-1 Z-1 85.5 2.5 12 B-10 X-2 Y-1 Z-2 66 22.5 11.5

[0248] The following shows the repeating units (X-1, X-2, Y-1, Z-1, and Z-2) shown in Table 2.

[0249] [Chemical Formula 18]

[0250] <Resin B-11~B-12> The structures of resins B-11 to B-12 are shown below. Furthermore, resin B-11 was synthesized using the method described in Japanese Patent Application Publication No. 2014-177614.

[0251] (Resin B-11) [Chemical Formula 19]

[0252] (Resin B-12) [Chemical Formula 20]

[0253] Pigment dispersion Dispersions 1 and 2 were used as the pigment dispersions shown in Table 3. The preparation methods of dispersions 1 and 2 will be described below.

[0254] <Preparation of Dispersion Liquid 1> (Preparation of titanium black (A-1)) 120g of titanium dioxide TTO-51N (trade name: ISHHIHARA SANGYO KAISHA, LTD.) with a BET surface area of ​​110 m² / g, 25g of silica particles AEROS IL300 (registered trademark) 300 / 30 (EVONIK) with a BET surface area of ​​300 m² / g, and 100g of dispersant Disperbyk 190 (trade name: BYK-Chemie GmbH) were weighed, along with 71g of ion-exchanged water. The mixture was treated for 30 minutes using a KURABO MAZERSTAR KK-400W furnace at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm, thereby obtaining a homogeneous aqueous solution. This aqueous solution was filled into a quartz container and heated to 920°C in an oxygen atmosphere using a small rotary kiln (Motoyama Co., Ltd.). Subsequently, the atmosphere inside the small rotary kiln was replaced with nitrogen, and ammonia gas was circulated inside the small rotary kiln at the same temperature at a rate of 100 mL / min for 5 hours, thereby performing nitriding reduction treatment. After completion, the recovered powder was pulverized in a mortar to obtain powdered titanium black (A-1) containing Si atoms and with a specific surface area of ​​85 m² / g [a dispersed body containing titanium black particles and Si atoms].

[0255] (Preparation of Dispersion 1) Using a mixer (EUROSTAR manufactured by IKA), the components shown in composition 1 below were mixed for 15 minutes to obtain dispersion a.

[0256] Composition 1 • Titanium black (A-1) synthesized in the above sequence • 25.0 parts by mass • A 20% by weight solution of propylene glycol monomethyl ether acetate for dispersion resin A-1 as described below • 37.5 parts by weight Propylene glycol monomethyl ether acetate (PGMEA) · 10.5 parts by weight Butyl acetate (solvent) 27.0 parts by mass

[0257] (Dispersion resin A-1: ​​The structure is as follows. The weight average molecular weight is shown in Table 3. The acid value is 57.2 mg KOH / g, and the glass transfer temperature is 33 °C.) Furthermore, in the following structural formulas, the units of the values ​​marked in parentheses in the main chain are mass%, and the values ​​marked in parentheses in the side chain are equivalent to the average additive number.

[0258] [Chemical Formula 21]

[0259] NPM-Pilot was prepared using SHINMARU ENTERPRISES CORPORATION. Dispersion 1 was obtained by dispersing dispersion a under the following conditions. Dispersion Conditions Bead diameter: φ0.05mm, made of zirconium dioxide Bead filling rate: 65% by volume • Grinding circumferential speed: 10m / sec • Separator circumferential speed: 11 m / s ·Amount of mixed liquid for dispersion treatment: 15kg • Circulation flow rate (pump supply): 60 kg / hour • Processing solution temperature: 19~21℃ Cooling water: water Number of passes: 90

[0260] <Preparation of Dispersion Liquid 2> Dispersion 2 was prepared in the same order as in <Preparation of Dispersion 1>, except that dispersion resin A-2 with the structure described below was used instead of dispersion resin A-1.

[0261] (Dispersion resin A-2: The structure is as follows. The weight average molecular weight is shown in Table 3. The acid value is 55.7 mg KOH / g, and the glass transfer temperature is 55 °C.) Furthermore, in the following structural formulas, the units of the values ​​marked in parentheses in the main chain are mass%, and the values ​​marked in parentheses in the side chain are equivalent to the average additive number.

