WO2023190567A1 - Light-shielding film, solid-state imaging element, image display device, and infrared sensor - Google Patents

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

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Publication number
WO2023190567A1
WO2023190567A1 PCT/JP2023/012618 JP2023012618W WO2023190567A1 WO 2023190567 A1 WO2023190567 A1 WO 2023190567A1 JP 2023012618 W JP2023012618 W JP 2023012618W WO 2023190567 A1 WO2023190567 A1 WO 2023190567A1
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Prior art keywords
light
shielding film
group
resin
mass
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PCT/JP2023/012618
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French (fr)
Japanese (ja)
Inventor
鉄平 阿部
宏明 出井
貴規 田口
憲文 横山
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富士フイルム株式会社
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Publication of WO2023190567A1 publication Critical patent/WO2023190567A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Definitions

  • the present invention relates to a light shielding film, a solid-state image sensor, an image display device, and an infrared sensor.
  • Image display devices such as liquid crystal display devices, and solid-state imaging devices such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors, have light-shielding films placed at predetermined positions.
  • a light shielding film called a black matrix is sometimes disposed between colored pixels on a color filter in order to improve contrast by blocking light between colored pixels.
  • a light-shielding film is sometimes applied for the purpose of preventing noise generation and improving image quality.
  • a composition containing a black pigment is usually used to form a light-shielding film.
  • Patent Document 1 a pigment dispersion composition containing two types of dispersants with different SP values is used, and due to the phase separation effect of the two types of dispersants, the surface has an uneven structure and the film has an uneven structure. discloses that it is possible to form a light-shielding film in which black pigment is uniformly dispersed.
  • the present inventors studied the light-shielding film described in Patent Document 1 and found that there is room for further improvement in infrared light reflectivity.
  • a light-shielding film containing a black pigment 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 a 1 ⁇ 1 ⁇ m 2 area in a cross section perpendicular to the surface of the light shielding film, the total length of the boundary line between the first phase and the second phase is 2.50 to 15.00 ⁇ m.
  • Light-shielding film [2] The light shielding film according to [1], which has a surface roughness Ra of 400 to 2000 ⁇ .
  • the light-shielding film according to [1] which is formed using a composition containing a black pigment, a resin, and a polymerizable compound.
  • the first phase includes a first resin having an acid value of 40 to 100 mgKOH/g,
  • the weight average molecular weight of the first resin is 20,000 to 40,000, The light shielding film according to [5], wherein the second resin has a weight average molecular weight of 15,000 to 40,000.
  • the first resin has a glass transition temperature of -10 to 60°C, The light shielding film according to [5] or [6], wherein the second resin has a glass transition temperature of 0 to 70°C.
  • a solid-state imaging device comprising the light-shielding film according to any one of [1] to [9].
  • An image display device comprising the light shielding film according to any one of [1] to [9].
  • An infrared sensor comprising the light shielding film according to any one of [1] to [9].
  • the present invention it is possible to provide a light-shielding film that has excellent light-shielding properties and low reflectance of infrared light. Further, according to the present invention, it is possible to provide a solid-state image sensor, an image display device, and an infrared sensor including the light-shielding film.
  • FIG. 2 is a schematic diagram showing an example of a phase separation structure (sea-island structure) of a cross section T of a light shielding film.
  • FIG. 2 is a schematic diagram showing an example of a phase separation structure (co-continuous structure) of a cross section T of a light shielding film.
  • It is a schematic diagram which shows an example of the SEM image of the cross section T after trimming.
  • 4 is a schematic diagram showing an image after the SEM image of FIG. 3 is converted into black and white binarized.
  • FIG. 5 is a schematic diagram for explaining a method of edge search for the black-and-white binarized image of FIG. 4.
  • alkyl group includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
  • actinic rays or “radiation” in this specification means, for example, far ultraviolet rays, extreme ultraviolet lithography (EUV), X-rays, and electron beams.
  • light means actinic rays and radiation.
  • exposure in this specification includes not only exposure with deep ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams.
  • (meth)acrylate represents acrylate and methacrylate.
  • (meth)acrylic represents acrylic and methacrylic.
  • (meth)acryloyl represents acryloyl and methacryloyl.
  • (meth)acrylamide represents acrylamide and methacrylamide.
  • “monomer” and “monomer” have the same meaning.
  • the weight average molecular weight (Mw) is a polystyrene equivalent value determined by GPC (Gel Permeation Chromatography) method.
  • GPC Gel Permeation Chromatography
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID x 15 cm) as a column, and THF (tetra hydrofuran) Based on the method used.
  • the solid content of a composition means a composition layer formed using the composition, and when the composition contains a solvent, it means all components except the solvent.
  • liquid components are also considered solid components as long as they form a composition layer.
  • the light shielding film of the present invention is A light-shielding film containing a black pigment, which has a phase-separated structure consisting of a first phase containing the black pigment and a second phase that does not substantially contain the black pigment, and has a phase-separated structure consisting of a first phase containing the black pigment and a second phase that does not substantially contain the black pigment.
  • boundary distance L the total length of the boundary line between the first phase and the second phase
  • a first feature of the light-shielding film of the present invention is that it has a phase-separated structure composed of a first phase containing a black pigment and a second phase that does not substantially contain the black pigment.
  • the boundary distance L between the first phase and the second phase is within a predetermined numerical range.
  • the light-shielding film of the present invention having the above structure has a fine uneven structure formed on the surface of the film, and it is presumed that as a result of this, it exhibits excellent low reflection characteristics.
  • the light-shielding film of the present invention has a phase-separated structure composed of a first phase and a second phase, and controls the domain size and distribution state of each of the first and second phases to increase the boundary distance.
  • L is adjusted to a predetermined length, an uneven structure resulting from the phase separation structure is formed on the surface of the light-shielding film, and it is believed that this surface uneven structure provides low reflection characteristics. There is.
  • the correlation between this boundary distance L and low reflection characteristics is as shown in the Examples section of this specification.
  • the boundary distance L is less than 2.50 ⁇ m, the first phase region is too large (the first phase region is larger than the wavelength of the light), and the desired low reflection characteristics are not expressed. Further, if the boundary distance L is more than 15.00 ⁇ m, the first phase region is too small (that is, the uneven structure on the surface of the light-shielding film is too small), and the desired low-reflectivity characteristics are not exhibited. Note that a method for measuring the boundary distance L will be described later. Furthermore, since the light-shielding film of the present invention contains a black pigment, it also has excellent light-shielding properties.
  • the fact that the light-shielding film of the present invention has better low reflection characteristics and/or the light-shielding property of the light-shielding film of the present invention is better may be referred to as "the effects of the present invention are better.”
  • the light shielding film of the present invention is typically a resin film containing a black pigment.
  • the light-shielding film has a phase-separated structure composed of a first phase containing a black pigment and a second phase substantially free of the black pigment.
  • Examples of the phase-separated structure include a sea-island structure, a co-continuous structure, and a structure in which a sea-island structure and a co-continuous structure coexist.
  • cross section T a cross section perpendicular to the surface of the light shielding film (in other words, a cross section exposed when the light shielding film is cut perpendicular to the film surface direction; hereinafter also referred to as "cross section T") is When observed, for example, as shown in Figure 1, a structure in which the first phase (dispersed phase (A in the diagram)) is scattered within the second phase (continuous phase (B in the diagram)) is observed. Ru.
  • the light shielding film has a co-continuous structure
  • the first phase (A in the figure) and the second phase (B in the figure) are complicated.
  • a structure forming a three-dimensional network is observed.
  • the surface structure of the cross section T can be observed using a scanning electron microscope (SEM) (for example, "S-4800” manufactured by Hitachi High-Technologies, Inc.).
  • SEM scanning electron microscope
  • As conditions for SEM observation for example, it is preferable to observe the backscattered electron image under conditions of observation magnification: 5,000 to 25,000 times and acceleration voltage: 3.0 to 5.0 keV.
  • the first phase containing black pigment is typically a phase containing black pigment and resin.
  • the second phase that does not substantially contain black pigment is typically a phase that does not substantially contain black pigment and contains a resin.
  • the determination as to whether a phase contains a black pigment is made by observing and elementally analyzing the cross section T of the light shielding film according to energy dispersive X-ray spectroscopy (SEM-EDX). The specific judgment method is as follows. First, a surface structure image of the cross section T of the light shielding film is obtained by SEM.
  • a gray pattern for example, a sea-island structure, a co-continuous structure, and a co-existence of a sea-island structure and a co-continuous structure
  • a pattern of shading is observed.
  • an area of 0.1 ⁇ m x 0.1 ⁇ m (vertical x horizontal) (hereinafter also referred to as "area A") is arbitrarily selected from the light image area of the shading pattern within the observation field, and elemental analysis in area A is performed. (EDX) to determine the atomic composition (atom%) of region A.
  • an area of 0.1 ⁇ m x 0.1 ⁇ m (vertical x horizontal) (hereinafter also referred to as "area B") is arbitrarily selected from the dark image area in the shading pattern within the observation field, and elemental analysis in area B is performed. is carried out to determine the atomic composition (atom%) of region B. Then, in each region of region A and region B, the content (atom %) of atoms occupying the maximum content among the atoms contained in the black pigment is determined.
  • the atom that occupies the maximum content among the atoms contained in the black pigment refers to the atom that has the largest content (% by mass) based on the total mass of the black pigment, among the atoms that constitute the black pigment.
  • the black pigment when the black pigment is titanium black, the atom that occupies the maximum content among the atoms constituting the black pigment is a titanium atom.
  • region A if the content (atom%) of the atoms that account for the maximum content among the atoms contained in the black pigment is 15 atom% or less, the entire light image region including region A does not contain the black pigment. If the content (atom%) of the atom that occupies the maximum content among the atoms contained in the black pigment is more than 15 atom%, the entire light image area including area A is considered to contain the black pigment.
  • the dark image area including area B As with area A, if the content (atom%) of the atoms that account for the maximum content among the atoms contained in the black pigment is 15 atom% or less, the dark image area including area B If the entire dark image area including area A is considered to be free of black pigment, and the content (atom%) of atoms that account for the maximum content among the atoms contained in the black pigment is more than 15 atom%, the entire dark image area including area A is Considered to contain black pigment. In addition, when the area
  • the total length of the boundary line between the first phase and the second phase (boundary distance L) is 2.50 to 15.00 ⁇ m. It is. A method for measuring the boundary distance L will be described below with reference to FIGS. 3 to 5.
  • a surface structure image of the cross section T of the light shielding film is acquired by SEM.
  • the device for example, “S-4800” manufactured by Hitachi High-Technologies Corporation can be used.
  • observation conditions it is preferable to observe a backscattered electron image under conditions of, for example, observation magnification: 5.0k (5000 times) and acceleration voltage: 2.0 keV.
  • an arbitrary 6 ⁇ m ⁇ 15 ⁇ m area in the acquired SEM image of the cross section T is trimmed.
  • FIG. 3 shows an example of a SEM image after trimming to a predetermined size. In the SEM image in FIG. 3, gray areas correspond to the first phase, and black areas correspond to the second phase.
  • FIG. 4 is a schematic diagram of an image after the SEM image of FIG. 3 is converted into black and white binarized.
  • the parts displayed as "white” by binarization correspond to the first phase
  • the parts displayed as "black” by binarization correspond to the second phase.
  • FIG. 5 is a schematic diagram showing a state in which boundary lines are extracted from the black-and-white binarized image of FIG.
  • the calculated total boundary distance L 0 is normalized by the observation area (6 ⁇ m ⁇ 15 ⁇ m) of the trimmed SEM image, and the total interface distance L 1 (the distance in the 1 ⁇ 1 ⁇ m 2 range of cross section T) per 1 ⁇ m ⁇ 1 ⁇ m is calculated.
  • the total length of the boundary line between the first phase and the second phase (boundary distance L 1 ) is determined.
  • the boundary distance L1 for each of the three cross sections of the light-shielding film is determined by the above procedure, and the average value thereof is defined as the boundary distance L.
  • the boundary distance L is 2.50 to 15.00 ⁇ m, preferably 2.50 to 10.00 ⁇ m, and 2.50 to 7. 00 ⁇ m is more preferable. If the boundary distance L is less than 2.50 ⁇ m, the first phase region is too large (the first phase region is larger than the wavelength of the light), and the desired low reflectivity characteristics are not expressed. Furthermore, if the boundary distance L is more than 15.00 ⁇ m, the first phase region is too small (that is, the uneven structure on the surface of the light-shielding film is too small), and the desired low-reflectivity characteristics are not exhibited.
  • the surface roughness of the light-shielding film of the present invention is not particularly limited, but the surface roughness Ra is preferably 20 to 3000 ⁇ , more preferably 200 to 2000 ⁇ , since the effects of the present invention are more likely to be achieved. is more preferable, and even more preferably 400 to 2000 ⁇ .
  • the above numerical value corresponds to a value obtained by measuring the surface roughness at a distance of 1 mm of the resin film at a resolution of 1 ⁇ m/point using DektakXT manufactured by BRUKER.
  • the thickness of the light-shielding film of the present invention is not particularly limited, but it is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m, since the effects of the present invention are more likely to be achieved.
  • the light shielding film contains a black pigment.
  • black pigment refers to a pigment that has absorption over the entire wavelength range of 400 to 700 nm. More specifically, for example, a black pigment that meets evaluation criteria Z described below is preferable.
  • a composition containing a black pigment, a transparent resin matrix (such as an acrylic resin), and a solvent is prepared, in which the content of the black pigment is 60% by mass based on the total solid content. The obtained composition is applied onto a glass substrate so that the thickness of the cured film after drying is 1 ⁇ m to form a cured film.
  • the light-shielding properties of the cured film after drying are evaluated using a spectrophotometer (UV-3600, manufactured by Hitachi, Ltd., etc.). If the maximum transmittance of the cured film after drying at a wavelength of 400 to 700 nm is less than 10%, it can be determined that the coloring material is a black pigment that meets evaluation criteria Z. Regarding the black pigment, in evaluation criterion Z, the maximum transmittance of the cured film after drying at a wavelength of 400 to 700 nm is more preferably less than 8%, and even more preferably less than 5%.
  • the black pigment a plurality of pigments that cannot be used alone as a black pigment may be combined and adjusted to give a black color as a whole to form a black pigment.
  • a combination of a plurality of pigments having a color other than black when used alone may be used as a black pigment.
  • the black pigment a pigment that expresses black color by itself is preferable. Further, a black pigment that alone expresses black color and absorbs infrared rays may be used.
  • the black pigment that absorbs infrared rays has absorption in the infrared wavelength region (preferably a wavelength of 650 to 1300 nm). A black pigment having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is also preferred.
  • the black pigment various known black pigments can be used.
  • the black pigment may be an inorganic pigment or an organic pigment.
  • the black pigment is preferably an inorganic pigment, and more preferably a metal nitride particle or a metal oxynitride particle, since the effects of the present invention are more excellent.
  • the inorganic pigment used as the black pigment is not particularly limited as long as it has light blocking properties and contains an inorganic compound, but any known inorganic pigment can be used.
  • the inorganic pigment include metal oxides, metal nitrides, and metal oxynitrides, and metal nitrides or metal oxynitrides are preferable because they provide better effects of the present invention.
  • Inorganic pigments include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), yttrium (Y), and aluminum (Al). , cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag).
  • Examples include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the following.
  • metal elements selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V), yttrium (Y), aluminum (Al), and iron (Fe).
  • Metal oxides, metal nitrides, or metal oxynitrides containing metal oxides are preferred. That is, the inorganic pigment may contain two or more types of metal atoms.
  • the metal oxide, metal nitride, and metal oxynitride particles containing other metal atoms may also be used.
  • metal nitride-containing particles further containing an atom (preferably an oxygen atom and/or a sulfur atom) selected from elements of groups 13 to 17 of the periodic table can be used.
  • the metal oxide, metal nitride, and metal oxynitride may be coated with an inorganic substance and/or an organic substance.
  • the inorganic substance include metal atoms contained in the inorganic pigment.
  • the above-mentioned organic substance include the above-mentioned organic substances having a hydrophobic group, and silane compounds are preferable.
  • the method for producing the above metal nitride, metal oxide, or metal oxynitride is not particularly limited as long as a black pigment having desired physical properties can be obtained, but known methods such as gas phase reaction method can be used. Manufacturing methods can be used. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable because it is less likely to contain impurities, the particle size is easily uniform, and productivity is high.
  • the above metal nitride, metal oxide, or metal oxynitride may be subjected to a surface modification treatment. For example, the surface may be modified with a surface treatment agent having both a silicone group and an alkyl group. Examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • nitrides or oxynitrides of one or more metals selected from the group consisting of titanium, vanadium, zirconium, niobium, and iron are more preferred from the standpoint of suppressing the occurrence of undercuts when forming a light-shielding film.
  • Titanium black is black particles containing titanium oxynitride.
  • the surface of titanium black can be modified as necessary for the purpose of improving dispersibility, suppressing agglomeration, and the like.
  • Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconium oxide, and can also be coated with a water-repellent material as disclosed in JP-A No. 2007-302836. Processing is also possible.
  • Methods for producing titanium black include a method in which a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing atmosphere (Japanese Unexamined Patent Publication No. 49-05432), and ultrafine carbon dioxide obtained by high-temperature hydrolysis of titanium tetrachloride.
  • a method for reducing titanium in a reducing atmosphere containing hydrogen Japanese Unexamined Patent Publication No. 57-205322
  • a method for reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia Japanese Unexamined Patent Publication No. 60-065069
  • Examples include a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Application Laid-Open No. 61-201610).
  • the particle size of titanium black is not particularly limited, but is preferably 10 to 45 nm, more preferably 12 to 20 nm.
  • the specific surface area of titanium black is not particularly limited, but in order for the water repellency after surface treatment with a water repellent agent to achieve a specified performance, the value measured by the BET (Brunauer, Emmett, Teller) method should be 5 to 5. It is preferably 150 m 2 /g, more preferably 20 to 100 m 2 /g.
  • titanium black examples include Titanium Black 10S, 12S, 13R, 13M, 13MC, 13R, 13R-N, 13M-T (product name, manufactured by Mitsubishi Materials Corporation), Tilac D (product name). , manufactured by Ako Kasei Co., Ltd.) and MT-150A (trade name, manufactured by Teika Co., Ltd.).
  • the light shielding film contains titanium black as a dispersed element containing titanium black and Si atoms.
  • titanium black is included as a dispersed element in the light shielding film.
  • the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersed body is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, in terms of mass.
  • the above-mentioned object to be dispersed includes both titanium black in the state of primary particles and titanium black in the state of aggregates (secondary particles).
  • titanium oxide and silica particles are dispersed using a dispersion machine to obtain a dispersion, and this mixture is reduced at a high temperature (for example, 850 to 1000°C) to make titanium black particles as the main component.
  • a high temperature for example, 850 to 1000°C
  • Titanium black with adjusted Si/Ti can be produced, for example, by the method described in paragraphs [0005] and [0016] to [0021] of JP-A-2008-266045.
  • the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersed material can be determined, for example, by the method (2-1) described in paragraphs [0054] to [0056] of International Publication No. 2011/049090. ) or method (2-3).
  • the titanium black described above can be used.
  • this dispersed material also contains composite oxides of a plurality of metals selected from Cu, Fe, Mn, V, Ni, etc., cobalt oxide, Black pigments such as iron oxide, carbon black, and aniline black may be used alone or in combination as a dispersion object.
  • the dispersible material made of titanium black accounts for 50% by mass or more of the total dispersible material.
  • Carbon black can also be mentioned as an inorganic pigment.
  • examples of carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.
  • carbon black carbon black manufactured by a known method such as an oil furnace method may be used, or a commercially available product may be used.
  • Specific examples of commercially available carbon blacks include C. I.
  • examples include inorganic pigments such as Pigment Black 7.
  • surface-treated carbon black is preferable.
  • the surface treatment include coating treatment with a resin, surface treatment to introduce an acidic group, and surface treatment with a silane coupling agent.
  • the carbon black carbon black coated with a resin is preferable.
  • the coating resin include epoxy resin, polyamide, polyamideimide, novolak resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkylbenzene resin, polystyrene, polycarbonate, polybutylene terephthalate, and modified polyphenylene oxide.
  • the content of the coating resin is preferably 0.1 to 40% by mass, and 0.5 to 30% by mass based on the total of carbon black and coating resin, from the viewpoint of better light shielding properties and insulation properties of the light shielding film. More preferred.
  • black pigment examples include zirconium disclosed in JP2017-222559A, WO2019/130772A, WO2019/059359A, and JP2009-091205A, the contents of which are disclosed in this specification. incorporated into the book.
  • organic pigment used as the black pigment is not particularly limited as long as it has light blocking properties and contains an organic compound, but any known organic pigment can be used.
  • examples of the organic pigment include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds or perylene compounds being preferred.
  • Examples of the bisbenzofuranone compound include compounds described in Japanese Translated Patent Publication No. 2010-534726, Japanese Translated Patent Publication No. 2012-515233, and Japanese Translated Transparent Publication No. 2012-515234.
  • the bisbenzofuranone compound is available as "Irgaphor Black” (trade name) manufactured by BASF.
  • Examples of perylene compounds include compounds described in JP-A-62-001753 and JP-B-63-026784.
  • the perylene compound is C. I. Pigment Black 21, 30, 31, 32, 33 and 34.
  • the content of the black pigment is preferably 20 to 90% by mass, more preferably 30 to 70% by mass, and still more preferably 30 to 60% by mass, based on the total mass of the light shielding film, in order to achieve better effects of the present invention. preferable.
  • the total content is within the above range.
  • "light shielding" in the light shielding film of the present invention is a concept that also includes light attenuation in which light is allowed to pass through the light shielding film while being attenuated. In a light-shielding film as a light-attenuating film having such a function, it is also preferable that the content of black pigment in the light-shielding film is less than the above-mentioned preferred range.
  • the light-shielding film may contain a coloring material other than the black pigment.
  • the light-shielding film may contain, for example, a black dye.
  • a black dye for example, dyes that express black color by themselves can be used, such as pyrazole azo compounds, pyrromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, Pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. can be used.
  • black dyes include, for example, JP-A-64-90403, JP-A-64-91102, JP-A-01-94301, JP-A-06-11614, Japanese Patent No. 2,592,207, and U.S. Pat. 4808501 specification, US Patent No. 5667920, US Patent No. 505950, US Patent No. 5667920, JP 05-333207, JP 06-35183, JP 06-51115, Also, reference can be made to the compounds described in JP-A-06-194828, etc., the contents of which are incorporated herein.
  • black dyes examples include dyes defined by Color Index (C.I.) of Solvent Black 27 to 47, and C.I. of Solvent Black 27, 29, or 34. I. Dyes defined by are preferred.
  • Commercially available products of these black dyes include, for example, Spiron Black MH, Black BH (all manufactured by Hodogaya Chemical Industry Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (all manufactured by Orient Chemical Industry Co., Ltd.). ), Savinyl Black RLSN (manufactured by Clariant), KAYASET Black K-R, K-BL (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • a polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available dyes include the RDW series manufactured by Wako Pure Chemical Industries, Ltd.
  • a pigment multimer may be used as the black dye.
  • the dye multimer include compounds described in JP-A No. 2011-213925 and JP-A No. 2013-041097.
  • a combination of a plurality of dyes having a color other than black when used alone may be used as the black dye.
  • Such colored dyes include, for example, chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), as well as paragraphs 0027 to 4 of JP-A No. 2014-42375. Dyes described in 0200 can also be used.
  • the light-shielding film may contain a colorant having a color other than black.
  • the light-shielding properties of the light-shielding film can be adjusted by using both a black colorant having a black color (including the black pigment described above) and one or more colorants. Further, for example, when a light shielding film is used as a light attenuation film, it is easy to attenuate each wavelength equally for light including a wide wavelength component.
  • the coloring agent include pigments and dyes other than black coloring materials.
  • a chromatic coloring agent or a white coloring agent may be included as a coloring agent. Examples of chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants.
  • the chromatic colorant or white colorant may be a pigment or a dye. Pigments and dyes may be used in combination. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or an organic-inorganic pigment partially substituted with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.
  • the total content of the black colorant and the colorant is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and more preferably 40 to 70% by mass, based on the total mass of the light shielding film. More preferably 60% by mass.
  • the total content of a black coloring material and a coloring agent is less than the said suitable range.
  • the mass ratio of the colorant content to the black colorant content is preferably 0.1 to 9.0.
  • the light shielding film may further contain an infrared absorber.
  • the infrared absorber refers to a compound having absorption in the infrared wavelength region (preferably a wavelength of 650 to 1300 nm).
  • the infrared absorber is preferably a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm.
  • 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, and quatarylene. compounds, dithiol metal complex compounds, croconium compounds, and the like.
  • phthalocyanine compound As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, compounds disclosed in paragraphs 0010 to 0081 of JP-A No. 2010-111750 may be used, and the contents thereof are disclosed in this specification. incorporated into the book.
  • the cyanine compound for example, "Functional Pigment, Written by Makoto Okawara/Ken Matsuoka/Teijiro Kitao/Tsunesuke Hirashima, Kodansha Scientific" can be referred to, the contents of which are incorporated herein.
  • the compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
  • the infrared absorber is preferably a compound that dissolves in water at 25°C in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25°C in an amount of 10% by mass or more. By using such a compound, solvent resistance is improved.
  • the light shielding film may contain resin.
  • the resin include a first resin and a second resin described below.
  • the first resin and the second resin are different types of resin.
  • the content of the first resin in 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, based on the total mass of the light shielding film.
  • the content of the second resin in 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, based on the total mass of the light shielding film.
  • the content ratio of the first resin and the second resin (first resin/second resin) in the light shielding film is preferably 0.3 to 0.8, more preferably 0.3 to 0.6.
  • the resin is preferably contained in both the first phase and the second phase, the first phase preferably containing the first resin described below, and the second phase containing the resin described later. It is preferable to include two resins. Below, the first resin and the second resin will be explained respectively.
  • the type of the first resin is not particularly limited and includes, for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly(meth)acrylate, (meth) Examples include resins commonly used as dispersants such as acrylic copolymers and naphthalene sulfonic acid formalin condensates; polyoxyethylene alkyl phosphates; polyoxyethylene alkyl amines; pigment derivatives, and the like.
  • the first resin is typically the dispersant itself in the dispersion composition in which the black pigment is dispersed, which is introduced into the composition for forming the light-shielding film.
  • Resins derived from the above-mentioned dispersants fall under this category.
  • the first resin may include a structural unit containing a graft chain, which may also be included in a dispersant described below.
  • the content of the structural unit containing a graft chain is the total mass of the first resin. It is preferably 2 to 90% by mass, more preferably 5 to 30% by mass.
  • the first resin may include a hydrophobic structural unit that may also be included in the dispersant described below.
  • the content of the hydrophobic structural unit is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the first resin.
  • the first resin may include a structural unit containing a functional group capable of forming an interaction with a pigment or the like that may be included in a dispersant described below.
  • the content of the structural unit containing a functional group capable of forming an interaction with a pigment, etc. is determined based on the total mass of the first resin.
  • the amount is preferably 0.05 to 90% by weight, more preferably 1.0 to 80% by weight, and even more preferably 10 to 70% by weight. Only one type of first resin may be used, or two or more types may be used.
  • the acid value of the first resin is preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, even more preferably 40 to 100 mgKOH/g, and particularly preferably 40 to 60 mgKOH/g.
  • “acid value” can be calculated from the average content of acid groups in a compound, for example. Further, by changing the content of structural units containing acid groups, which are constituent components of the resin, a resin having a 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, even more preferably 15,000 to 40,000, and even more preferably 20,000 to 40. ,000 is particularly preferred, and 25,000 to 40,000 is most preferred.
  • the glass transition temperature of the first resin is preferably -20 to 100°C, more preferably -20 to 80°C, even more preferably -10 to 60°C. The glass transition temperature can be measured using DSC 3500 Sirius (manufactured by Netzsch).
  • the type of the second resin is not particularly limited, and examples include alkali-soluble resins.
  • Alkali-soluble resins are typically resins that have acid groups. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups.
  • the second resin may have only one type of acid group, or may have two or more types of acid groups. It is preferable that the second resin contains a repeating unit having an acid group in a side chain. Examples of the repeating unit having an acid group in its side chain include a repeating unit represented by the below-mentioned formula (2RB) that may be included in the alkali-soluble resin that may be included in the composition for forming a light-shielding film shown below. .
  • the second resin contains a repeating unit having an acid group in its side chain, the content thereof is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, based on the total repeating units of the resin. More preferably 30% by mass.
  • the second resin contains a repeating unit derived from a compound having a ClogP value of 1.0 or more.
  • the repeating unit derived from a compound having a ClogP value of 1.0 or more is preferably selected from repeating units derived from (meth)acrylate. Note that the definition of the ClogP value will be explained in the latter part.
  • Examples of the repeating unit derived from (meth)acrylate include a repeating unit represented by the below-mentioned formula (2RA) that may be included in the alkali-soluble resin that may be included in the composition for forming a light-shielding film shown below. .
  • the repeating unit derived from (meth)acrylate has a hydroxyl group as a substituent.
  • the content thereof is preferably 30% by mass or more, more preferably 60% by mass or more, and 70% by mass based on the total repeating units of the resin. The above is more preferable, and 80% by mass or more is particularly preferable.
  • 99 mass % or less is preferable, and 95 mass % or less is more preferable, for example.
  • One embodiment of the second resin includes a repeating unit having an acid group in a side chain and a repeating unit derived from (meth)acrylate, and the repeating unit derived from (meth)acrylate accounts for all repeating units of the resin.
  • Examples include resins in which the amount is 60% by mass or more.
  • the second resin is typically the alkali-soluble resin itself that is introduced as a binder component into the composition for forming the light-shielding film, or is derived from the alkali-soluble resin mentioned above. This applies to the following resins.
  • the number of second resins may be one, or two or more.
  • the acid value of the second resin is preferably 0 to 150 mgKOH/g, more preferably 20 to 100 mgKOH/g, even more preferably 40 to 90 mgKOH/g, and most preferably 60 to 90 mgKOH/g.
  • the weight average molecular weight of the second resin is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, even more preferably 15,000 to 40,000, and even more preferably 18,000 to 25,000. Particularly preferred.
  • the glass transition temperature of the second resin is preferably -20 to 120°C, preferably -20 to 110°C, more preferably -5 to 80°C, and even more preferably 0 to 70°C. The glass transition temperature can be measured using DSC 3500 Sirius (manufactured by Netzsch).
  • the light-shielding film may further contain other optional components other than the above-mentioned components.
  • colorants other than black pigments (pigments or dyes may be used), ultraviolet absorbers, surfactants, plasticizers, adhesion promoters to the substrate surface, and other auxiliary agents (e.g., conductive particles, fillers, , antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be included as necessary.
  • the method for manufacturing the light-shielding film of the present invention is not particularly limited, but examples include a method using a composition for forming a light-shielding film containing a black pigment. More specifically, an embodiment 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. preferable.
  • 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
  • an exposure step of exposing the composition layer preferable.
  • an exposure step of exposing the composition layer to pattern light through a predetermined mask, and a composition layer after exposure are performed.
  • the method further includes a developing step of developing the material layer to form a light-shielding film.
  • the development treatment may be either solvent development or alkali development, but alkali development is preferable.
  • the composition for forming a light-shielding film will be explained below.
  • composition for forming a light-shielding film preferably contains a black pigment, a resin, and a polymerizable compound. Each component will be explained below.
  • the composition for forming a light-shielding film contains a black pigment.
  • the black pigment include those similar to the black pigment contained in the light-shielding film.
  • the content of the black pigment is preferably 20 to 90% by mass, more preferably 30 to 70% by mass, and 30 to 60% by mass, based on the total solid content of the light shielding film, in order to obtain better effects of the present invention. More preferred.
  • the total content is within the above range.
  • the content of the black pigment in the light-shielding film is less than the above-mentioned preferred range.
  • the composition includes a polymerizable compound.
  • the term "polymerizable compound” refers to an organic compound (for example, an organic compound containing an ethylenically unsaturated group) that can be polymerized under the action of a polymerization initiator or the like described below.
  • the composition contains a solvent, the polymerizable compound is preferably present dissolved in the solvent.
  • the polymerizable compound is a low-molecular polymerizable compound, and is a separate component from the resin described below.
  • the content of the polymerizable compound in the composition is preferably 5 to 60% by mass, preferably 7 to 30% by mass, and more preferably 10 to 30% by mass, based on the total solid content of the composition.
  • the composition may contain only one kind of polymerizable compound, or may contain two or more kinds. When two or more types are included, it is preferable that their total amount falls within the above range.
  • the molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound is not particularly limited, but is preferably 2,500 or less. The lower limit is preferably 100 or more.
  • the polymerizable compound is preferably a compound containing an ethylenically unsaturated group (a group containing an ethylenically unsaturated bond). That is, the composition preferably contains a low molecular weight compound containing an ethylenically unsaturated group as a polymerizable compound.
  • the polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more, still more preferably a compound containing three or more, and particularly preferably a compound containing four or more.
  • the upper limit is, for example, 15 or less.
  • Examples of the ethylenically unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.
  • the polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a multimer thereof.
  • the polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
  • the polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher under normal pressure.
  • a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher under normal pressure.
  • the polymerizable compounds include dipentaerythritol triacrylate (as a commercially available product, for example, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (as a commercially available product, for example, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.).
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 penentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.
  • KAYARAD DPEA-12LT KAYARAD DPHA LT
  • KAYARAD RP-3060 KAYARAD DPEA-12
  • KAYARAD DPEA-12 all product names, (manufactured by Nippon Kayaku Co., Ltd.
  • a urethane (meth)acrylate compound having both a (meth)acryloyl group and a urethane bond may be used.
  • KAYARAD DPHA-40H trade name, Nippon Chemical Co., Ltd. (manufactured by Yakuhin Co., Ltd.) may also be used.
  • Preferred embodiments of the polymerizable compound are shown below.
  • the polymerizable compound may have acid groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups.
  • the polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. It is more preferable to use a polymerizable compound in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol.
  • Commercially available products include, for example, Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei.
  • the acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, development and dissolution characteristics are good, and if it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, it has good photopolymerization performance and excellent curability.
  • a preferred embodiment of the polymerizable compound is a compound containing a caprolactone structure.
  • Compounds containing a caprolactone structure are not particularly limited as long as they contain a caprolactone structure in the molecule, but examples include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.
  • Examples include ⁇ -caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerin, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ⁇ -caprolactone.
  • a compound containing a caprolactone structure represented by the following formula (Z-1) is preferred.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • * represents a bonding position
  • R 1 represents a hydrogen atom or a methyl group
  • "*" represents a bonding position
  • M-350 trade name (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd. may be mentioned.
  • E represents -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)-, and y represents an integer from 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group.
  • the total number of (meth)acryloyl groups is 3 or 4
  • m represents an integer of 0 to 10
  • the sum of each m is an integer of 0 to 40.
  • the total number of (meth)acryloyl groups is 5 or 6
  • n represents an integer of 0 to 10
  • the total of each n is an integer of 0 to 60.
  • m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each 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.
  • -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- in formula (Z-4) or formula (Z-5) is on the oxygen atom side. A form in which the terminal of is bonded to X is preferable.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
  • all six X are acryloyl groups
  • all six X are acryloyl groups
  • a preferred embodiment is a mixture with a compound having at least one hydrogen atom. With such a configuration, the developability can be further improved.
  • the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more.
  • pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.
  • the polymerizable compound may contain a cardo skeleton.
  • the polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton.
  • Examples of the polymerizable compound containing a cardo skeleton include Oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogusol (manufactured by Osaka Gas Chemical Co., Ltd.).
  • the polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core.
  • a polymerizable compound is NK Ester A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.).
  • the content of ethylenically unsaturated groups in the polymerizable compound (meaning 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 5.0 mmol/ g or more is preferable.
  • the upper limit is preferably 20.0 mmol/g or less.
  • the composition includes a resin.
  • the resin include dispersants and alkali-soluble resins.
  • the light-shielding film of the present invention is preferably formed by phase separation of a dispersant and an alkali-soluble resin.
  • the light-shielding film of the present invention is formed using the composition according to the light-shielding film manufacturing procedure described below, the light-shielding film contains the black pigment and the dispersant itself, or a resin derived from the dispersant (a dispersion having a polymerizable group).
  • a domain part composed of a resin formed by polymerizing the agent and an alkali-soluble resin itself or a resin derived from the above-mentioned alkali-soluble resin (an alkali-soluble resin having a polymerizable group).
  • a matrix portion (corresponding to the second phase) is formed from a polymerized resin.
  • the molecular weight of the resin is greater than 2,000.
  • the weight average molecular weight is more than 2,000.
  • 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, based on the total solid content of the composition. .
  • the dispersants may be used alone or in combination of two or more. When two or more types of dispersants are used together, the total content is preferably within the above range.
  • dispersant for example, known dispersants can be appropriately selected and used. Among these, polymer compounds are preferred. Examples of dispersants include polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymers, and General-purpose resins such as so-called dispersion resins such as naphthalene sulfonic acid formalin condensates; polyoxyethylene alkyl phosphates; polyoxyethylene alkyl amines; pigment derivatives and the like can be mentioned.
  • dispersants include polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymers, and General-purpose resins such as so-called dispersion resins such as
  • a high molecular compound is adsorbed onto the surface of a dispersion object such as a black pigment and various pigments that can optionally be included in the composition (hereinafter, these pigments are also collectively referred to simply as "pigments"). , acts to prevent re-agglomeration of the dispersed elements. Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, or a block-type polymer is preferable, which includes an anchor site to the pigment surface.
  • the above-mentioned polymer compound may contain a curable group.
  • the curable group include ethylenically unsaturated groups (eg, (meth)acryloyl group, vinyl group, styryl group, etc.), cyclic ether groups (eg, epoxy group, oxetanyl group, etc.), and the like.
  • ethylenically unsaturated groups are preferred as the curable group since polymerization can be controlled by radical reaction.
  • a (meth)acryloyl group is preferable.
  • the polymer compound containing a curable group preferably contains one or more types selected from the group consisting of a polyester structure and a polyether structure.
  • the main chain may contain a polyester structure and/or a polyether structure, or as described later, if the polymer compound contains a structural unit containing a graft chain, the graft chain may have a polyester structure. and/or may contain a polyether structure.
  • the above-mentioned polymer compound it is more preferable that the above-mentioned graft chain contains a polyester structure.
  • the polymer compound contains a structural unit containing a graft chain.
  • a "structural unit” is synonymous with a “repeat unit.”
  • a polymer compound containing a structural unit containing such a graft chain has affinity with a solvent due to the graft chain, and therefore has excellent dispersibility of pigments and the like and dispersion stability over time.