[0262] [Chemical Formula 22]

[0263] 〔Polymerizable compounds〕 The polymerizable compounds (D-1 to D-3) shown in Table 3 are shown below. D-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentatriol pentaacrylate and dipentatriol hexaacrylate) • D-2:NK Ester A-DPH-12E (Ethoxylated dinepentylenetetraethylene polyacrylate manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd) • D-3:NK Ester A-TMMT (Shin-NAKAMURA CHEMICAL Co., Ltd., which produces neopentyl terephthalate tetraacrylate)

[0264] [Initiator] The following table shows the initiators (E-1 to E-4) listed in Table 3. E-1: ADEKA ARKLS NCI-831E (oxime ester polymerization initiator manufactured by ADEKA CORPORATION) E-2: Compounds with the following structure (oxime ester polymerization initiators)

[0265] [Chemical Formula 23]

[0266] E-3: IRGACURE OXE02 (manufactured by BASF, oxime ester polymerization initiator) • E-4: IRGACURE OXE01 (manufactured by BASF, oxime ester polymerization initiator)

[0267] [Solvent] The solvents shown in Table 3 are listed below. Cyclopentanone (manufactured by FUJIFILM Wako Pure Chemical Corporation) Propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko KK) Butyl acetate (manufactured by SANKYO CHEMICAL CO.,LTD.)

[0268] [Surfactants] The surfactants (W-1) shown in Table 3 are shown below. ·W-1:KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0269] 〔additive〕 The additives shown in Table 3 (X-1) are listed below. X-1: EHPE 3150 (manufactured by Daicel Corporation) (CAS No. 244772-00-7)

[0270] [Preparation of composition] Each composition (compositions-1 to 21, R1 to R2) was prepared by mixing according to the ingredients and proportions shown in Table 3 below. Furthermore, as composition-R3, the same composition as that in Example 1 of International Publication No. 2017 / 057192 was prepared. Furthermore, solvents A through C are described in the table below. "Solvent A": Cyclopentanone Solvent B: Propylene glycol monomethyl ether acetate (PGMEA) Solvent C: Butyl acetate Also, in Table 3, the unit of acid value is mgKOH / g.

[0271] [Table 3] Table 3 (Part 1) Composition for forming light-shielding film Pigment dispersion Adhesive resin (Alkali-soluble resin) polymerizable compounds Polymerization initiator solvent surfactants Additives type dispersion resin parts by mass type Acid value Mw Tg(℃) parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type Mw Composition-1 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-2 Dispersion 1 A-1 30,000 49.2 B-2 60 19000 112 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-3 Dispersion 1 A-1 30,000 49.2 B-3 60 13000 65 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-4 Dispersion 1 A-1 30,000 49.2 B-4 60 8000 65 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-5 Dispersion 1 A-1 30,000 49.2 B-5 70 25000 105 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-6 Dispersion 1 A-1 30,000 49.2 B-6 70 30,000 105 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-7 Dispersion 1 A-1 30,000 49.2 B-7 70 20000 105 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-8 Dispersion 1 A-1 30,000 49.2 B-8 70 15000 105 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-9 Dispersion 1 A-1 30,000 49.2 B-9 40 19000 112 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-10 Dispersion 1 A-1 30,000 49.2 B-10 90 19000 112 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-11 Dispersion 2 A-2 15000 49.2 B-1 60 19000 65 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-12 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.93 D-2 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-13 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.93 D-3 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 - - Composition-14 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.93 D-1 D-3 3.92 3.92 E-1 2.26 Solvent A 7.06 W-1 0.02 - -