  • the polymer compound containing the structural unit containing the graft chain has an affinity with the polymerizable compound or other resins that can be used in combination. As a result, residues are less likely to be produced during alkaline development.
  • the number of atoms in the graft chain excluding hydrogen atoms is preferably 40 to 10,000, more preferably 50 to 2,000, even more preferably 60 to 500.
  • the graft chain refers to the region from the root of the main chain of the copolymer (the atom bonded to the main chain in a group branching from the main chain) to the end of the group branching from the main chain.
  • the graft chain comprises a polymeric structure, such as a poly(meth)acrylate structure (e.g. a poly(meth)acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure. , and a polyether structure.
  • a poly(meth)acrylate structure e.g. a poly(meth)acrylic structure
  • the graft chain is one selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure.
  • a graft chain containing at least one species is preferable, and a graft chain containing at least one of a polyester structure and a polyether structure is more preferable.
  • Macromonomers containing such graft chains are not particularly limited, but include reactive double bonding groups. Macromonomers can be suitably used.
  • AA-6 (trade name, manufactured by Toagosei Co., Ltd.) and AA-10 (trade name).
  • AA-6 product name, manufactured by Toagosei Co., Ltd.
  • AA-10 product name, manufactured by Toagosei Co., Ltd.
  • AB-6 product name, manufactured by Toagosei Co., Ltd.
  • AS-6 product name, (manufactured by Toagosei Co., Ltd.)
  • AN-6 trade name, manufactured by Toagosei Co., Ltd.
  • Blenmar PME-4000 trade name, manufactured by NOF Corporation
  • the dispersant preferably contains one or more structures selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester, and includes polymethyl acrylate, polymethyl methacrylate, and More preferably, it contains one or more structures selected from the group consisting of chain polyesters, and one selected from the group consisting of polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure, and polyvalerolactone structure. It is even more preferable to include more than one type of structure.
  • the dispersant may be a dispersant containing only one of the above structures in one dispersant, or may be a dispersant containing a plurality of these structures in one dispersant.
  • the polycaprolactone structure refers to a structure containing a ring-opened structure of ⁇ -caprolactone as a repeating unit.
  • the polyvalerolactone structure refers to a structure containing a ring-opened structure of ⁇ -valerolactone as a repeating unit.
  • Specific examples of dispersants containing a polycaprolactone structure include dispersants in which j and k are 5 in the following formulas (1) and (2). Further, specific examples of dispersants containing a polyvalerolactone structure include dispersants in which j and k are 4 in the following formulas (1) and (2).
  • a specific example of a dispersant containing a polymethyl acrylate structure includes a dispersant in which X 5 is a hydrogen atom and R 4 is a methyl group in the following formula (4). Further, a specific example of a dispersant containing a polymethyl methacrylate structure includes a dispersant in which X 5 is a methyl group and R 4 is a methyl group in the following formula (4).
  • the structural unit containing a graft chain is preferably a structural unit represented by any of the following formulas (1) to (4).
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • oxygen atoms are preferable.
  • X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthetic constraints, each of X 1 , X 2 , X 3 , X 4 and X 5 is preferably independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Each independently, a hydrogen atom or a methyl group is more preferable, and a methyl group is even more preferable.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly structurally restricted.
  • Specific examples of the divalent linking groups represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following linking groups (Y-1) to (Y-21). .
  • a and B mean the bonding site with the left end group and the right end group in formulas (1) to (4), respectively.
  • (Y-2) or (Y-13) is more preferred for ease of synthesis.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a hydroxyl group, an amino group, or a monovalent organic group.
  • the structure of the organic group is not particularly limited, specific examples include an alkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
  • groups having a steric repulsion effect are preferred, particularly from the viewpoint of improving dispersibility, and alkyl groups having 5 to 24 carbon atoms or An alkoxy group is more preferred, and a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is even more preferred.
  • the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.
  • the methylene group in the alkoxy group may be substituted with -O-.
  • each of the above groups may have a substituent (for example, a hydroxyl group, an ethylenically unsaturated group such as a (meth)acryloyloxy group, etc.).
  • the moiety represented by -COZ 1 in the formula may be anionized (-COO - ).
  • examples of the counter cation include quaternary ammonium salts, and a structure represented by formula (TY) is particularly preferred.
  • R 1f and R 1g each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group represented by R 1f and R 1g is preferably linear or branched. Further, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
  • R 1e represents an alkyl group.
  • the alkyl group represented by R 1e is preferably linear. Further, the number of carbon atoms is preferably 10 to 24, more preferably 10 to 20.
  • L 2 represents an alkylene group.
  • the alkylene group represented by L 2 is preferably linear or branched, more preferably linear. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 12.
  • the alkylene group may have a substituent (for example, a hydroxyl group). Furthermore, the methylene group in the alkylene group may be substituted with -O-.
  • R 1h represents a hydrogen atom or an ethylenically unsaturated group such as a (meth)acryloyloxy group.
  • n, m, p, and q each independently represent an integer of 1 to 500.
  • j and k each independently represent an integer from 2 to 8.
  • j and k in formulas (1) and (2) are preferably integers of 4 to 6, more preferably 5, from the viewpoint of the viscosity stability over time and developability of the composition.
  • n and m are preferably integers of 5 or more, more preferably 8 or more, and even more preferably 10 or more.
  • the dispersant when the dispersant includes a polycaprolactone structure and a polyvalerolactone structure, the sum of the number of repeats of the polycaprolactone structure and the number of repeats of polyvalerolactone is preferably an integer of 10 or more, and an integer of 20 or more is preferable. More preferred.
  • R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 's may be the same or different.
  • R 4 represents a hydrogen atom or a monovalent organic group, and this monovalent organic group is not particularly limited in terms of structure.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
  • 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.
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different.
  • the polymer compound can include two or more structural units that have different structures and include graft chains. That is, the molecules of the polymer compound may contain structural units represented by formulas (1) to (4) that have mutually different structures, and in formulas (1) to (4), n, m, p , and q each represent an integer of 2 or more, in formulas (1) and (2), j and k may include structures different from each other in the side chain, and formulas (3) and (4) In , a plurality of R 3 , R 4 , and X 5 present in the molecule may be the same or different.
  • the content of structural units having a graft chain is, in terms of mass, relative to the total mass of the polymer compound. It is preferably 2 to 90% by weight, more preferably 5 to 30% by weight.
  • the content of structural units having graft chains is 5% by mass or more, the dispersibility of the pigment is high and the effects of the present invention are enhanced. Excellent.
  • the polymer compound preferably contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the graft chain).
  • a hydrophobic structural unit is a structural unit that does not have an acid group (eg, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).
  • the hydrophobic structural unit is preferably a structural unit (corresponding to) derived from a compound (monomer) having a ClogP value of 1.2 or more, and is a structural unit derived from a compound having a ClogP value of 1.2 to 8. is more preferable. Thereby, the effects of the present invention can be more reliably expressed.
  • ClogP values are determined by Daylight Chemical Information System, Inc. This value was calculated using the program “CLOGP” available from This program provides the value of "computed logP” calculated by the fragment approach of Hansch, Leo (see below). The fragment approach is based on the chemical structure of a compound and estimates the logP value of the compound by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments. The details are described in the following documents. In this specification, ClogP values calculated by the program CLOGP v4.82 are used. A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds.
  • the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably 20 to 80%, based on the total mass of the polymer compound. preferable. Sufficient pattern formation can be obtained when the content is within the above range.
  • a functional group capable of forming an interaction with a pigment, etc. (for example, a light-shielding pigment) can be introduced into the polymer compound.
  • the polymer compound further includes a structural unit containing a functional group capable of forming an interaction with a pigment or the like.
  • the functional group capable of forming an interaction with the pigment include an acid group, a basic group, a coordinating group, and a reactive functional group.
  • a polymer compound contains an acid group, a basic group, a coordinating group, or a reactive functional group
  • the structural unit containing an acid group, the structural unit containing a basic group, or a coordinating group is It is preferable to include a structural unit that contains or a structural unit that has reactivity.
  • the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be given developability for pattern formation by alkali development. That is, if an alkali-soluble group is introduced into the polymer compound, in the composition, the polymer compound serving as a dispersant that contributes to the dispersion of pigments and the like contains alkali-solubility.
  • a composition containing such a polymer compound has excellent light-shielding properties of a light-shielding film formed by exposure, and the alkali developability of unexposed areas is improved. Furthermore, if the polymer compound contains a structural unit containing an acid group, the polymer compound will be more compatible with the solvent, and its coating properties will tend to be improved. This is because acid groups in structural units containing acid groups easily interact with pigments, etc., and the polymer compound stably disperses the pigment, etc., and the viscosity of the polymer compound that disperses the pigment, etc. is low. This is presumably because the polymer compound itself is easily dispersed stably.
  • the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the above-mentioned structural unit containing a graft chain, or may be a different structural unit;
  • the structural unit containing is a structural unit different from the above-mentioned hydrophobic structural unit (that is, it does not correspond to the above-mentioned hydrophobic structural unit).
  • acid groups that are functional groups that can interact with pigments include carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups. It is preferable that it is one or more types selected from the group consisting of acid groups, and carboxylic acid groups are more preferable.
  • Carboxylic acid groups have good adsorption power to pigments and the like, and have high dispersibility. That is, the polymer compound preferably contains a structural unit containing one or more types selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the polymer compound may have one or more types of structural units containing acid groups.
  • the polymer compound does not need to contain a structural unit containing an acid group, but if it does, the content of the structural unit containing an acid group is 5% relative to the total mass of the polymer compound in terms of mass.
  • the amount is preferably from 10 to 80% by mass, and more preferably from 10 to 60% by mass from the viewpoint of suppressing damage to image strength due to alkaline development.
  • Examples of basic groups that are functional groups that can interact with pigments include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, and amide groups.
  • a preferred basic group is a tertiary amino group because it has good adsorption power to pigments and the like and high dispersibility.
  • the polymer compound may contain one or more of these basic groups.
  • the polymer compound does not need to contain a structural unit containing a basic group, but if it does, the content of the structural unit containing a basic group is calculated based on the total mass of the polymer compound. , is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass from the viewpoint of suppressing development inhibition.
  • Coordinating groups that are functional groups that can interact with pigments, etc., and reactive functional groups include, for example, acetylacetoxy groups, trialkoxysilyl groups, isocyanate groups, acid anhydrides, and acid chlorides. etc.
  • a preferred functional group is an acetylacetoxy group because it has good adsorption power to pigments and the like and has high dispersibility of pigments and the like.
  • the polymer compound may have one or more of these groups.
  • the polymer compound does not need to contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it does, the content of these structural units in terms of mass is , based on the total weight of the polymer compound, is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass from the viewpoint of suppressing development inhibition.
  • the content of structural units containing functional groups that can interact with pigments, etc. is determined based on the total mass of the polymer compound, from the viewpoints of interaction with pigments, viscosity stability over time, and permeability to the developer. On the other hand, it is preferably 0.05 to 90% by weight, more preferably 1.0 to 80% by weight, and even more preferably 10 to 70% by weight.
  • the polymer compound may contain structural units containing graft chains, hydrophobic structural units, pigments, etc., as long as the effects of the present invention are not impaired. It further has other structural units that have various functions (for example, structural units that include a functional group that has affinity with a solvent as described below), which is different from the structural unit that includes a functional group that can form an interaction. It's okay. Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound can use one or more of these other structural units, and the content thereof is preferably 0 to 80% by mass, and 10 to 80% by mass, based on the total mass of the polymer compound. 60% by mass is more preferred. When the content is within the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably 0 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, even more preferably 40 to 100 mgKOH/g, particularly 40 mgKOH/g or more and less than 60 mgKOH/g. preferable. If the acid value of the polymer compound is 200 mgKOH/g or less, pattern peeling during development of the exposed composition layer can be more effectively suppressed. Further, if the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability will be better.
  • the weight average molecular weight of the polymer compound is preferably 5,000 to 100,000, more preferably 6,000 to 80,000, even more preferably 15,000 to 40,000, and even more preferably 20,000 to 40. ,000 is particularly preferred, and 25,000 to 40,000 is most preferred.
  • the glass transition temperature of the polymer compound is preferably -20 to 100°C, more preferably -20 to 80°C, even more preferably -10 to 60°C. The glass transition temperature can be measured using DSC 3500 Sirius (manufactured by Netzsch). A polymer compound can be synthesized based on a known method.
  • polymer compound examples include "DA-7301” manufactured by Kusumoto Kasei Co., Ltd., "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid group)” manufactured by BYK Chemie, 111 (phosphoric acid dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 167, 170, 190 (polymer copolymer), BYK-P104, P105 (polymer copolymer) EFKA 4047, 4050-4010-4165 (polyurethane type), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (manufactured by EFKA) 6220 (fatty acid polyester), 6750 (azo pigment derivative), Ajisper PB821, PB822, PB880, PB881 manufactured by Ajinomoto Fine Techno
  • amphoteric resins containing acid groups and basic groups are also preferred.
  • the amphoteric resin a resin having an acid value of 5 mgKOH/g or more and an amine value of 5 mgKOH/g or more is preferable.
  • Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, and DISPER manufactured by BYK Chemie.
  • polymer compound for example, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A-2013-249417, the contents of which are incorporated herein.
  • examples of dispersants include graft copolymers described in paragraphs 0037 to 0115 of JP-A No. 2010-106268 (corresponding columns 0075 to 0133 of US 2011/0124824). The contents of the following are incorporated herein by reference. In addition to the above, it also includes a side chain structure in which acid groups are bonded via a linking group as described in paragraphs 0028 to 0084 of JP 2011-153283 (corresponding columns 0075 to 0133 of US 2011/0279759). Examples include polymeric compounds containing constituent components, the contents of which are incorporated herein by reference.
  • examples of the dispersant include resins described in paragraphs 0033 to 0049 of JP-A No. 2016-109763, the content of which is incorporated herein.
  • the alkali-soluble resin refers to a resin containing a group that promotes alkali solubility (hereinafter also simply referred to as an "alkali-soluble group"; for example, an acid group such as a carboxylic acid group), Different resins than the dispersants already described are contemplated. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups.
  • the alkali-soluble resin preferably contains a repeating unit having an acid group in its side chain. Examples of the repeating unit having an acid group in its side chain include a repeating unit represented by the below-mentioned formula (2RB).
  • the second resin contains a repeating unit having an acid group in its side chain, the content thereof is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, based on the total repeating units of the resin. More preferably 30% by mass.
  • alkali-soluble resins examples include polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic/(meth)acrylamide copolymer resins, epoxy resins, and polyimide resins. etc.
  • alkali-soluble resin examples include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
  • Unsaturated carboxylic acids are not particularly limited, but include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinyl acetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or their acid anhydrides; , polyhydric carboxylic acid monoesters such as mono(2-(meth)acryloyloxyethyl) phthalate; and the like.
  • copolymerizable ethylenically unsaturated compounds examples include methyl (meth)acrylate and the like. Further, compounds described in paragraph 0027 of JP-A No. 2010-097210 and paragraphs 0036 to 0037 of JP-A No. 2015-068893 can also be used, and the above content is incorporated into the present specification.
  • an alkali-soluble resin containing a curable group is also preferable since the effects of the present invention are more excellent.
  • the curable group include the curable groups that the above-mentioned polymer compound may contain, and the preferred ranges are also the same.
  • One embodiment of the alkali-soluble resin containing a curable group includes an acrylic resin containing an ethylenically unsaturated group in the side chain.
  • An acrylic resin containing an ethylenically unsaturated group in the side chain can be obtained by, for example, adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to the carboxylic acid group of an acrylic resin containing a carboxylic acid group. It will be done.
  • an alkali-soluble resin containing a curable group an alkali-soluble resin having a curable group in a side chain is preferable.
  • the alkali-soluble resin contains a repeating unit derived from a compound having a ClogP value of 1.0 or more.
  • the above ClogP value is preferably 1.0 to 8.0.
  • the definition of the ClogP value is as described above.
  • a repeating unit derived from (meth)acrylate is preferable.
  • the repeating unit derived from (meth)acrylate include a repeating unit represented by formula (2RA) described below.
  • the repeating unit derived from (meth)acrylate has a hydroxyl group as a substituent.
  • the alkali-soluble resin contains repeating units derived from (meth)acrylate, the content thereof is preferably 30% by mass or more, more preferably 60% by mass or more, and 70% by mass based on the total repeating units of the resin. The above is more preferable, and 80% by mass or more is particularly preferable.
  • 99 mass % or less is preferable, and 95 mass % or less is more preferable, for example.
  • the alkali-soluble resin contains a repeating unit represented by the following formula (2RA) and a repeating unit represented by the following formula (2RB), and has the formula (2RA) in that the light-shielding film of the present invention is easily formed.
  • a resin in which the content of repeating units represented by is 30% by mass or more (preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more) based on the total repeating units of the resin. is preferred.
  • R 1a represents a hydrogen atom or a methyl group.
  • R 2a represents a linear or branched alkyl group having 1 to 12 carbon atoms which may have a substituent or an aralkyl group having 7 to 18 carbon atoms which may have a substituent.
  • 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.
  • a linear alkyl group is preferable.
  • the number of carbon atoms in the aralkyl group represented by R 2a is preferably 7 to 18, more preferably 7 to 12, and even more preferably 7 to 10.
  • the substituents that the alkyl group and aralkyl group represented by R 2a may have are not particularly limited, and include, for example, a hydroxyl group.
  • R 1b represents a hydrogen atom or a methyl group.
  • L b represents a single bond or a divalent linking group.
  • the type of the divalent linking group is not particularly limited, and for example, a divalent hydrocarbon group (which may be a divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group).
  • the saturated hydrocarbon group may be linear, branched, or cyclic, and preferably has 1 to 10 carbon atoms, such as an alkylene group.Also, divalent aromatic hydrocarbon
  • R A represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
  • the content of the repeating unit represented by formula (2RA) is preferably 30% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and 80% by mass, based on the total repeating units of the resin.
  • the above is particularly preferable.
  • the upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less.
  • the content of the repeating unit represented by formula (2RB) is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 30% by mass, based on the total repeating units of the resin. , 5 to 25% by weight is particularly preferred.
  • the alkali-soluble resin containing the repeating unit represented by the formula (2RA) and the repeating unit represented by the formula (2RB) may contain other repeating units other than the above.
  • Other repeating units include repeating units having a curable group.
  • the curable group include the curable groups that the above-mentioned polymer compound may contain, and the preferred ranges are also the same.
  • the alkali-soluble resin contains a repeating unit having a curable group, the content thereof is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, based on the total repeating units of the resin.
  • the alkali-soluble resin has a structure including a repeating unit represented by formula (2RA-1) and a repeating unit represented by formula (2RA-2) as the repeating unit represented by formula (2RA).
  • the repeating unit represented by formula (2RA-1) is a repeating unit represented by formula (2RA) above, in which R 2a is an unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms. This is an aspect that represents.
  • the repeating unit represented by formula (2RA-2) is a linear unit having 1 to 12 carbon atoms in which R 2a has a substituent containing a hydroxyl group in the repeating unit represented by formula (2RA) above.
  • the alkali-soluble resin has a structure including a repeating unit represented by formula (2RA-1) and a repeating unit represented by formula (2RA-2), the repeating unit represented by formula (2RA-1) is The content is preferably 60 to 90% by mass based on the total repeating units of the resin, and the content of the repeating unit represented by formula (2RA-2) is preferably 60 to 90% by mass based on the total repeating units of the resin. The amount is preferably 2 to 15% by mass.
  • alkali-soluble resin examples include, but are not limited to, the following resins.
  • "Copolymerization component” in Table 1 below represents the type of repeating unit contained in the polymer.
  • “Copolymerization component ratio (mass%)” represents the content (mass%) of each repeating unit with respect to all repeating units of the polymer.
  • the acid value of the alkali-soluble resin is preferably 0 to 150 mgKOH/g, more preferably 20 to 100 mgKOH/g, even more preferably 40 to 90 mgKOH/g, and most preferably 60 to 90 mgKOH/g.
  • the weight average molecular weight of the alkali-soluble resin is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, even more preferably 15,000 to 40,000, and even more preferably 18,000 to 25,000. Particularly preferred.
  • the glass transition temperature of the alkali-soluble resin is preferably -20 to 120°C, preferably -20 to 110°C, more preferably -5 to 80°C, and even more preferably 0 to 70°C. The glass transition temperature can be measured using DSC 3500 Sirius (manufactured by Netzsch).
  • the content of the alkali-soluble resin in the composition is not particularly limited, but is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and 5 to 25% by mass based on the total solid content of the composition. More preferred.
  • One type of alkali-soluble resin may be used alone, or two or more types may be used in combination. When two or more types of alkali-soluble resins are used together, the total content is preferably within the above range.
  • the content of the resin (including an alkali-soluble resin and a dispersant) in the composition is not particularly limited, but is preferably 3 to 70% by mass, more preferably 9 to 50% by mass, and 10 to 50% by mass. 40% by mass is more preferred.
  • the composition may also include a polymerization initiator.
  • the polymerization initiator is not particularly limited, and any known polymerization initiator can be used. Examples of the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, with photopolymerization initiators being preferred. In addition, as the polymerization initiator, a so-called radical polymerization initiator is preferable.
  • thermal polymerization initiator examples include 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismarenonitrile, and dimethyl-(2,2')-azobis(2- Examples include azo compounds such as methyl propionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • AIBN 2,2'-azobisisobutyronitrile
  • 3-carboxypropionitrile examples include azo compounds such as methyl propionate) [V-601]
  • organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • Specific examples of the polymerization initiator include those described on pages 65 to 148 of "Ultraviolet Curing System" by Kiyoshi Kato (Published by Sogo Gijutsu Center Co., Ltd., 1989). .
  • the photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and any known photopolymerization initiator can be used.
  • the photopolymerization initiator for example, a photopolymerization initiator having photosensitivity from the ultraviolet region to the visible light region is preferable.
  • the activator may be an activator that generates active radicals by having some effect with the photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of polymerizable compound.
  • photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives.
  • oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.
  • paragraphs 0265 to 0268 of JP-A No. 2013-029760 can be referred to, the contents of which are incorporated herein.
  • Examples of the photopolymerization initiator include the aminoacetophenone initiator described in JP-A-10-291969 and the acylphosphine initiator 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 the aminoacetophenone compound include commercially available products Omnirad-907, Omnirad-369, and Omnirad-379EG (trade names: all manufactured by IGM RESINS BV).
  • Examples of the aminoacetophenone compound include compounds described in JP-A No.
  • acylphosphine compound examples include commercially available Omnirad-819 and Omnirad-TPO (trade names: both manufactured by IGM RESINS BV).
  • oxime compound As the photopolymerization initiator, an oxime ester polymerization initiator (oxime compound) is preferable.
  • oxime compounds are preferred because they have high sensitivity and high polymerization efficiency, and it is easy to design a high content of light-shielding pigment in the composition.
  • Examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166.
  • oxime compounds examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Examples include oxyimino-1-phenylpropan-1-one. Also, J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • IRGACURE-OXE03 manufactured by BASF
  • IRGACURE-OXE04 manufactured by BASF
  • TR-PBG-304 manufactured by Changzhou Strong Electronics New Materials Co., Ltd.
  • ADEKA ARCLES NCI-730 ADEKA ARCLES NCI-831
  • ADEKA ARCLES NCI-930 manufactured by ADEKA
  • N-1919 carboxymethyl methacrylate
  • Carbazole ⁇ An oxime ester skeleton-containing photoinitiator manufactured by ADEKA
  • Another example is Omnirad 1316 (IGM).
  • examples of oxime compounds other than the above include compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced at the benzophenone moiety; Compounds described in JP-A No. 2010-015025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety; Ketoxime compounds described in International Publication No. 2009-131189; and compounds in which the triazine skeleton and the oxime skeleton are the same Examples include the compound described in US Pat. No.
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
  • these groups may have one or more substituents.
  • the above-mentioned substituents may be further substituted with other substituents.
  • the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group, and more preferably an aryl group or a heterocyclic group. . These groups may have one or more substituents. Examples of the substituent include the substituents described above.
  • the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
  • photopolymerization initiators include oxime compounds containing fluorine atoms.
  • oxime compounds containing a fluorine atom include compounds described in JP-A No. 2010-262028; compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852; and compounds described in JP-A No. 2013-164471. Compound (C-3); and the like. This content is incorporated herein.
  • Examples of the polymerization initiator include compounds represented by the following formulas (1) to (4).
  • R 1 and R 2 are each independently 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 a carbon represents an arylalkyl group of 7 to 30, and when R 1 and R 2 are phenyl groups, the phenyl groups may combine with each other to form a fluorene group, and R 3 and R 4 each independently represent hydrogen.
  • X is a direct bond or a carbonyl group. shows.
  • R 1 , R 2 , R 3 , and R 4 are synonymous with R 1 , R 2 , R 3 , and R 4 in formula (1)
  • R 5 is -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN , a halogen atom, or a hydroxyl group
  • R 6 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocycle having 4 to 20 carbon atoms.
  • X represents a direct bond or a carbonyl group
  • a represents an integer of 0 to 4.
  • R 1 is 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 arylalkyl group having 7 to 30 carbon atoms.
  • R 3 and R 4 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 arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 4 carbon atoms.
  • X represents a direct bond or a carbonyl group.
  • R 1 , R 3 , and R 4 are synonymous with R 1 , R 3 , and R 4 in formula (3)
  • R 5 is -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, halogen atom, or hydroxyl group
  • R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms
  • X is , represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
  • Examples of the compounds represented by formula (1) and formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein.
  • a compound represented by the following formula (1) is also preferable.
  • R represents a group represented by the following formula (1a).
  • n represents an integer from 1 to 5.
  • m represents an integer from 1 to 6. * represents the bonding position.
  • the compound represented by formula (1) can be synthesized, for example, according to the synthesis method described in JP-A-2012-519191.
  • oxime compounds preferably used in the above composition are shown below. Further, examples of the oxime compound include the compounds described in Table 1 of International Publication No. 2015-036910, the contents of which are incorporated herein.
  • the oxime compound preferably has a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably has a maximum absorption wavelength in a wavelength range of 360 to 480 nm, and even more preferably has high absorbance at wavelengths of 365 nm and 405 nm.
  • the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000.
  • the molar absorption coefficient of a compound can be determined using a known method.
  • Photopolymerization initiators may be used in combination of two or more types, if necessary.
  • an oxime ester polymerization initiator is preferable, and a compound represented by the above formula (1) is more preferable, since the effects of the present invention are more excellent.
  • the content of the polymerization initiator in the composition is not particularly limited, but it is preferably 0.5 to 20% by mass, and 1.0 to 20% by mass, based on the total solid content of the composition, in order to achieve better effects of the present invention.
  • the content is more preferably 10% by weight, and even more preferably 1.5 to 8% by weight.
  • the polymerization initiators may be used alone or in combination of two or more. When two or more types of polymerization initiators are used together, it is preferable that the total content is within the above range.
  • the composition may also include a surfactant.
  • the surfactant contributes to improving the coating properties of the composition.
  • examples of the surfactant include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants. Among these, silicone surfactants are preferred because they provide better effects of the present invention.
  • silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into side chains and/or terminals, and the like.
  • silicone surfactants examples include DOWSIL (registered trademark) series DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (all manufactured by Dow Corning Toray); X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, KF-6000, KF-6004, KP-323, KP-341, KF-6001, and KF-6002 (manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (manufactured by Momentive Performance Materials); BYK307, BYK323, and BYK330 (manufactured by BYK Chemie).
  • DOWSIL registered trademark
  • a preferred embodiment of the silicone surfactant is an aromatic group-modified silicone surfactant (a silicone surfactant having an aromatic group), and a phenyl-modified silicone surfactant, since the effects of the present invention are more excellent.
  • type silicone surfactants silicone surfactants having a phenyl group are more preferred.
  • fluorine-based surfactants examples include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, F482, F554, and F780 (manufactured by DIC Corporation); Florado FC430, FC431, and FC171 (manufactured by Sumitomo 3M Corporation); Surflon S-382, SC-101 , SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.); and Examples include PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA).
  • the content of the surfactant in the composition is not particularly limited, but the content of the surfactant in the composition is not particularly limited. It is preferably 2.0% by weight, more preferably 0.005 to 0.5% by weight, and even more preferably 0.01 to 0.1% by weight.
  • the surfactants 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.
  • the composition may also include a solvent.
  • the solvent is not particularly limited, and any known solvent can be used, such as organic solvents and water.
  • the content of solids in the composition is preferably 10 to 90% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 50% by mass, based on the total mass of the composition. That is, although the content of the solvent in the composition is not particularly limited, it is preferable that the solid content of the composition is adjusted to the above content.
  • One type of solvent may be used alone or two or more types may be used in combination. When two or more types of solvents are used together, it is preferable that the total solid content of the composition is adjusted to fall within the above range.
  • organic solvents examples include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and acetylacetone.
  • cyclohexanone, cyclopentanone, diacetone alcohol ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, 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, ⁇ -butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N- Examples include, but are not limited to, methyl-2-pyrrolidone and ethyl lactate.
  • the composition may include a compound containing an epoxy group.
  • the compound containing an epoxy group include compounds having one or more epoxy groups, and preferably compounds having two or more epoxy groups. It is preferable to have 1 to 100 epoxy groups.
  • the upper limit may be, for example, 10 or less, or 5 or less.
  • the lower limit is preferably two or more.
  • the compound containing an epoxy group is intended to be a component different from the above-mentioned dispersant, alkali-soluble resin, and polymerizable compound.
  • the compound containing an epoxy group may be a low-molecular compound (e.g., molecular weight less than 2000) or a macromolecule (e.g., molecular weight 2000 or more, in the case of a polymer, the weight average molecular weight is 2000 or more).
  • the weight average molecular weight of the compound containing an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less.
  • a commercially available compound may be used as the compound containing an epoxy group.
  • Examples include EHPE3150 (manufactured by Daicel) and EPICLON N-695 (manufactured by DIC).
  • Compounds containing epoxy groups are described in paragraphs 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0092 of JP2014-089408. Examples include compounds that have been Their contents are incorporated herein.
  • the content of the compound containing an epoxy group in the composition is preferably 0.001 to 10% by mass, and 0.01% by mass based on the total solid content in the composition. It is more preferably 8% by mass, and even more preferably 0.01% by mass to 6% by mass.
  • the compounds containing epoxy groups may be used alone or in combination of two or more.
  • the total content thereof is preferably within the above range.
  • the composition may also include a silane coupling agent.
  • the silane coupling agent functions as an adhesive that improves the adhesion between the substrate and the light-shielding film when forming the light-shielding film on the substrate.
  • a silane coupling agent is a compound containing a hydrolyzable group and other functional groups in its molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
  • a hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through a hydrolysis reaction and/or a condensation reaction.
  • the hydrolyzable group examples include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
  • the number of carbon atoms is preferably 6 or less, more preferably 4 or less.
  • an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferred.
  • the silane coupling agent is used to improve the adhesion between the substrate and the light-shielding film.
  • the silane coupling agent may contain an ethylenically unsaturated group such as a (meth)acryloyl group. When containing ethylenically unsaturated groups, the number is preferably 1 to 10, more preferably 4 to 8.
  • a silane coupling agent containing an ethylenically unsaturated group (for example, a compound containing a hydrolyzable group and an ethylenically unsaturated group and having a molecular weight of 2000 or less) does not correspond to the above-mentioned polymerizable compound.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Examples include vinyltrimethoxysilane and vinyltriethoxysilane.
  • the content of the silane coupling agent in the composition is preferably 0.1 to 10% by mass, and 0.5 to 8% by mass, based on the total solid content in the composition.
  • the amount is more preferably 1.0 to 6% by weight, and even more preferably 1.0 to 6% by weight.
  • the composition may contain one type of silane coupling agent alone, or may contain two or more types of silane coupling agents. When the composition contains two or more types of silane coupling agents, the total may be within the above range.
  • the composition may also include a UV absorber.
  • a UV absorber examples include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers.
  • compounds in paragraphs 0137 to 0142 of JP2012-068418 are also mentioned, and the contents thereof can be cited and incorporated herein.
  • UV absorber examples include diethylamino-phenylsulfonyl ultraviolet absorbers (manufactured by Daito Kagaku Co., Ltd., trade name: UV-503).
  • examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP-A No. 2012-032556.
  • the content of the UV absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, based on the total solid content of the composition. .1 to 5% by mass is more preferred.
  • the composition may include optional colorants, which can be selected from pigments, dyes, infrared absorbers, and the like.
  • the colorant is other than the above-mentioned carbon black, barium sulfate, and metal-containing particles.
  • the composition may further contain other optional components other than those mentioned above.
  • optional components include polymerization inhibitors, sensitizers, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and sensitizing agents.
  • adhesion promoters and other auxiliary agents e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling promoters, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc.
  • These components are described, for example, in paragraphs 0183 to 0228 of JP2012-003225A (corresponding paragraphs 0237 to 0309 of US Patent Application Publication No.
  • the composition is first prepared by producing a dispersion composition in which a black pigment is dispersed, and then the obtained dispersion composition is further mixed with other components to form a composition.
  • the dispersion composition is preferably prepared by mixing a black pigment, a resin (dispersion resin), and a solvent. It is also preferable to introduce a polymerization inhibitor into the dispersion composition.
  • the above-mentioned dispersion composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, etc.).
  • the dispersion composition After preparing the dispersion composition, it can be prepared by mixing the dispersion composition, resin (alkali-soluble resin), polymerizable compound, polymerization initiator, and solvent.
  • resin alkali-soluble resin
  • polymerizable compound polymerizable compound
  • solvent solvent
  • each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then blended sequentially. Furthermore, the order of addition and working conditions during blending are not particularly limited.
  • the composition is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
  • a filter for example, any filter that has been conventionally used for filtration purposes can be used without particular restriction.
  • filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP).
  • PTFE polytetrafluoroethylene
  • nylon polyamide resins
  • polyolefin resins including high density and ultra-high molecular weight
  • PP polypropylene
  • polypropylene including high-density polypropylene
  • nylon is preferred.
  • the pore diameter of the filter is preferably 0.1 to 7.0 ⁇ m, more preferably 0.2 to 2.5 ⁇ m, even more preferably 0.2 to 1.5 ⁇ m, and particularly preferably 0.3 to 0.7 ⁇ m. Within this range, fine foreign substances such as impurities and aggregates contained in the pigments can be reliably removed while suppressing the clogging of the filtration of pigments (including black pigments).
  • the composition preferably does not contain impurities such as metals, metal salts containing halogens, acids, and alkalis.
  • the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and substantially free of impurities (measured). most preferably below the detection limit of the device).
  • impurities can be measured using an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
  • the light shielding film is a cured film.
  • a "cured film” is a film formed by subjecting a composition layer formed using a composition to a curing treatment such as an exposure treatment.
  • a method for manufacturing a light-shielding film (cured film) in the case where the light-shielding film is a cured film will be described.
  • the method for manufacturing a light shielding film preferably includes the following steps. By going through the above steps, for example, a patterned light shielding film can be formed. Note that if the light-shielding film is not patterned, the development step may not be performed. Each step will be explained below.
  • composition layer forming process In the composition layer forming step, prior to exposure, a composition is applied onto a support or the like to form a composition layer (composition layer).
  • a support for example, a substrate for a solid-state image sensor in which an image sensor (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate) is used.
  • an undercoat layer may be provided on the support, if necessary, for improving adhesion with the upper layer, preventing substance diffusion, flattening the substrate surface, and the like.
  • Examples of methods for applying the composition onto the support include various coating methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, and screen printing.
  • the thickness of the composition layer is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and even more preferably 0.2 to 3 ⁇ m. Drying (prebaking) of the composition layer coated on the support can be performed at a temperature of 50 to 140° C. for 10 to 300 seconds using a hot plate, oven, or the like.
  • the exposure step is a step of exposing the composition layer formed in the composition layer forming step by irradiating actinic rays or radiation.
  • the exposure step is a step of irradiating and exposing the composition layer formed in the composition layer forming step with actinic rays or radiation, and curing the light irradiated area of the composition layer.
  • the method of light irradiation is not particularly limited, it is preferable to irradiate light through a photomask having patterned openings.
  • Exposure is preferably carried out by irradiation with radiation, and the radiation that can be used for exposure is particularly preferably ultraviolet rays such as G-line, H-line, and I-line, and a high-pressure mercury lamp is preferable as the light source.
  • the irradiation intensity is preferably 5 to 1500 mJ/cm 2 , more preferably 10 to 1000 mJ/cm 2 .
  • a composition contains a thermal polymerization initiator, it is also preferable to heat a composition layer in the said exposure process.
  • the heating temperature is not particularly limited, but is preferably 80 to 250°C.
  • the heating time is not particularly limited, but is preferably 30 to 300 seconds.
  • the composition layer when heating the composition layer, it may also serve as a post-heating process described below.
  • the method for producing a light shielding film when heating the composition layer in the exposure step, the method for producing a light shielding film does not need to include a post-heating step.
  • the developing step is a step of subjecting the exposed composition layer to a developing treatment. Through this step, the composition layer in the photoexposed area in the exposure step is eluted, leaving only the photocured portion. For example, when light is irradiated through a photomask having patterned openings in the exposure process, a patterned light shielding film is obtained.
  • the type of developer used in the developing step is not particularly limited, but an alkaline developer is preferable because it does not cause damage to the underlying image sensor, circuits, etc.
  • the developing temperature is, for example, 20 to 30°C.
  • the developing time is, for example, 20 to 90 seconds. In order to remove more residue, in recent years, it is sometimes carried out for 120 to 180 seconds. Furthermore, in order to further improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying new developer may be repeated several times.
  • 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).
  • alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropyl.
  • Examples include ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among these, organic alkalis are preferred).
  • washing treatment with water is generally performed after development.
  • Post bake It is preferable to perform a heat treatment (post-bake) after the exposure step.
  • Post-bake is a heat treatment after development to complete curing.
  • the heating temperature is preferably 240°C or lower, more preferably 220°C or lower. Although there is no particular lower limit, in consideration of efficient and effective treatment, the temperature is preferably 50°C or higher, more preferably 100°C or higher.
  • Post-baking can be performed in a continuous or batch manner using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater.
  • the above post-bake is preferably performed in an atmosphere with a low oxygen concentration.
  • the oxygen concentration is preferably 19 vol% or less, more preferably 15 vol% or less, even more preferably 10 vol% or less, particularly preferably 7 vol% or less, and most preferably 3 vol% or less. Although there is no particular lower limit, 10 volume ppm or more is practical.
  • the composition described above preferably further contains a UV curing agent.
  • the UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of a polymerization initiator added for a lithography process using normal i-line exposure.
  • Examples of the UV curing agent include Ciba Irgacure 2959 (trade name).
  • the composition layer is preferably made of a material that hardens at a wavelength of 340 nm or less.