[0272] [Table 4] Table 3 (Part 2) Composition for forming light-shielding film Pigment dispersion Adhesive resin (Alkali-soluble resin) polymerizable compounds Polymerization initiator solvent surfactants Additives type dispersion resin parts by mass type Acid value Mw Tg(℃) parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type Mw Composition-15 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.93 D-1 7.83 E-2 2.26 Solvent A 7.06 W-1 0.02 Composition-16 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.93 D-1 7.83 E-1 E-3 1.13 1.13 Solvent A 7.06 W-1 0.02 Composition-17 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.93 D-1 7.83 E-1 2.26 Solvent B 7.06 W-1 0.02 Composition-18 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.93 D-1 7.83 E-1 2.26 Solvent C 7.06 W-1 0.02 Composition-19 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.83 D-1 7.73 E-1 E-4 1.13 1.13 Solvent A 7.06 W-1 0.02 X-1 0.3 Composition-20 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.69 D-1 7.59 E-1 E-4 1.13 1.13 Solvent A 7.06 W-1 0.02 X-1 0.7 Composition-21 Dispersion 1 A-1 30,000 49.2 B-1 60 19000 65 6.60 D-1 7.5 E-1 E-4 1.13 1.13 Solvent A 7.06 W-1 0.02 X-1 1.1 Composition-R1 Dispersion 1 A-1 15000 49.2 B-11 70 9200 65 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 Composition - R2 Dispersion 1 A-1 15000 49.2 B-12 70 11000 65 6.93 D-1 7.83 E-1 2.26 Solvent A 7.06 W-1 0.02 Composition - R3 The composition disclosed in Example 1 of International Publication No. 2017 / 057192

[0273] [Making of Sun-Shielding Film] The obtained composition was coated onto a glass substrate using spin coating to create a film with a post-exposure thickness of 5.0 μm. After pre-baking at 90°C for 120 seconds, the entire substrate was exposed using a UX-1000SM-EH04 (manufactured by Ushio Inc.) high-pressure mercury lamp (50 mW / cm²) at an exposure dose of 1000 mJ / cm². The exposed substrate was then post-baked at 220°C for 300 seconds to obtain a substrate with a light-shielding film (hardening film).

[0274] [evaluate] [Evaluation of light-blocking properties (determination of OD)] The transmittance spectrum of the fabricated substrate with a light-shielding film was measured from 400 to 1100 nm using a U-4100 spectrophotometer (manufactured by Hitachi High-Tech Corporation) and an integrating sphere light-receiving unit. The OD value was calculated from the transmittance (%) at the wavelength showing the maximum transmittance using the following formula, and evaluated according to the following criteria. If the evaluation is A~B, it is determined that there are no problems in practical application. The results are shown in Table 4. OD = -log10 (transmittance / 100) (Evaluation Criteria) "A": OD value of 3.0 or above "B": OD is 2.5 or higher but less than 3.0 “C”: OD not reaching 2.5

[0275] [Evaluation of reflectivity] For the fabricated substrate with a light-shielding film, the VAR unit of the JASCO Corporation V7200 beam splitter (trade name) was used to incident light with wavelengths of 350~1200nm at an incident angle of 5°, and the reflectance spectrum was evaluated based on the obtained data. Specifically, the reflectance of light with a wavelength of 940nm was used as the evaluation criterion, and the evaluation was carried out according to the following classification. If the evaluation is A~C, it is determined that there is no problem in practical application. The results are shown in Table 4. (Evaluation Criteria) "A": Reflectivity less than 1% "B": Reflectivity is above 1% but below 3%. "C": Reflectivity is 3% or higher but less than 5%. "D": Reflectivity is above 5%.

[0276] 〔Evaluation of surface roughness〕 After spin-coating each component onto a glass substrate (Corning 1737 [trade name], manufactured by Corning Corporation), a heat treatment (pre-baking) was performed for 2 minutes using a heating plate at 100°C. Subsequently, the entire substrate was exposed using a UX-1000SM-EH04 (manufactured by Ushio Inc.) with a high-pressure mercury lamp (lamp power of 50mW / cm 2) and an exposure dose of 1000mJ / cm 2. Subsequently, the substrate was subjected to a 10-60 second immersion development using a 0.29% by mass TMAH (tetramethylammonium hydroxide) developer. After washing and drying, the substrate was subjected to a 300-second heat treatment (post-baking) using a 220°C heating plate, thereby producing a substrate with a resin film. The surface roughness (Ra) of the resin film on the obtained substrate was measured within a 1 mm distance using a DektakXT manufactured by BRUKER (resolution: 1 μm / point), and the surface roughness Ra (Å) was determined. The results are shown in Table 4.