  • the wavelength it is generally 220 nm or more.
  • the exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and still more preferably 800 to 3500 mJ.
  • This UV curing step is preferably performed after the lithography step in order to more effectively perform low temperature curing. It is preferable to use an ozone-free mercury lamp as the exposure light source.
  • the light-shielding film has an excellent light-shielding property, and the optical density (OD) per film thickness of 5.0 ⁇ m in the wavelength region of 400 to 1100 nm is preferably 3.0 or more, more preferably 3.5 or more. preferable.
  • the upper limit is not particularly limited, but is generally preferably 10 or less.
  • the optical density per 5.0 ⁇ m of film thickness in the wavelength region of 400 to 1100 nm is 3.0 or more means that the optical density per 5.0 ⁇ m of film thickness in the wavelength range of 400 to 1100 nm is 3.0 or more.
  • a light-shielding film is formed on a glass substrate, and then the optical density is measured using a spectrophotometer (for example, U-4100 manufactured by Hitachi High-Technologies, Inc.). Measure.
  • the thickness of the light shielding film is, for example, preferably 0.1 to 6.0 ⁇ m, more preferably 1.0 to 5.0 ⁇ m, and even more preferably 1.0 to 2.5 ⁇ m. Further, the light shielding film may be made thinner or thicker than this range depending on the purpose.
  • the light-shielding film has excellent low reflectivity, and the maximum reflectance (at an incident angle of 5°) per film thickness of 5.0 ⁇ m in the wavelength range of 350 to 1200 nm is preferably less than 5%, and preferably less than 3%. is more preferable.
  • the lower limit is not particularly limited, but is generally 0% or more.
  • a method for measuring the maximum reflectance of a light shielding film first, a light shielding film is formed on a glass substrate, and a spectrometer (for example, a VAR unit of a spectrometer V7200 manufactured by JASCO Corporation) is used. A reflectance spectrum for an incident angle of 5° is obtained using the method, and the reflectance of light having a maximum reflectance in the wavelength range of 350 to 1200 nm is determined.
  • the light-shielding film can be applied to portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multifunction printers and scanners; surveillance cameras, barcode readers, and automated teller machines.
  • Industrial equipment such as automated teller machines (ATMs), high-speed cameras, and devices with personal authentication functions using facial image authentication; vehicle-mounted camera equipment; endoscopes, capsule endoscopes, catheters, etc. medical camera equipment; and space applications such as biosensors, biosensors, military reconnaissance cameras, stereo mapping cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomical and deep space targets. It is suitable for light-shielding members and light-shielding films of optical filters and modules used in industrial equipment, etc., as well as anti-reflection members and anti-reflection films.
  • the light shielding film can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes).
  • the light-shielding film is suitable for optical filters and optical films used in micro-LEDs and micro-OLEDs, as well as members that provide a light-shielding function or an antireflection function. Examples of micro LEDs and micro OLEDs include those described in Japanese Translated Patent Publication No. 2015-500562 and Japanese Translated Patent Publication No. 2014-533890.
  • the light-shielding film is also suitable as an optical film used in quantum dot sensors and quantum dot solid-state imaging devices. Further, it is suitable as a member that provides a light shielding function and an antireflection function. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313 pamphlet.
  • the solid-state image sensor of the present invention is a solid-state image sensor that has the light-shielding film of the present invention.
  • the form in which the solid-state image sensor includes a light-shielding film is not particularly limited, and for example, it may include a plurality of photodiodes, polysilicon, etc. that constitute the light receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on the substrate.
  • Examples include a configuration in which the support has a light-receiving element and a light-shielding film on the side of the support where the light-receiving element is formed (for example, a portion other than the light-receiving part and/or a color adjustment pixel, etc.) or on the opposite side of the formation surface.
  • a light-shielding film as a light-attenuating film, for example, if the light-attenuating film is arranged so that some light passes through the light-attenuating film and then enters the light-receiving element, the dynamic range of the solid-state image sensor can be improved. can be improved.
  • the solid-state imaging device includes the solid-state imaging device described above.
  • the light shielding film is also preferably applied to an image display device.
  • the image display device of the present invention is an image display device having the light shielding film of the present invention.
  • An example of a mode in which the image display device has a light-shielding film is a mode in which a color filter including a black matrix including a light-shielding film is applied to the image display device.
  • a black matrix and a color filter including a black matrix will be explained, and further, a liquid crystal display device including such a color filter will be explained as a specific example of an image display device.
  • a black matrix may be included in a color filter, a solid-state image sensor, and an image display device such as a liquid crystal display device.
  • Examples of the black matrix include those already explained above; a black edge provided at the periphery of an image display device such as a liquid crystal display; a lattice-like and/or stripe-like matrix between red, blue, and green pixels; Examples include black portions; dot-like and/or linear black patterns for TFT (thin film transistor) light shielding; and the like.
  • this black matrix For the definition of this black matrix, see, for example, Taihei Kanno, “Liquid Crystal Display Manufacturing Equipment Terminology Dictionary,” 2nd edition, Nikkan Kogyo Shimbun, 1996, p. It is described in 64.
  • the black matrix is used to improve display contrast, and in the case of active matrix drive type liquid crystal display devices using thin film transistors (TFTs), to prevent image quality from deteriorating due to light current leakage. 3 or more).
  • TFTs thin film transistors
  • the method for producing the black matrix is not particularly limited, but it can be produced by a method similar to the method for producing the light-shielding film described above.
  • a patterned light-shielding film (black matrix) can be manufactured by applying a composition to a substrate to form a composition layer, exposing it to light, and developing it.
  • the thickness of the light shielding film (black matrix) is preferably 0.1 to 4.0 ⁇ m.
  • the above substrate is not particularly limited, but preferably has a transmittance of 80% or more for visible light (wavelength 400 to 800 nm).
  • base materials include glasses such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; From the viewpoint of heat resistance, alkali-free glass or quartz glass is preferable.
  • the light shielding film is included in the color filter.
  • the color filter includes a light-shielding film include, but are not particularly limited to, a color filter including a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
  • a color filter containing a black matrix can be manufactured, for example, by the following method.
  • a coating film (composition layer) of a composition containing a pigment corresponding to each colored pixel of a 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 any known composition can be used; however, in the composition described in this specification, a composition in which the black pigment is replaced with a coloring agent corresponding to each pixel may be used. is preferred.
  • the composition layer is exposed to light through a photomask having a pattern corresponding to the openings in the black matrix.
  • it is baked to form colored pixels in the openings of the black matrix. For example, by performing a series of operations using compositions for each color containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be manufactured.
  • the light shielding film is included in the liquid crystal display device.
  • the form in which the liquid crystal display device includes a light shielding film is not particularly limited, but may include a form including a color filter including the black matrix (light shielding film) described above.
  • An example of a liquid crystal display device is one that includes a pair of substrates placed opposite to each other and a liquid crystal compound sealed between the substrates.
  • the above-mentioned substrate is as already explained as a black matrix substrate.
  • liquid crystal display device for example, from the user side, polarizing plate/substrate/color filter/transparent electrode layer/alignment film/liquid crystal layer/alignment film/transparent electrode layer/TFT (Thin Film Transistor) Examples include a laminate including an element/substrate/polarizing plate/backlight unit in this order.
  • liquid crystal display devices are not limited to those mentioned above, and include, for example, “Electronic Display Device (written by Akio Sasaki, published by Industrial Research Association Co., Ltd. in 1990)" and “Display Device (authored by Junaki Ibuki, published by Sangyo Tosho Co., Ltd.)".
  • An example of this is the liquid crystal display device described in ⁇ 1989 (Published in 1989)''.
  • Another example is the liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd. in 1994)".
  • the solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light emitting diode, and the like.
  • paragraphs 0032 to 0036 of JP-A No. 2011-233983 can be referred to, and the contents thereof are incorporated into the present specification.
  • Binder resin The following resins were used as the binder resins (resins B-1 to B-12) shown in Table 3.
  • Table 2 shows the structures of resins B-1 to B-10. Resins B-1 to B-10 were synthesized. A synthesis example of resin B-1 is shown below as an example. Note that Resins B-2 to B-10 were synthesized in the same manner as in the synthesis example of Resin B-1, except that the types and blending ratios of raw material monomers were changed.
  • Pigment dispersion As the pigment dispersions shown in Table 3, Dispersions 1 and 2 were used. Hereinafter, methods for preparing dispersion liquid 1 and dispersion liquid 2 will be explained.
  • ⁇ Preparation of dispersion liquid 1> 120 g of titanium oxide TTO-51N (trade name: manufactured by Ishihara Sangyo) with a BET specific surface area of 110 m 2 /g, 25 g of silica particles AEROSIL 300 (registered trademark) 300/30 (manufactured by Evonik) with a BET surface area of 300 m 2 /g, and Weighed 100g of the dispersant Disperbyk190 (trade name: manufactured by BYK Chemie), added 71g of ionized electric exchange water, and mixed the mixture for 30 minutes at a revolution speed of 1360 rpm and an autorotation speed of 1047 rpm using KURABO MAZERSTAR KK-400W.
  • a homogeneous aqueous solution was obtained by treatment.
  • This aqueous solution was filled into a quartz container and heated to 920° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the atmosphere in the small rotary kiln was replaced with nitrogen, and a nitriding reduction treatment was performed by flowing ammonia gas at 100 mL/min into the small rotary kiln for 5 hours at the same temperature.
  • the collected powder was ground in a mortar to obtain a powdered titanium black (A-1) [dispersed element containing titanium black particles and Si atoms] containing Si atoms and having a specific surface area of 85 m 2 /g.
  • A-1 powdered titanium black [dispersed element containing titanium black particles and Si atoms] containing Si atoms and having a specific surface area of 85 m 2 /g.
  • Dispossion resin A-1 The following structure. Table 3 shows the weight average molecular weight. The acid value is 57.2 mgKOH/g, and the glass transition temperature is 33°C.) In the structural formula below, the unit of the numerical value appended to the parentheses of the main chain is mass %, and the value appended to the parentheses of the side chain corresponds to the average number of additions.
  • the obtained dispersion a was subjected to a dispersion treatment using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. under the following conditions to obtain dispersion liquid 1.
  • ⁇ Dispersion conditions ⁇ Bead diameter: ⁇ 0.05mm, made of zirconia ⁇ Bead filling rate: 65% by volume ⁇ Mill peripheral speed: 10m/sec ⁇ Separator peripheral speed: 11m/s ⁇ Amount of mixed liquid to be dispersed: 15kg ⁇ Circulation flow rate (pump supply amount): 60kg/hour ⁇ Processing liquid temperature: 19-21°C ⁇ Cooling water: water ⁇ Number of passes: 90 passes
  • Dispersion 2 was prepared in the same manner as ⁇ Preparation of Dispersion 1> except that Dispersion Resin A-2 having the following structure was used instead of Dispersion Resin A-1.
  • Dispossion resin A-2 The following structure. Table 3 shows the weight average molecular weight. The acid value is 55.7 mgKOH/g, and the glass transition temperature is 55°C.) In the structural formula below, the unit of the numerical value appended to the parentheses of the main chain is mass %, and the value appended to the parentheses of the side chain corresponds to the average number of additions.
  • ⁇ D-1 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
  • ⁇ D-2 NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated dipentaerythritol polyacrylate)
  • ⁇ D-3 NK ester A-TMMT (manufactured by Shin Nakamura Chemical Co., Ltd., pentaerythritol tetraacrylate)
  • E-1 to E-4 The initiators (E-1 to E-4) shown in Table 3 are shown below.
  • ⁇ E-1 ADEKA Arkles NCI-831E (manufactured by ADEKA, oxime ester polymerization initiator)
  • ⁇ E-2 Compound with the following structure (oxime ester polymerization initiator)
  • ⁇ E-3 IRGACURE OXE02 (manufactured by BASF, oxime ester polymerization initiator)
  • ⁇ E-4 IRGACURE OXE01 (manufactured by BASF, oxime ester polymerization initiator)
  • the surfactant (W-1) shown in Table 3 is shown below.
  • ⁇ W-1 KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • compositions-1 to 21, R1 to R2 were prepared by mixing the components and amounts shown in Table 3 below.
  • a composition similar to Example 1 of International Publication No. 2017/057192 was prepared as Composition-R3.
  • solvents A to C are as follows.
  • Solvent A Cyclopentanone
  • Solvent B Propylene glycol monomethyl ether acetate (PGMEA)
  • Solvent C Butyl acetate
  • the unit of acid value is mgKOH/g.
  • the obtained composition was applied onto a glass substrate by a spin coating method to produce a coating film having a film thickness of 5.0 ⁇ m after exposure.
  • the entire surface of the substrate was exposed to 1000 mJ/cm 2 using a high-pressure mercury lamp (lamp power 50 mW/cm 2 ) using UX-1000SM-EH04 (manufactured by Ushio Inc.). exposed to light.
  • the exposed substrate was post-baked at 220° C. for 300 seconds to obtain a substrate with a light-shielding film (cured film).
  • Each composition was spin-coated onto a glass substrate (Corning 1737 [trade name], manufactured by Corning Inc.), and then heat-treated (prebaked) for 2 minutes using a 100° C. hot plate. Thereafter, the entire surface of the substrate was exposed to light at an exposure dose of 1000 mJ/cm 2 using a high-pressure mercury lamp (lamp power 50 mW/cm 2 ) using UX-1000SM-EH04 (manufactured by Ushio Inc.). After this, the substrate was paddle-developed for 10 to 60 seconds using a developer containing 0.29% by mass of TMAH (tetramethylammonium hydroxide), washed with water, and dried.
  • TMAH tetramethylammonium hydroxide
  • a heat treatment (post-bake) was performed for a second to produce a substrate with a resin film.
  • DektakXT manufactured by BRUKER
  • the surface roughness of the resin film on the obtained substrate was measured at a distance of 1 mm (resolution: 1 ⁇ m/point), and the surface roughness Ra ( ⁇ ) was determined.
  • the results are shown in Table 4.
  • Example 1 using Composition-1
  • Example 17 using Composition-17
  • Example 18 using Composition-17
  • cyclopentane was used as a solvent for the composition for forming a light-shielding film. It was confirmed that the light-shielding film had better low-reflection properties when non-containing material was used.
  • Example 1 using composition-1) and Example 2 (using composition-2), when the glass transition temperature of the alkali-soluble resin in the composition for forming a light-shielding film is 70°C or lower, light-shielding It was confirmed that the film had better low reflection properties. Also, a comparison between Example 1 (using composition-1), Example 3 (using composition-3) and Example 4 (using composition-4), and Example 5 (using composition-5) ⁇ From comparison with Example 8 (using composition-8), it was confirmed that when the weight average molecular weight of the alkali-soluble resin was 18,000 to 25,000, the light-shielding film had better low reflection characteristics.
  • Example 1 using composition-1)
  • Example 11 using composition-11
  • the dispersion resin of the composition for forming a light-shielding film is dispersion resin A-1
  • the light-shielding film is It was confirmed that the low reflection characteristics were better.
  • the light-shielding film of the comparative example prepared by changing the composition of the light-shielding film-forming composition did not exhibit the expected effect.
  • [Preparation of light shielding film] [Preparation of light-shielding composition A] The above dispersion liquid 2 (78.0 parts by mass), the above 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, polymerization initiation
  • the above E-1 (0.6 parts by mass) and TR-PBG-304 (manufactured by Tronly, 0.6 parts by mass) were used as agents, cyclopentanone (15.8 parts by mass) was used as a solvent, and 4-methoxy was used as a polymerization inhibitor.
  • Phenol (0.002 part), the following compound (0.3 part) and EHPE 3150 (manufactured by Daicel, 0.3 part) as additives, and the above W-1 (0.02 part by mass) as a surfactant.
  • a light-shielding composition A was prepared by mixing.
  • n is 2 to 4, and m represents 1 or 2.
  • the following compounds are mixtures of compounds in which n and m have any of the above numerical ranges.
  • Composition-19 (see Table 3) prepared in the upper section was applied onto a 10 cm square glass substrate by spin coating to produce a coating film with a film thickness of 6.0 ⁇ m after exposure. After pre-baking the obtained coating film at 90°C for 120 seconds, a frame-like pattern with an outer dimension of 10 mm, an inner dimension of 9.5 mm, and a width of 0.5 mm was formed using EVG610 (manufactured by EVG). Exposure treatment was performed with a high-pressure mercury lamp (lamp power 20 mW/cm 2 ) at an exposure dose of 200 mJ/cm 2 through a mask that could be formed. Paddle development was performed at 23° C.
  • TMAH tetramethylammonium hydroxide
  • Light-shielding composition A was applied to the frame-shaped light-shielding patterned glass by spin coating to produce a coating film having a film thickness of 1.0 ⁇ m after exposure.
  • Exposure treatment was carried out using a high-pressure mercury lamp (lamp power 20 mW/cm 2 ) with an exposure amount of 200 mJ/cm 2 through a high-pressure mercury lamp (lamp power 20 mW/cm 2 ).
  • Paddle development was performed at 23° C.
  • TMAH tetramethylammonium hydroxide

Abstract

A first problem of the present invention is to provide a light shielding film which is excellent in light shielding property and low in reflectance of infrared light. A second problem of the present invention is to provide a solid-state imaging element, an image display device, and an infrared sensor provided with this light shielding film.　The light shielding film according to the present invention contains black pigment and has a phase separation structure formed of a first phase containing the black pigment and a second phase not substantially containing the black pigment, and a total length of a boundary line between the first phase and the second phase is 2.50 to 15.00 μm when a range of 1×1 μm2 of a cross section orthogonal to a surface of the light shielding film is observed.

Description

遮光膜、固体撮像素子、画像表示装置、赤外線センサLight shielding film, solid-state image sensor, image display device, infrared sensor
　本発明は、遮光膜、固体撮像素子、画像表示装置、及び赤外線センサに関する。 The present invention relates to a light shielding film, a solid-state image sensor, an image display device, and an infrared sensor.
　液晶表示装置等の画像表示装置、並びに、ＣＣＤ（Charge Coupled Device）イメージセンサ及びＣＭＯＳ（Complementary Metal-Oxide Semiconductor）イメージセンサ等の固体撮像装置には、所定の位置に遮光膜が配置されている場合が多い。例えば、液晶表示装置では、着色画素間の光を遮蔽してコントラストの向上させる目的で、カラーフィルタ上の着色画素間にブラックマトリクスと呼ばれる遮光膜を配置する場合がある。また、固体撮像素子では、ノイズ発生防止及び画質の向上等を目的として遮光膜を適用する場合がある。遮光膜の形成には、通常、黒色顔料を含む組成物が使用される。 Image display devices such as liquid crystal display devices, and solid-state imaging devices such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors, have light-shielding films placed at predetermined positions. There are many. For example, in a liquid crystal display device, a light shielding film called a black matrix is sometimes disposed between colored pixels on a color filter in order to improve contrast by blocking light between colored pixels. Furthermore, in solid-state image sensors, a light-shielding film is sometimes applied for the purpose of preventing noise generation and improving image quality. A composition containing a black pigment is usually used to form a light-shielding film.
　例えば、特許文献１では、２種のＳＰ値の異なる分散剤を含む顔料分散組成物を使用し、上記２種の分散剤による相分離作用によって、表面に凹凸構造を有し、且つ、膜中において黒色顔料が均一に分散した遮光膜を形成できる旨が開示されている。 For example, in Patent Document 1, a pigment dispersion composition containing two types of dispersants with different SP values is used, and due to the phase separation effect of the two types of dispersants, the surface has an uneven structure and the film has an uneven structure. discloses that it is possible to form a light-shielding film in which black pigment is uniformly dispersed.
国際公開第２０１６／１２９３４２号International Publication No. 2016/129342
　本発明者らは、特許文献１に記載された遮光膜について検討したところ、赤外光の反射性を更に改善する余地があることを明らかとした。 The present inventors studied the light-shielding film described in Patent Document 1 and found that there is room for further improvement in infrared light reflectivity.
　そこで、本発明は、遮光性に優れ、且つ、赤外光の反射率が低い、遮光膜を提供することを課題とする。
　また、本発明は、上記遮光膜を備えた固体撮像素子、画像表示装置、及び赤外線センサを提供することも課題とする。 Therefore, an object of the present invention is to provide a light-shielding film that has excellent light-shielding properties and a low reflectance of infrared light.
Another object of the present invention is to provide a solid-state image sensor, an image display device, and an infrared sensor that include the above light-shielding film.
　本発明者は、上記課題を解決すべく鋭意検討した結果、以下の構成により上記課題を解決できることを見出した。 As a result of intensive study to solve the above problems, the present inventor found that the above problems could be solved by the following configuration.
　〔１〕　黒色顔料を含む遮光膜であって、
　上記遮光膜が、上記黒色顔料を含む第１相と、上記黒色顔料を実質的に含まない第２相とからなる相分離構造を有し、
　上記遮光膜の表面に直交する断面の１×１μｍ２の範囲を観察した際に、上記第１相と上記第２相との境界線の合計長さが２．５０～１５．００μｍである、遮光膜。
　〔２〕　表面粗さＲａが、４００～２０００Åである、〔１〕に記載の遮光膜。
　〔３〕　黒色顔料、樹脂、及び重合性化合物を含む組成物を用いて形成された、〔１〕に記載の遮光膜。
　〔４〕　上記合計長さが、２．５０～７．００μｍである、〔１〕～〔３〕のいずれかに記載の遮光膜。
　〔５〕　上記第１相が、酸価が４０～１００ｍｇＫＯＨ／ｇである第１樹脂を含み、
　上記第２相が、酸価が４０～９０ｍｇＫＯＨ／ｇである第２樹脂を含む、〔１〕～〔４〕のいずれかに記載の遮光膜。
　〔６〕　上記第１樹脂の重量平均分子量が、２０，０００～４０，０００であり、
　上記第２樹脂の重量平均分子量が、１５，０００～４０，０００である、〔５〕に記載の遮光膜。
　〔７〕　上記第１樹脂のガラス転移温度が、－１０～６０℃であり、
　上記第２樹脂のガラス転移温度が、０～７０℃である、〔５〕又は〔６〕に記載の遮光膜。
　〔８〕　上記黒色顔料が、金属窒化物粒子及び金属酸窒化物粒子からなる群より選ばれる粒子を含む、〔１〕～〔７〕のいずれかに記載の遮光膜。
　〔９〕　パターン状である、〔１〕～〔８〕のいずれかに記載の遮光膜。
　〔１０〕　〔１〕～〔９〕のいずれかに記載の遮光膜を含む、固体撮像素子。
　〔１１〕　〔１〕～〔９〕のいずれかに記載の遮光膜を含む、画像表示装置。
　〔１２〕　〔１〕～〔９〕のいずれかに記載の遮光膜を含む、赤外センサ。 [1] A light-shielding film containing a black pigment,
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 a 1×1 μm 2 area in a cross section perpendicular to the surface of the light shielding film, the total length of the boundary line between the first phase and the second phase is 2.50 to 15.00 μm. Light-shielding film.
[2] The light shielding film according to [1], which has a surface roughness Ra of 400 to 2000 Å.
[3] The light-shielding film according to [1], which is formed using a composition containing a black pigment, a resin, and a polymerizable compound.
[4] The light-shielding film according to any one of [1] to [3], wherein the total length is 2.50 to 7.00 μm.
[5] The first phase includes a first resin having an acid value of 40 to 100 mgKOH/g,
The light shielding film according to any one of [1] to [4], wherein the second phase contains a second resin having an acid value of 40 to 90 mgKOH/g.
[6] The weight average molecular weight of the first resin is 20,000 to 40,000,
The light shielding film according to [5], wherein the second resin has a weight average molecular weight of 15,000 to 40,000.
[7] The first resin has a glass transition temperature of -10 to 60°C,
The light shielding film according to [5] or [6], wherein the second resin has a glass transition temperature of 0 to 70°C.
[8] The light-shielding film according to any one of [1] to [7], wherein the black pigment contains particles selected from the group consisting of metal nitride particles and metal oxynitride particles.
[9] The light-shielding film according to any one of [1] to [8], which is patterned.
[10] A solid-state imaging device comprising the light-shielding film according to any one of [1] to [9].
[11] An image display device comprising the light shielding film according to any one of [1] to [9].
[12] An infrared sensor comprising the light shielding film according to any one of [1] to [9].
　本発明によれば、遮光性に優れ、且つ、赤外光の反射率が低い、遮光膜を提供できる。
　また、本発明によれば、上記遮光膜を備えた固体撮像素子、画像表示装置、及び赤外線センサを提供できる。 According to the present invention, it is possible to provide a light-shielding film that has excellent light-shielding properties and low reflectance of infrared light.
Further, according to the present invention, it is possible to provide a solid-state image sensor, an image display device, and an infrared sensor including the light-shielding film.
遮光膜の断面Ｔの相分離構造の一例（海島構造）を示す概略模式図である。FIG. 2 is a schematic diagram showing an example of a phase separation structure (sea-island structure) of a cross section T of a light shielding film. 遮光膜の断面Ｔの相分離構造の一例（共連続構造）を示す概略模式図である。FIG. 2 is a schematic diagram showing an example of a phase separation structure (co-continuous structure) of a cross section T of a light shielding film. トリミング後の断面ＴのＳＥＭ画像の一例を示す模式図である。It is a schematic diagram which shows an example of the SEM image of the cross section T after trimming. 図３のＳＥＭ画像を白黒２値化した後の画像を示す模式図である。4 is a schematic diagram showing an image after the SEM image of FIG. 3 is converted into black and white binarized. FIG. 図４の白黒２値化画像のエッジ検索の方法を説明するための模式図である。5 is a schematic diagram for explaining a method of edge search for the black-and-white binarized image of FIG. 4. FIG.
　以下、本発明について詳細に説明する。
　以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされる場合があるが、本発明はそのような実施態様に制限されない。
　なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。 The present invention will be explained in detail below.
Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit.
　また、本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を含有しない基と共に置換基を含む基をも包含する。例えば、「アルキル基」とは、置換基を含有しないアルキル基（無置換アルキル基）のみならず、置換基を含むアルキル基（置換アルキル基）をも包含する。 In addition, in the description of groups (atomic groups) in this specification, descriptions that do not indicate substituted or unsubstituted include groups that contain a substituent as well as groups that do not contain a substituent. For example, the term "alkyl group" includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
　また、本明細書中における「活性光線」又は「放射線」とは、例えば、遠紫外線、極紫外線（ＥＵＶ：Ｅｘｔｒｅｍｅ　ｕｌｔｒａｖｉｏｌｅｔ　ｌｉｔｈｏｇｒａｐｈｙ）、Ｘ線、及び電子線等を意味する。また本明細書において光とは、活性光線及び放射線を意味する。本明細書中における「露光」とは、特に断らない限り、遠紫外線、Ｘ線、及びＥＵＶ光等による露光のみならず、電子線及びイオンビーム等の粒子線による描画も包含する。 In addition, "actinic rays" or "radiation" in this specification means, for example, far ultraviolet rays, extreme ultraviolet lithography (EUV), X-rays, and electron beams. Moreover, in this specification, light means actinic rays and radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure with deep ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams.
　また、本明細書において、「（メタ）アクリレート」はアクリレート及びメタアクリレートを表す。また、本明細書において、「（メタ）アクリル」はアクリル及びメタアクリルを表す。また、本明細書において、「（メタ）アクリロイル」は、アクリロイル及びメタクリロイルを表す。また、本明細書において、「（メタ）アクリルアミド」は、アクリルアミド及びメタアクリルアミドを表す。また、本明細書中において、「単量体」と「モノマー」とは同義である。 Additionally, in this specification, "(meth)acrylate" represents acrylate and methacrylate. Moreover, in this specification, "(meth)acrylic" represents acrylic and methacrylic. Moreover, in this specification, "(meth)acryloyl" represents acryloyl and methacryloyl. Moreover, in this specification, "(meth)acrylamide" represents acrylamide and methacrylamide. Furthermore, in this specification, "monomer" and "monomer" have the same meaning.
　本明細書において重量平均分子量（Ｍｗ）は、ＧＰＣ（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ：ゲル浸透クロマトグラフィー）法によるポリスチレン換算値である。
　本明細書においてＧＰＣ法は、ＨＬＣ－８０２０ＧＰＣ（東ソー製）を用い、カラムとしてＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｈ、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ４０００、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ２０００（東ソー製、４．６ｍｍＩＤ×１５ｃｍ）を、溶離液としてＴＨＦ（テトラヒドロフラン）を用いる方法に基づく。 In this specification, the weight average molecular weight (Mw) is a polystyrene equivalent value determined by GPC (Gel Permeation Chromatography) method.
In this specification, the GPC method uses HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID x 15 cm) as a column, and THF (tetra hydrofuran) Based on the method used.
　本明細書において、組成物における固形分とは、組成物を用いて形成される組成物層を意味し、組成物が溶媒を含む場合、溶媒を除いた全ての成分を意味する。また、組成物層を形成する成分であれば、液体状の成分も固形分とみなす。 As used herein, the solid content of a composition means a composition layer formed using the composition, and when the composition contains a solvent, it means all components except the solvent. In addition, liquid components are also considered solid components as long as they form a composition layer.
［遮光膜］
　本発明の遮光膜は、
　黒色顔料を含む遮光膜であって、黒色顔料を含む第１相と、黒色顔料を実質的に含まない第２相とからなる相分離構造を有し、遮光膜の表面に直交する断面の１×１μｍ２の範囲を観察した際に、上記第１相と上記第２相との境界線の合計長さ（以下「境界距離Ｌ」ともいう。）が２．５０～１５．００μｍである。 [Light-shielding film]
The light shielding film of the present invention is
A light-shielding film containing a black pigment, which has a phase-separated structure consisting of a first phase containing the black pigment and a second phase that does not substantially contain the black pigment, and has a phase-separated structure consisting of a first phase containing the black pigment and a second phase that does not substantially contain the black pigment. When observing a range of ×1 μm 2 , the total length of the boundary line between the first phase and the second phase (hereinafter also referred to as “boundary distance L”) is 2.50 to 15.00 μm.
　本発明の遮光膜の第１の特徴点としては、黒色顔料を含む第１相と黒色顔料を実質的に含まない第２相とから構成された相分離構造を有する点が挙げられる。また、本発明の第２の特徴点として、遮光膜の表面に直交する断面の１×１μｍ２の範囲を観察した際に、第１相と第２相との境界距離Ｌが所定数値範囲である点が挙げられる。
　以下、本発明の構成と効果との推測される作用機序について説明する。
　上記構成の本発明の遮光膜は、膜の表面に微細な凹凸構造が形成されており、この結果として、優れた低反射性特性を発現していると推測される。つまり、本発明の遮光膜は、第１相と第２相とから構成される相分離構造を有し、第１相及び第２相のそれぞれのドメインサイズ及び分布状態を制御して、境界距離Ｌが所定の長さになるように調整すると、結果として、遮光膜の表面に相分離構造に由来する凹凸構造が形成され、この表面凹凸構造によって低反射特性がもたらされていると考えている。この境界距離Ｌと低反射特性との相関については、本明細書の実施例欄に示されるとおりである。境界距離Ｌが２．５０μｍ未満である場合、第１相の領域が大きすぎて（第１相の領域が光の波長よりも大きくなり）、所望の低反射性特性が発現しない。また、境界距離Ｌが１５．００μｍ超である場合、第１相の領域が小さすぎて（つまり、遮光膜の表面の凹凸構造が小さすぎて）、所望の低反射性特性が発現しない。なお、境界距離Ｌの測定方法については後述する。
　更に、本発明の遮光膜は、黒色顔料を含むことから、遮光性にも優れている。 A first feature of the light-shielding film of the present invention is that it has a phase-separated structure composed of a first phase containing a black pigment and a second phase that does not substantially contain the black pigment. In addition, as a second characteristic point of the present invention, when observing a 1×1 μm 2 area of a cross section perpendicular to the surface of the light shielding film, the boundary distance L between the first phase and the second phase is within a predetermined numerical range. One point can be mentioned.
Hereinafter, the structure and effect of the present invention and the presumed mechanism of action will be explained.
The light-shielding film of the present invention having the above structure has a fine uneven structure formed on the surface of the film, and it is presumed that as a result of this, it exhibits excellent low reflection characteristics. In other words, the light-shielding film of the present invention has a phase-separated structure composed of a first phase and a second phase, and controls the domain size and distribution state of each of the first and second phases to increase the boundary distance. When L is adjusted to a predetermined length, an uneven structure resulting from the phase separation structure is formed on the surface of the light-shielding film, and it is believed that this surface uneven structure provides low reflection characteristics. There is. The correlation between this boundary distance L and low reflection characteristics is as shown in the Examples section of this specification. If the boundary distance L is less than 2.50 μm, the first phase region is too large (the first phase region is larger than the wavelength of the light), and the desired low reflection characteristics are not expressed. Further, if the boundary distance L is more than 15.00 μm, the first phase region is too small (that is, the uneven structure on the surface of the light-shielding film is too small), and the desired low-reflectivity characteristics are not exhibited. Note that a method for measuring the boundary distance L will be described later.
Furthermore, since the light-shielding film of the present invention contains a black pigment, it also has excellent light-shielding properties.
　以下、本発明の遮光膜の低反射特性がより優れること、及び／又は、本発明の遮光膜の遮光性がより優れることを、「本発明の効果がより優れる」という場合もある。 Hereinafter, the fact that the light-shielding film of the present invention has better low reflection characteristics and/or the light-shielding property of the light-shielding film of the present invention is better may be referred to as "the effects of the present invention are better."
　以下、まず、本発明の遮光膜の構造について詳述し、その後、遮光膜の各成分及び形成方法について詳述する。
　本発明の遮光膜は、典型的には、黒色顔料を含む樹脂膜である。
　遮光膜は、黒色顔料を含む第１相と黒色顔料を実質的に含まない第２相とから構成された、相分離構造を有する。
　相分離構造としては、例えば、海島構造、共連続構造、並びに、海島構造と共連続構造が共存した構造が挙げられる。遮光膜が海島構造を有する場合、遮光膜の表面に直交する断面（換言すると、遮光膜を膜面方向に対して垂直に割断したときに露出する断面。以下「断面Ｔ」ともいう。）を観察すると、例えば、図１に示すように、第１相（分散相（図中のＡ））が第２相（連続相（図中のＢ））の中に散在している構造が観察される。また、遮光膜が共連続構造を有する場合、断面Ｔを観察すると、例えば、図２に示すように、第１相（図中のＡ）と第２相（図中のＢ）とが複雑な三次元の網目状を形成している構造が観察される。断面Ｔの表面構造は、走査型電子顕微鏡（ＳＥＭ：Scanning Electron Microscope）（例えば、（株）日立ハイテクノロジーズ社製の「Ｓ－４８００」）により観察できる。ＳＥＭ観察の条件としては、例えば、観察倍率：５０００～２５０００倍、加速電圧：３．０～５．０ｋｅＶの条件にて反射電子像を観察するのが好ましい。 Hereinafter, first, the structure of the light-shielding film of the present invention will be explained in detail, and then each component of the light-shielding film and the formation method will be explained in detail.
The light shielding film of the present invention is typically a resin film containing a black pigment.
The light-shielding film has a phase-separated structure composed of a first phase containing a black pigment and a second phase substantially free of the black pigment.
Examples of the phase-separated structure include a sea-island structure, a co-continuous structure, and a structure in which a sea-island structure and a co-continuous structure coexist. When the light shielding film has a sea-island structure, a cross section perpendicular to the surface of the light shielding film (in other words, a cross section exposed when the light shielding film is cut perpendicular to the film surface direction; hereinafter also referred to as "cross section T") is When observed, for example, as shown in Figure 1, a structure in which the first phase (dispersed phase (A in the diagram)) is scattered within the second phase (continuous phase (B in the diagram)) is observed. Ru. In addition, when the light shielding film has a co-continuous structure, when observing the cross section T, for example, as shown in FIG. 2, the first phase (A in the figure) and the second phase (B in the figure) are complicated. A structure forming a three-dimensional network is observed. The surface structure of the cross section T can be observed using a scanning electron microscope (SEM) (for example, "S-4800" manufactured by Hitachi High-Technologies, Inc.). As conditions for SEM observation, for example, it is preferable to observe the backscattered electron image under conditions of observation magnification: 5,000 to 25,000 times and acceleration voltage: 3.0 to 5.0 keV.
　黒色顔料を含む第１相は、典型的には、黒色顔料と樹脂とを含む相である。
　また、黒色顔料を実質的に含まない第２相は、典型的には、黒色顔料を実質的に含まず、樹脂を含む相である。
　なお、本明細書において相が黒色顔料を含むか否かの判断は、遮光膜の断面Ｔをエネルギー分散型Ｘ線分光法（ＳＥＭ－ＥＤＸ）に準じて観察及び元素分析することにより実施する。判断方法としては、具体的には以下の通りである。
　まず、遮光膜の断面Ｔの表面構造画像をＳＥＭにより取得する。取得したＳＥＭ画像を目視にて観察すると、濃淡がある２つの領域（濃画像領域及び淡画像領域）からなる濃淡模様（例えば、海島構造、共連続構造、並びに、海島構造と共連続構造が共存した構造等の濃淡模様）が観察される。
　次いで、観察視野内の濃淡模様における淡画像領域から、任意で、０．１μｍ×０．１μｍ（縦×横）の領域（以下「領域Ａ」ともいう。）を選択し、領域Ａにおける元素分析（ＥＤＸ）を実施し、領域Ａの原子組成（ａｔｏｍ％）を求める。また、観察視野内の濃淡模様における濃画像領域から、任意で、０．１μｍ×０．１μｍ（縦×横）の領域（以下「領域Ｂ」ともいう。）を選択し、領域Ｂにおける元素分析を実施し、領域Ｂの原子組成（ａｔｏｍ％）を求める。そして、領域Ａ及び領域Ｂの各領域において、黒色顔料が含む原子のうち最大含有量を占める原子の含有量（ａｔｏｍ％）を求める。
　ここで、黒色顔料が含む原子のうち最大含有量を占める原子とは、黒色顔料を構成する原子のうち、黒色顔料の全質量に対する含有量（質量％）が最も大きい原子をいう。なお、例えば、黒色顔料がチタンブラックの場合、黒色顔料を構成する原子のうち最大含有量を占める原子は、チタン原子が該当する。
　ここで、領域Ａにおいて、黒色顔料が含む原子のうち最大含有量を占める原子の含有量（ａｔｏｍ％）が１５ａｔｏｍ％以下である場合、領域Ａを含む淡画像領域の全体が、黒色顔料を含まないとみなし、黒色顔料が含む原子のうち最大含有量を占める原子の含有量（ａｔｏｍ％）が１５ａｔｏｍ％超である場合、領域Ａを含む淡画像領域の全体が、黒色顔料を含むとみなす。また、領域Ｂに関しても、上記領域Ａと同様に、黒色顔料が含む原子のうち最大含有量を占める原子の含有量（ａｔｏｍ％）が１５ａｔｏｍ％以下である場合、領域Ｂを含む濃画像領域の全体が、黒色顔料を含まないとみなし、黒色顔料が含む原子のうち最大含有量を占める原子の含有量（ａｔｏｍ％）が１５ａｔｏｍ％超である場合、領域Ａを含む濃画像領域の全体が、黒色顔料を含むとみなす。
　なお、領域Ａ及び領域Ｂが黒色顔料を含む場合、黒色顔料が含む原子のうち最大含有量を占める原子の含有量（ａｔｏｍ％）は、４０ａｔｏｍ％以上であるのが好ましい。
　本発明においては、領域Ａを含む淡画像領域においては黒色顔料が含まれ、領域Ｂを含む濃画像領域において黒色顔料が含まれない場合が多い。 The first phase containing black pigment is typically a phase containing black pigment and resin.