[0277] [Confirmation of pattern shape] Using the above method, the total length (boundary distance L) of the boundary line between the first and second phases for every 1μm × 1μm section of the obtained light-shielding film cross-section was calculated. The results are shown in Table 4. Furthermore, the light-shielding films of each embodiment and comparative example have a phase separation structure consisting of a first phase and a second phase.

[0278] [Table 5] Table 4 Types of components Structure of the light-shielding film Evaluation results Boundary distance L (μm) Surface roughness Ra (Å) OD Reflectivity Example 1 Composition-1 5.15 500 A A Example 2 Composition-2 9.80 1200 A B Example 3 Composition-3 11.20 100 A C Example 4 Composition-4 14.87 50 A C Example 5 Composition-5 6.76 1400 A A Example 6 Composition-6 10.34 2500 A C Example 7 Composition-7 8.96 320 A B Example 8 Composition-8 10.78 90 A C Example 9 Composition-9 4.92 1200 A B Example 10 Composition-10 4.92 1200 A B Example 11 Composition-11 12.30 20 A C Example 12 Composition-12 5.65 1000 A A Example 13 Composition-13 6.78 800 A A Example 14 Composition-14 5.82 600 A A Example 15 Composition-15 4.22 600 A A Example 16 Composition-16 2.56 900 A A Example 17 Composition-17 8.99 300 A B Example 18 Composition-18 10.22 300 A B Example 19 Composition-19 5.30 450 A A Example 20 Composition-20 5.20 430 A A Example 21 Composition-21 6.10 400 A A Comparative Example 1 Composition-R1 35.20 30 A D Comparative Example 2 Composition - R2 37.00 20 A D Comparative Example 3 Composition - R3 25.64 40 B D

[0279] The results in the table show that the light-shielding films of the examples have excellent light-shielding properties and exhibit excellent low-reflection characteristics. Furthermore, based on the comparison between Example 1 (using composition-1), Example 17 (using composition-17), and Example 18 (using composition-17), it was confirmed that when cyclopentanone is used as the solvent for the composition for forming the light-shielding film, the low-reflection characteristics of the light-shielding film are more excellent. Furthermore, based on a comparison between Example 1 (using composition-1) and Example 2 (using composition-2), it was confirmed that when the glass transfer temperature of the alkali-soluble resin of the composition for forming the light-shielding film is below 70°C, the low-reflection characteristics of the light-shielding film are more superior. Furthermore, based on the comparison of Example 1 (using composition-1) with Example 3 (using composition-3) and Example 4 (using composition-4), and the comparison of Example 5 (using composition-5) to Example 8 (using composition-8), it was confirmed that when the weight average molecular weight of the alkali-soluble resin is 18,000 to 25,000, the low reflectance characteristics of the light-shielding film are more superior.

[0280] Furthermore, based on the comparison between Example 1 (using composition-1) and Example 11 (using composition-11), it was confirmed that when the dispersion resin of the composition for forming the light-shielding film is dispersion resin A-1, the low-reflection characteristics of the light-shielding film are more superior.

[0281] The light-shielding film of the comparative example produced by changing the composition of the light-shielding film-forming composition did not exhibit the desired effect.

[0282] [Making of Sun-Shielding Film] [Preparation of light-shielding component A] The dispersion 2 (78.0 parts by mass), the resin B-12 (0.3 parts by mass), ARONIX M-305 (manufactured by TOAGOSEI CO., LTD., 4.2 parts by mass) as a polymerizable compound, E-1 (0.6 parts by mass) as a polymerization initiator, cyclopentanone (15.8 parts by mass) as a solvent for TR-PBG-304 (manufactured by TRonly, 0.6 parts by mass), 4-methoxyphenol (0.002 parts) as a polymerization inhibitor, the following compound (0.3 parts) and EHPE 3150 (manufactured by Daicel Corporation, 0.3 parts) as additives, and W-1 (0.02 parts by mass) as a surfactant were mixed to prepare a light-shielding composition A. Furthermore, in the following compounds, n is 2 to 4, and m represents 1 or 2. The following compounds are mixtures of compounds in which n and m represent any range of the above numerical values.

[0283] [Chemical Formula 24]

[0284] [Making glass with a light-shielding pattern / black matrix] Composition 19 (see Table 3) prepared in the previous section was applied to a 10 cm square glass substrate by spin coating, resulting in a film with a thickness of 6.0 μm after exposure. The resulting film was pre-baked at 90°C for 120 seconds. Then, using an EVG610 (manufactured by EVG), exposure was performed at an exposure dose of 200 mJ / cm² using a high-pressure mercury lamp (lamp power of 20 mW / cm²) through a mask capable of forming a frame-shaped pattern with an outer dimension of 10 mm, an inner dimension of 9.5 mm, and a width of 0.5 mm. Spin-immersion development was performed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). The film was then rinsed with pure water using a spin spray. Subsequently, the film was heated at 200°C for 5 minutes (post-baking) on ​​a hot plate to form a frame-shaped pattern.

[0285] On the aforementioned glass with a bordered light-shielding pattern, a light-shielding component A was spin-coated to create a film with a post-exposure thickness of 1.0 μm. After pre-baking the obtained film at 90°C for 120 seconds, exposure was performed using an EVG610 (manufactured by EVG Corporation) through a mask capable of creating a grid pattern with a line width of 100 μm and a line spacing of 600 μm within the border pattern, using a high-pressure mercury lamp (lamp power of 20 mW / cm²) at an exposure dose of 200 mJ / cm². Immersion development was performed for 60 seconds at 23°C using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Afterwards, rinsing was performed using pure water via a rotating spray. Then, heating was performed at 200°C for 5 minutes (post-baking) using a heated plate, thereby forming a black matrix pattern. The glass with the light-shielding pattern / black matrix exhibits excellent light-shielding properties and reflectivity.

[0286] A: Phase 1 B: Phase 2

Claims

1. A light-shielding film comprising a black pigment, wherein the light-shielding film has a phase-separated structure consisting of a first phase comprising the aforementioned black pigment and a second phase substantially not comprising the aforementioned black pigment, wherein when observing a 1×1μm² section of the light-shielding film orthogonal to the surface, the total length of the boundary lines of the aforementioned first phase and the aforementioned second phase is 2.50 to 15.00μm.

2. The light-shielding film as described in claim 1, wherein the surface roughness Ra is 400 to 2000 Å.

3. The light-shielding film as described in claim 1 is formed using a composition comprising a black pigment, a resin, and a polymeric compound.

4. The light-shielding film as described in any one of claims 1 to 3, wherein the total length of the aforementioned film is 2.50 to 7.00 μm.

5. The light-shielding film as described in any one of claims 1 to 3, wherein the first phase comprises a first resin with an acid value of 40 to 100 mg KOH / g, and the second phase comprises a second resin with an acid value of 40 to 90 mg KOH / g.

6. The light-shielding film as claimed in claim 5, wherein the weight average molecular weight of the first resin is 20,000 to 40,000, and the weight average molecular weight of the second resin is 15,000 to 40,000.

7. The light-shielding film as claimed in claim 5, wherein the glass transition temperature of the first resin is -10 to 60°C and the glass transition temperature of the second resin is 0 to 70°C.

8. The light-shielding film as described in any one of claims 1 to 3, wherein the aforementioned black pigment comprises particles selected from the group consisting of metal nitride particles and metal oxide nitride particles.

9. The light-shielding film as described in any one of claims 1 to 3 is patterned.

10. A solid-state imaging element comprising the light-shielding film described in any one of claims 1 to 9.

11. An image display device comprising a light-shielding film as described in any one of claims 1 to 9.

12. An infrared sensor comprising a light-shielding film as described in any one of claims 1 to 9.

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