Further, the second phase that does not substantially contain black pigment is typically a phase that does not substantially contain black pigment and contains a resin.
In this specification, the determination as to whether a phase contains a black pigment is made by observing and elementally analyzing the cross section T of the light shielding film according to energy dispersive X-ray spectroscopy (SEM-EDX). The specific judgment method is as follows.
First, a surface structure image of the cross section T of the light shielding film is obtained by SEM. Visual observation of the acquired SEM image reveals a gray pattern (for example, a sea-island structure, a co-continuous structure, and a co-existence of a sea-island structure and a co-continuous structure) consisting of two areas (a dark image area and a light image area). A pattern of shading (shaded structures, etc.) is observed.
Next, an area of 0.1 μm x 0.1 μm (vertical x horizontal) (hereinafter also referred to as "area A") is arbitrarily selected from the light image area of the shading pattern within the observation field, and elemental analysis in area A is performed. (EDX) to determine the atomic composition (atom%) of region A. In addition, an area of 0.1 μm x 0.1 μm (vertical x horizontal) (hereinafter also referred to as "area B") is arbitrarily selected from the dark image area in the shading pattern within the observation field, and elemental analysis in area B is performed. is carried out to determine the atomic composition (atom%) of region B. Then, in each region of region A and region B, the content (atom %) of atoms occupying the maximum content among the atoms contained in the black pigment is determined.
Here, the atom that occupies the maximum content among the atoms contained in the black pigment refers to the atom that has the largest content (% by mass) based on the total mass of the black pigment, among the atoms that constitute the black pigment. Note that, for example, when the black pigment is titanium black, the atom that occupies the maximum content among the atoms constituting the black pigment is a titanium atom.
Here, in region A, if the content (atom%) of the atoms that account for the maximum content among the atoms contained in the black pigment is 15 atom% or less, the entire light image region including region A does not contain the black pigment. If the content (atom%) of the atom that occupies the maximum content among the atoms contained in the black pigment is more than 15 atom%, the entire light image area including area A is considered to contain the black pigment. Regarding area B, as with area A, if the content (atom%) of the atoms that account for the maximum content among the atoms contained in the black pigment is 15 atom% or less, the dark image area including area B If the entire dark image area including area A is considered to be free of black pigment, and the content (atom%) of atoms that account for the maximum content among the atoms contained in the black pigment is more than 15 atom%, the entire dark image area including area A is Considered to contain black pigment.
In addition, when the area|region A and the area|region B contain a black pigment, it is preferable that the content (atom%) of the atom which occupies the maximum content among the atoms contained in the black pigment is 40 atom% or more.
In the present invention, in many cases, a light image area including area A contains black pigment, and a dark image area including area B does not contain black pigment.
　本発明の遮光膜において、断面Ｔの１×１μｍ２の範囲を観察した際に、第１相と第２相との境界線の合計長さ（境界距離Ｌ）が２．５０～１５．００μｍである。以下、図３～図５を参照して、境界距離Ｌの測定方法について説明する。 In the light-shielding film of the present invention, when observing a 1×1 μm 2 area of cross section T, the total length of the boundary line between the first phase and the second phase (boundary distance L) is 2.50 to 15.00 μm. It is. A method for measuring the boundary distance L will be described below with reference to FIGS. 3 to 5.
〔境界距離Ｌの測定方法〕
　まず、遮光膜の断面Ｔの表面構造画像をＳＥＭにより取得する。
　装置としては、例えば、（株）日立ハイテクノロジーズ製の「Ｓ－４８００」を使用できる。また、観察条件としては、例えば、観察倍率：５．０ｋ（５０００倍）、加速電圧：２．０ｋｅＶの条件にて反射電子像を観察するのが好ましい。
　次に、取得した断面ＴのＳＥＭ画像における任意の６μｍ×１５μｍの領域をトリミングする。図３に、所定サイズにトリミングした後のＳＥＭ画像の一例を示す。図３におけるＳＥＭ画像において、灰色の領域が第１相に該当し、黒色の領域が第２相に該当する。 [Measurement method of boundary distance L]
First, a surface structure image of the cross section T of the light shielding film is acquired by SEM.
As the device, for example, “S-4800” manufactured by Hitachi High-Technologies Corporation can be used. Moreover, as observation conditions, it is preferable to observe a backscattered electron image under conditions of, for example, observation magnification: 5.0k (5000 times) and acceleration voltage: 2.0 keV.
Next, an arbitrary 6 μm×15 μm area in the acquired SEM image of the cross section T is trimmed. FIG. 3 shows an example of a SEM image after trimming to a predetermined size. In the SEM image in FIG. 3, gray areas correspond to the first phase, and black areas correspond to the second phase.
　次に、トリミングしたＳＥＭ画像を画像処理ソフトウェア（ＩｍａｇｅＪ）を用いて２値化処理する（ＩｍａｇｅＪにおける「Ｐｒｏｃｅｓｓ」メニューから「Ｍａｋｅ　Ｂｉｎａｒｙ」メニューを選択）。
　上記手順により、画素が所定階調以下であれば画素を「黒」とし、画素が所定階調超であれば画素を「白」として２値化処理する。図４は、図３のＳＥＭ画像を白黒２値化した後の画像の模式図である。図４において、２値化により「白」で表示された箇所が第１相に該当し、２値化により「黒」で表示された箇所が第２相に該当する。
　なお、上記手順における画素の階調の閾値を設定するに際して、ＩｍａｇｅＪにおける「Ａｄｊｕｓｔ」メニューから「Ｔｈｒｅｓｈｏｌｄ」メニューを選択し、表示されるＴｈｒｅｈｏｌｄウィンドウ中の２つのバーの位置を調整して、Ｔｈｒｅｈｏｌｄウィンドウ中のヒストグラムの下に表示される値が４０～６０％の範囲になるように設定するのが好ましい。 Next, the trimmed SEM image is binarized using image processing software (ImageJ) (select the "Make Binary" menu from the "Process" menu in ImageJ).
According to the above procedure, if the pixel is below a predetermined gradation level, the pixel is set as "black", and if the pixel is above the predetermined gradation level, the pixel is set as "white" and binarized. FIG. 4 is a schematic diagram of an image after the SEM image of FIG. 3 is converted into black and white binarized. In FIG. 4, the parts displayed as "white" by binarization correspond to the first phase, and the parts displayed as "black" by binarization correspond to the second phase.
When setting the pixel gradation threshold in the above procedure, select the "Threshold" menu from the "Adjust" menu in ImageJ, adjust the positions of the two bars in the displayed Threshold window, and then It is preferable to set the value displayed below the histogram in the range of 40 to 60%.
　次に、画像処理ソフトウェア（ＩｍａｇｅＪ）を用いて、取得した２値化後の画像の第１相と第２相との境界線（「エッジ部」ともいう。境界線は、第１相と第２相の境界の輪郭線に相当する。）を検索して抽出する（ＩｍａｇｅＪにおける「Ｐｒｏｃｅｓｓ」メニューから「Ｆｉｎｄ　Ｅｄｇｅｓ」メニューを選択）。
　図５は、図４の白黒２値化画像において境界線を抽出した状態を示す模式図である。上記手順により、第１相（「白」で表示された箇所）と第２相（「黒」で表示された箇所）の境界線が抽出される。
　そして、画像処理ソフトウェア（ＩｍａｇｅＪ）を用いて上記境界線の画素数を計測し、得られた画素数を距離（画素数×画素ピッチ（μｍ））に換算することによって、第１相と第２相の境界線の合計長さ（境界総距離Ｌ０）を算出する（ＩｍａｇｅＪにおける「Ａｎａｒｉｚｅ」メニューから「Ｈｉｓｔｇｒａｍ」メニューを選択し、更に「Ｈｉｓｔｇｒａｍ」メニューから「Ｌｉｓｔ」メニューを選択）。 Next, using image processing software (ImageJ), the boundary line (also referred to as the "edge part") between the first phase and the second phase of the acquired binarized image is ) is searched and extracted (select the "Find Edges" menu from the "Process" menu in ImageJ).
FIG. 5 is a schematic diagram showing a state in which boundary lines are extracted from the black-and-white binarized image of FIG. By the above procedure, the boundary line between the first phase (the part displayed in "white") and the second phase (the part displayed in "black") is extracted.
Then, by measuring the number of pixels on the boundary line using image processing software (ImageJ) and converting the obtained number of pixels into distance (number of pixels x pixel pitch (μm)), the first phase and second phase are determined. The total length of phase boundaries (total boundary distance L 0 ) is calculated (select the "Histgram" menu from the "Anarize" menu in ImageJ, and then select the "List" menu from the "Histgram" menu).
　次いで、算出した境界総距離Ｌ０を、トリミングしたＳＥＭ画像の観察面積（６μｍ×１５μｍ）で規格化して、１μｍ×１μｍ当たりの界面総距離Ｌ１（断面Ｔの１×１μｍ２の範囲における第１相と第２相との境界線の合計長さ（境界距離Ｌ１））を求める。 Next, the calculated total boundary distance L 0 is normalized by the observation area (6 μm × 15 μm) of the trimmed SEM image, and the total interface distance L 1 (the distance in the 1 × 1 μm 2 range of cross section T) per 1 μm × 1 μm is calculated. The total length of the boundary line between the first phase and the second phase (boundary distance L 1 ) is determined.
　上記手順によって遮光膜の３箇所の断面に対して各々の境界距離Ｌ１を求め、その平均値を境界距離Ｌとする。 The boundary distance L1 for each of the three cross sections of the light-shielding film is determined by the above procedure, and the average value thereof is defined as the boundary distance L.
　本発明の遮光膜においては、境界距離Ｌは、２．５０～１５．００μｍであり、本発明の効果がより優れ易い点で、２．５０～１０．００μｍが好ましく、２．５０～７．００μｍがより好ましい。境界距離Ｌが２．５０μｍ未満である場合、第１相の領域が大きすぎて（第１相の領域が光の波長よりも大きくなり）、所望の低反射性特性が発現しない。また、境界距離Ｌが１５．００μｍ超である場合、第１相の領域が小さすぎて（つまり、遮光膜の表面の凹凸構造が小さすぎて）、所望の低反射性特性が発現しない。 In the light-shielding film of the present invention, the boundary distance L is 2.50 to 15.00 μm, preferably 2.50 to 10.00 μm, and 2.50 to 7. 00 μm is more preferable. If the boundary distance L is less than 2.50 μm, the first phase region is too large (the first phase region is larger than the wavelength of the light), and the desired low reflectivity characteristics are not expressed. Furthermore, if the boundary distance L is more than 15.00 μm, the first phase region is too small (that is, the uneven structure on the surface of the light-shielding film is too small), and the desired low-reflectivity characteristics are not exhibited.
　また、本発明の遮光膜の表面粗さとしては特に制限されないが、本発明の効果がより優れ易い点で、表面粗さＲａが、２０～３０００Åであるのが好ましく、２００～２０００Åであるのがより好ましく、４００～２０００Åであるのが更に好ましい。
　上記数値は、ＢＲＵＫＥＲ社製ＤｅｋｔａｋＸＴを用い、１μｍ/点の解像度で樹脂膜１ｍｍの距離における表面粗さを測定した値に相当する。 The surface roughness of the light-shielding film of the present invention is not particularly limited, but the surface roughness Ra is preferably 20 to 3000 Å, more preferably 200 to 2000 Å, since the effects of the present invention are more likely to be achieved. is more preferable, and even more preferably 400 to 2000 Å.
The above numerical value corresponds to a value obtained by measuring the surface roughness at a distance of 1 mm of the resin film at a resolution of 1 μm/point using DektakXT manufactured by BRUKER.
　本発明の遮光膜の厚みとしては特に制限されないが、本発明の効果がより優れ易い点で、０．２～１０μｍが好ましく、０．５～３μｍがより好ましい。 The thickness of the light-shielding film of the present invention is not particularly limited, but it is preferably 0.2 to 10 μm, more preferably 0.5 to 3 μm, since the effects of the present invention are more likely to be achieved.
〔遮光膜の各種成分〕
　次に、遮光膜の各種成分について説明する。
＜黒色顔料＞
　遮光膜は黒色顔料を含む。
　本明細書において、黒色顔料は、波長４００～７００ｎｍの全ての範囲にわたって吸収を有する顔料を意味する。
　より具体的には、例えば、以下に説明する評価基準Ｚに適合する黒色顔料が好ましい。
　まず、黒色顔料と、透明な樹脂マトリックス（アクリル樹脂等）と、溶媒とを含有し、全固形分に対する黒色顔料の含有量が６０質量％である組成物を調製する。得られた組成物を、ガラス基板上に、乾燥後の硬化膜の膜厚が１μｍになるように塗布し、硬化膜を形成する。乾燥後の硬化膜の遮光性を、分光光度計（日立株式会社製ＵＶ－３６００等）を用いて評価する。乾燥後の硬化膜の波長４００～７００ｎｍにおける透過率の最大値が１０％未満であれば、上記色材は評価基準Ｚに適合する黒色顔料であると判断できる。黒色顔料は、評価基準Ｚにおいて、乾燥後の硬化膜の波長４００～７００ｎｍにおける透過率の最大値が８％未満であることがより好ましく、５％未満であることが更に好ましい。 [Various components of light shielding film]
Next, various components of the light shielding film will be explained.
<Black pigment>
The light shielding film contains a black pigment.
As used herein, black pigment refers to a pigment that has absorption over the entire wavelength range of 400 to 700 nm.
More specifically, for example, a black pigment that meets evaluation criteria Z described below is preferable.
First, a composition containing a black pigment, a transparent resin matrix (such as an acrylic resin), and a solvent is prepared, in which the content of the black pigment is 60% by mass based on the total solid content. The obtained composition is applied onto a glass substrate so that the thickness of the cured film after drying is 1 μm to form a cured film. The light-shielding properties of the cured film after drying are evaluated using a spectrophotometer (UV-3600, manufactured by Hitachi, Ltd., etc.). If the maximum transmittance of the cured film after drying at a wavelength of 400 to 700 nm is less than 10%, it can be determined that the coloring material is a black pigment that meets evaluation criteria Z. Regarding the black pigment, in evaluation criterion Z, the maximum transmittance of the cured film after drying at a wavelength of 400 to 700 nm is more preferably less than 8%, and even more preferably less than 5%.
　黒色顔料としては、単独では黒色顔料として使用できない顔料を複数組み合わせ、全体として黒色になるように調整して黒色顔料としてもよい。
　例えば、単独では黒色以外の色を有する顔料を複数組み合わせて黒色顔料として使用してもよい。 As the black pigment, a plurality of pigments that cannot be used alone as a black pigment may be combined and adjusted to give a black color as a whole to form a black pigment.
For example, a combination of a plurality of pigments having a color other than black when used alone may be used as a black pigment.
　黒色顔料としては、単独で黒色を発現する顔料が好ましい。また、単独で黒色を発現し、かつ、赤外線を吸収する黒色顔料を使用してもよい。
　ここで、赤外線を吸収する黒色顔料は、赤外領域（好ましくは、波長６５０～１３００ｎｍ）の波長領域に吸収を有する。波長６７５～９００ｎｍの波長領域に極大吸収波長を有する黒色顔料も好ましい。 As the black pigment, a pigment that expresses black color by itself is preferable. Further, a black pigment that alone expresses black color and absorbs infrared rays may be used.
Here, the black pigment that absorbs infrared rays has absorption in the infrared wavelength region (preferably a wavelength of 650 to 1300 nm). A black pigment having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is also preferred.
　黒色顔料としては、各種公知の黒色顔料を使用できる。黒色顔料は、無機顔料であっても有機顔料であってもよい。
　黒色顔料は、本発明の効果がより優れる点で、無機顔料が好ましく、金属窒化物粒子又は金属酸窒化物粒子がより好ましい。 As the black pigment, various known black pigments can be used. The black pigment may be an inorganic pigment or an organic pigment.
The black pigment is preferably an inorganic pigment, and more preferably a metal nitride particle or a metal oxynitride particle, since the effects of the present invention are more excellent.
（無機顔料）
　黒色顔料として使用される無機顔料としては、遮光性を有し、無機化合物を含む粒子であれば、特に制限されないが、公知の無機顔料が使用できる。
　無機顔料としては、例えば、金属酸化物、金属窒化物、及び金属酸窒化物が挙げられ、本発明の効果がより優れる点で、金属窒化物又は金属酸窒化物が好ましい。 (Inorganic pigment)
The inorganic pigment used as the black pigment is not particularly limited as long as it has light blocking properties and contains an inorganic compound, but any known inorganic pigment can be used.
Examples of the inorganic pigment include metal oxides, metal nitrides, and metal oxynitrides, and metal nitrides or metal oxynitrides are preferable because they provide better effects of the present invention.
　無機顔料としては、チタン（Ｔｉ）及びジルコニウム（Ｚｒ）等の第４族の金属元素、バナジウム（Ｖ）及びニオブ（Ｎｂ）等の第５族の金属元素、イットリウム（Ｙ）、アルミニウム（Ａｌ）、コバルト（Ｃｏ）、クロム（Ｃｒ）、銅（Ｃｕ）、マンガン（Ｍｎ）、ルテニウム（Ｒｕ）、鉄（Ｆｅ）、ニッケル（Ｎｉ）、錫（Ｓｎ）、並びに、銀（Ａｇ）からなる群から選択される１種又は２種以上の金属元素を含む、金属酸化物、金属窒化物、及び金属酸窒化物が挙げられる。
　なかでも、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、バナジウム（Ｖ）、イットリウム（Ｙ）、アルミニウム（Ａｌ）、及び鉄（Ｆｅ）からなる群から選択される１種又は２種以上の金属元素を含む、金属酸化物、金属窒化物、又は金属酸窒化物が好ましい。つまり、無機顔料は、２種以上の金属原子を含んでもよい。
　上記金属酸化物、金属窒化物、及び金属酸窒化物としては、更に他の金属原子が混在した粒子を使用してもよい。上記としては、例えば、更に周期表１３～１７族元素から選択される原子（好ましくは酸素原子及び／又は硫黄原子）を含む金属窒化物含有粒子が使用できる。
　また、上記金属酸化物、金属窒化物、及び金属酸窒化物は、無機物及び／又は有機物で被覆されていてもよい。
　上記無機物としては、上記無機顔料に含まれる金属原子が挙げられる。
　上記有機物としては、上記疎水性基を有する有機物が挙げられ、シラン化合物が好ましい。 Inorganic pigments include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), yttrium (Y), and aluminum (Al). , cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag). Examples include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the following.
Among them, one or more metal elements selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V), yttrium (Y), aluminum (Al), and iron (Fe). Metal oxides, metal nitrides, or metal oxynitrides containing metal oxides are preferred. That is, the inorganic pigment may contain two or more types of metal atoms.
As the metal oxide, metal nitride, and metal oxynitride, particles containing other metal atoms may also be used. As the above, for example, metal nitride-containing particles further containing an atom (preferably an oxygen atom and/or a sulfur atom) selected from elements of groups 13 to 17 of the periodic table can be used.
Further, the metal oxide, metal nitride, and metal oxynitride may be coated with an inorganic substance and/or an organic substance.
Examples of the inorganic substance include metal atoms contained in the inorganic pigment.
Examples of the above-mentioned organic substance include the above-mentioned organic substances having a hydrophobic group, and silane compounds are preferable.
　上記の金属窒化物、金属酸化物、又は金属酸窒化物の製造方法としては、所望とする物性を有する黒色顔料が得られるものであれば、特に制限されないが、気相反応法等の公知の製造方法を使用できる。気相反応法としては、電気炉法及び熱プラズマ法等が挙げられるが、不純物の混入が少なく、粒子径が揃いやすく、また、生産性が高い点から、熱プラズマ法が好ましい。
　上記の金属窒化物、金属酸化物、又は金属酸窒化物には、表面修飾処理が施されていてもよい。例えば、シリコーン基とアルキル基とを併せ持つ表面処理剤で表面修飾処理が施されていてもよい。そのような無機粒子としては、「ＫＴＰ－０９」シリーズ（信越化学工業社製）が挙げられる。 The method for producing the above metal nitride, metal oxide, or metal oxynitride is not particularly limited as long as a black pigment having desired physical properties can be obtained, but known methods such as gas phase reaction method can be used. Manufacturing methods can be used. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable because it is less likely to contain impurities, the particle size is easily uniform, and productivity is high.
The above metal nitride, metal oxide, or metal oxynitride may be subjected to a surface modification treatment. For example, the surface may be modified with a surface treatment agent having both a silicone group and an alkyl group. Examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).
　中でも、遮光膜を形成する際のアンダーカットの発生を抑制できる点から、チタン、バナジウム、ジルコニウム、ニオブ及び鉄からなる群から選択される１種以上の金属の窒化物又は酸窒化物がより好ましく、ジルコニウムの窒化物若しくは酸窒化物、又は、チタンの窒化物若しくは酸窒化物（チタンブラック）が更に好ましい。 Among these, nitrides or oxynitrides of one or more metals selected from the group consisting of titanium, vanadium, zirconium, niobium, and iron are more preferred from the standpoint of suppressing the occurrence of undercuts when forming a light-shielding film. , zirconium nitride or oxynitride, or titanium nitride or oxynitride (titanium black).
　チタンブラックは、酸窒化チタンを含む黒色粒子である。
　チタンブラックは、分散性向上、凝集性抑制等の目的で必要に応じ、表面を修飾することが可能である。チタンブラックは、酸化ケイ素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム又は酸化ジルコニウムで被覆することが可能であり、また、特開２００７－３０２８３６号公報に表されるような撥水性物質での処理も可能である。 Titanium black is black particles containing titanium oxynitride.
The surface of titanium black can be modified as necessary for the purpose of improving dispersibility, suppressing agglomeration, and the like. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconium oxide, and can also be coated with a water-repellent material as disclosed in JP-A No. 2007-302836. Processing is also possible.
　チタンブラックの製造方法としては、二酸化チタンと金属チタンの混合体を還元雰囲気で加熱し還元する方法（特開昭４９－０５４３２号公報）、四塩化チタンの高温加水分解で得られた超微細二酸化チタンを、水素を含む還元雰囲気中で還元する方法（特開昭５７－２０５３２２号公報）、二酸化チタン又は水酸化チタンをアンモニア存在下で高温還元する方法（特開昭６０－０６５０６９号公報、特開昭６１－２０１６１０号公報）及び二酸化チタン又は水酸化チタンにバナジウム化合物を付着させ、アンモニア存在下で高温還元する方法（特開昭６１－２０１６１０号公報）が挙げられる。 Methods for producing titanium black include a method in which a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing atmosphere (Japanese Unexamined Patent Publication No. 49-05432), and ultrafine carbon dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method for reducing titanium in a reducing atmosphere containing hydrogen (Japanese Unexamined Patent Publication No. 57-205322), a method for reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Unexamined Patent Publication No. 60-065069, Examples include a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Application Laid-Open No. 61-201610).
　チタンブラックの粒子径は、特に制限されないが、１０～４５ｎｍが好ましく、１２～２０ｎｍがより好ましい。チタンブラックの比表面積は、特に制限されないが、撥水化剤で表面処理した後の撥水性が所定の性能となるために、ＢＥＴ（Ｂｒｕｎａｕｅｒ，Ｅｍｍｅｔｔ，Ｔｅｌｌｅｒ）法にて測定した値が５～１５０ｍ２／ｇであることが好ましく、２０～１００ｍ２／ｇであることがより好ましい。 The particle size of titanium black is not particularly limited, but is preferably 10 to 45 nm, more preferably 12 to 20 nm. The specific surface area of titanium black is not particularly limited, but in order for the water repellency after surface treatment with a water repellent agent to achieve a specified performance, the value measured by the BET (Brunauer, Emmett, Teller) method should be 5 to 5. It is preferably 150 m 2 /g, more preferably 20 to 100 m 2 /g.
　チタンブラックとしては、例えば、チタンブラック１０Ｓ、１２Ｓ、１３Ｒ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ、１３Ｒ－Ｎ、１３Ｍ－Ｔ（商品名、三菱マテリアル株式会社製）、ティラック（Ｔｉｌａｃｋ）Ｄ（商品名、赤穂化成株式会社製）及びＭＴ－１５０Ａ（商品名、テイカ株式会社製）が挙げられる。 Examples of titanium black include Titanium Black 10S, 12S, 13R, 13M, 13MC, 13R, 13R-N, 13M-T (product name, manufactured by Mitsubishi Materials Corporation), Tilac D (product name). , manufactured by Ako Kasei Co., Ltd.) and MT-150A (trade name, manufactured by Teika Co., Ltd.).
　遮光膜は、チタンブラックを、チタンブラック及びＳｉ原子を含む被分散体として含むことも好ましい。この形態において、チタンブラックは、遮光膜中において被分散体として含まれる。被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が質量換算で０．０５～０．５であることが好ましく、０．０７～０．４であることがより好ましい。ここで、上記被分散体は、チタンブラックが一次粒子の状態であるもの、凝集体（二次粒子）の状態であるものの双方を包含する。 It is also preferable that the light shielding film contains titanium black as a dispersed element containing titanium black and Si atoms. In this form, titanium black is included as a dispersed element in the light shielding film. The content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersed body is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, in terms of mass. Here, the above-mentioned object to be dispersed includes both titanium black in the state of primary particles and titanium black in the state of aggregates (secondary particles).
　被分散体のＳｉ／Ｔｉを変更する（例えば０．０５以上とする）ためには、以下のような手段を用いることができる。まず、酸化チタンとシリカ粒子とを分散機を用いて分散することにより分散物を得て、この混合物を高温（例えば、８５０～１０００℃）にて還元処理することにより、チタンブラック粒子を主成分とし、ＳｉとＴｉとを含む被分散体を得ることができる。Ｓｉ／Ｔｉが調整されたチタンブラックは、例えば、特開２００８－２６６０４５公報の段落［０００５］及び［００１６］～［００２１］に記載の方法により作製できる。
　なお、被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）は、例えば、国際公開第２０１１/０４９０９０号公報の段落［００５４］～［００５６］に記載の方法（２－１）又は方法（２－３）を用いて測定できる。 In order to change the Si/Ti ratio of the object to be dispersed (for example, to 0.05 or more), the following means can be used. First, titanium oxide and silica particles are dispersed using a dispersion machine to obtain a dispersion, and this mixture is reduced at a high temperature (for example, 850 to 1000°C) to make titanium black particles as the main component. By doing so, a dispersion containing Si and Ti can be obtained. Titanium black with adjusted Si/Ti can be produced, for example, by the method described in paragraphs [0005] and [0016] to [0021] of JP-A-2008-266045.
The content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersed material can be determined, for example, by the method (2-1) described in paragraphs [0054] to [0056] of International Publication No. 2011/049090. ) or method (2-3).
　チタンブラック及びＳｉ原子を含む被分散体において、チタンブラックは、上記したものを使用できる。また、この被分散体においては、チタンブラックと共に、分散性、着色性等を調整する目的で、Ｃｕ、Ｆｅ、Ｍｎ、Ｖ及びＮｉ等から選択される複数の金属の複合酸化物、酸化コバルト、酸化鉄、カーボンブラック、並びに、アニリンブラック等からなる黒色顔料を、１種又は２種以上を組み合わせて、被分散体として併用してもよい。この場合、全被分散体中の５０質量％以上をチタンブラックからなる被分散体が占めることが好ましい。 In the dispersion material containing titanium black and Si atoms, the titanium black described above can be used. In addition to titanium black, this dispersed material also contains composite oxides of a plurality of metals selected from Cu, Fe, Mn, V, Ni, etc., cobalt oxide, Black pigments such as iron oxide, carbon black, and aniline black may be used alone or in combination as a dispersion object. In this case, it is preferable that the dispersible material made of titanium black accounts for 50% by mass or more of the total dispersible material.
　無機顔料としては、カーボンブラックも挙げられる。
　カーボンブラックとしては、例えば、ファーネスブラック、チャンネルブラック、サーマルブラック、アセチレンブラック及びランプブラックが挙げられる。
　カーボンブラックとしては、オイルファーネス法等の公知の方法で製造されたカーボンブラックを使用してもよく、市販品を使用してもよい。
　カーボンブラックの市販品の具体例としては、Ｃ．Ｉ．ピグメントブラック７等の無機顔料が挙げられる。 Carbon black can also be mentioned as an inorganic pigment.
Examples of carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.
As the carbon black, carbon black manufactured by a known method such as an oil furnace method may be used, or a commercially available product may be used.
Specific examples of commercially available carbon blacks include C. I. Examples include inorganic pigments such as Pigment Black 7.
　カーボンブラックとしては、表面処理がされたカーボンブラックが好ましい。表面処理としては、樹脂による被覆処理、酸性基を導入する表面処理及びシランカップリング剤による表面処理が挙げられる。 As the carbon black, surface-treated carbon black is preferable. Examples of the surface treatment include coating treatment with a resin, surface treatment to introduce an acidic group, and surface treatment with a silane coupling agent.
　カーボンブラックとしては、樹脂による被覆処理がされたカーボンブラックが好ましい。カーボンブラックの粒子表面を絶縁性の樹脂で被覆することにより、遮光膜の遮光性及び絶縁性を向上させることができる。また、リーク電流の低減等により、画像表示装置の信頼性等を向上させることができる。このため、遮光膜を絶縁性が要求される用途に用いる場合等に好適である。
　被覆樹脂としては、エポキシ樹脂、ポリアミド、ポリアミドイミド、ノボラック樹脂、フェノール樹脂、ウレア樹脂、メラミン樹脂、ポリウレタン、ジアリルフタレート樹脂、アルキルベンゼン樹脂、ポリスチレン、ポリカーボネート、ポリブチレンテレフタレート及び変性ポリフェニレンオキサイドが挙げられる。
　被覆樹脂の含有量は、遮光膜の遮光性及び絶縁性がより優れる点から、カーボンブラック及び被覆樹脂の合計に対して、０．１～４０質量％が好ましく、０．５～３０質量％がより好ましい。 As the carbon black, carbon black coated with a resin is preferable. By coating the carbon black particle surface with an insulating resin, the light-shielding properties and insulation properties of the light-shielding film can be improved. Further, by reducing leakage current, etc., reliability of the image display device can be improved. Therefore, it is suitable for applications where the light shielding film is required to have insulation properties.
Examples of the coating resin include epoxy resin, polyamide, polyamideimide, novolak resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkylbenzene resin, polystyrene, polycarbonate, polybutylene terephthalate, and modified polyphenylene oxide.
The content of the coating resin is preferably 0.1 to 40% by mass, and 0.5 to 30% by mass based on the total of carbon black and coating resin, from the viewpoint of better light shielding properties and insulation properties of the light shielding film. More preferred.
　黒色顔料としては、例えば、特開２０１７－２２２５５９号公報、国際公開第２０１９／１３０７７２号、国際公開第２０１９／０５９３５９号及び特開２００９－０９１２０５号公報のジルコニウムが挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the black pigment include zirconium disclosed in JP2017-222559A, WO2019/130772A, WO2019/059359A, and JP2009-091205A, the contents of which are disclosed in this specification. incorporated into the book.
（有機顔料）
　黒色顔料として使用される有機顔料としては、遮光性を有し、有機化合物を含む粒子であれば、特に制限されないが、公知の有機顔料が使用できる。
　本発明において、有機顔料としては、例えば、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物及びアゾ系化合物が挙げられ、ビスベンゾフラノン化合物又はペリレン化合物が好ましい。 (organic pigment)
The organic pigment used as the black pigment is not particularly limited as long as it has light blocking properties and contains an organic compound, but any known organic pigment can be used.
In the present invention, examples of the organic pigment include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds or perylene compounds being preferred.
　ビスベンゾフラノン化合物としては、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３３号公報及び特表２０１２－５１５２３４号公報に記載された化合物が挙げられる。ビスベンゾフラノン化合物は、ＢＡＳＦ社製の「Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ」（商品名）として入手可能である。
　ペリレン化合物としては、特開昭６２－００１７５３号公報及び特公昭６３－０２６７８４号公報に記載された化合物が挙げられる。ペリレン化合物は、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　２１、３０、３１、３２、３３及び３４として入手可能である。 Examples of the bisbenzofuranone compound include compounds described in Japanese Translated Patent Publication No. 2010-534726, Japanese Translated Patent Publication No. 2012-515233, and Japanese Translated Transparent Publication No. 2012-515234. The bisbenzofuranone compound is available as "Irgaphor Black" (trade name) manufactured by BASF.
Examples of perylene compounds include compounds described in JP-A-62-001753 and JP-B-63-026784. The perylene compound is C. I. Pigment Black 21, 30, 31, 32, 33 and 34.
　黒色顔料の含有量は、本発明の効果がより優れる点から、遮光膜の全質量に対して、２０～９０質量％が好ましく、３０～７０質量％がより好ましく、３０～６０質量％が更に好ましい。
　２種以上の黒色顔料を使用する場合、その合計含有量が上記範囲内であるのが好ましい。なお、本発明の遮光膜における「遮光」とは、光を減衰させながら遮光膜を通過させる光減衰をも含む概念である。このような機能を有する光減衰膜としての遮光膜においては、遮光膜中の黒色顔料の含有量は、上記好適範囲より少ないことも好ましい。 The content of the black pigment is preferably 20 to 90% by mass, more preferably 30 to 70% by mass, and still more preferably 30 to 60% by mass, based on the total mass of the light shielding film, in order to achieve better effects of the present invention. preferable.
When using two or more types of black pigments, it is preferable that the total content is within the above range. Note that "light shielding" in the light shielding film of the present invention is a concept that also includes light attenuation in which light is allowed to pass through the light shielding film while being attenuated. In a light-shielding film as a light-attenuating film having such a function, it is also preferable that the content of black pigment in the light-shielding film is less than the above-mentioned preferred range.
＜その他の色材＞
　遮光膜は、黒色顔料以外の色材であるその他の色材を含んでもよい。 <Other coloring materials>
The light-shielding film may contain a coloring material other than the black pigment.
（黒色染料）
　遮光膜は、例えば、黒色染料を含んでもよい。
　黒色染料としては、例えば、単独で黒色を発現する染料が使用でき、例えば、ピラゾールアゾ化合物、ピロメテン化合物、アニリノアゾ化合物、トリフェニルメタン化合物、アントラキノン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、及び、ピロロピラゾールアゾメチン化合物等を使用できる。
　また、黒色染料としては、例えば、特開昭６４－９０４０３号公報、特開昭６４－９１１０２号公報、特開平０１－９４３０１号公報、特開平０６－１１６１４号公報、特許２５９２２０７号公報、米国特許４８０８５０１号明細書、米国特許５６６７９２０号明細書、米国特許５０５９５０号明細書、米国特許５６６７９２０号明細書、特開平０５－３３３２０７号公報、特開平０６－３５１８３号公報、特開平０６－５１１１５号公報、及び、特開平０６－１９４８２８号公報等に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。 (black dye)
The light-shielding film may contain, for example, a black dye.
As the black dye, for example, dyes that express black color by themselves can be used, such as pyrazole azo compounds, pyrromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, Pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. can be used.
In addition, examples of black dyes include, for example, JP-A-64-90403, JP-A-64-91102, JP-A-01-94301, JP-A-06-11614, Japanese Patent No. 2,592,207, and U.S. Pat. 4808501 specification, US Patent No. 5667920, US Patent No. 505950, US Patent No. 5667920, JP 05-333207, JP 06-35183, JP 06-51115, Also, reference can be made to the compounds described in JP-A-06-194828, etc., the contents of which are incorporated herein.
　これらの黒色染料としては、例えば、ソルベントブラック２７～４７のカラーインデックス（Ｃ．Ｉ．）で規定される染料が挙げられ、ソルベントブラック２７、２９又は３４のＣ．Ｉ．で規定される染料が好ましい。
　また、これらの黒色染料の市販品としては、例えば、スピロン　Ｂｌａｃｋ　ＭＨ、Ｂｌａｃｋ　ＢＨ（以上、保土谷化学工業株式会社製）、ＶＡＬＩＦＡＳＴ　Ｂｌａｃｋ　３８０４、３８１０、３８２０、３８３０（以上、オリエント化学工業株式会社製）、Ｓａｖｉｎｙｌ　Ｂｌａｃｋ　ＲＬＳＮ（以上、クラリアント社製）、ＫＡＹＡＳＥＴ　Ｂｌａｃｋ　Ｋ－Ｒ、Ｋ－ＢＬ（以上、日本化薬株式会社製）等の染料が挙げられる。また、分子内に重合性を有する重合性染料を用いてもよく、市販品としては、例えば、和光純薬工業社製ＲＤＷシリーズが挙げられる。 Examples of these black dyes include dyes defined by Color Index (C.I.) of Solvent Black 27 to 47, and C.I. of Solvent Black 27, 29, or 34. I. Dyes defined by are preferred.
Commercially available products of these black dyes include, for example, Spiron Black MH, Black BH (all manufactured by Hodogaya Chemical Industry Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (all manufactured by Orient Chemical Industry Co., Ltd.). ), Savinyl Black RLSN (manufactured by Clariant), KAYASET Black K-R, K-BL (manufactured by Nippon Kayaku Co., Ltd.), and the like. Further, a polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available dyes include the RDW series manufactured by Wako Pure Chemical Industries, Ltd.
　また、黒色染料は色素多量体を用いてもよい。色素多量体としては、例えば、特開２０１１－２１３９２５号公報、及び、特開２０１３－０４１０９７号公報に記載されている化合物が挙げられる。
　更に、上述の通り、単独では黒色以外の色を有する染料を複数組み合わせて黒色染料として使用してもよい。このような着色染料としては、例えば、Ｒ（レッド）、Ｇ（グリーン）、及び、Ｂ（ブルー）等の有彩色系の染料（有彩色染料）の他、特開２０１４－４２３７５の段落００２７～０２００に記載の染料も使用できる。 Moreover, a pigment multimer may be used as the black dye. Examples of the dye multimer include compounds described in JP-A No. 2011-213925 and JP-A No. 2013-041097.
Further, as described above, a combination of a plurality of dyes having a color other than black when used alone may be used as the black dye. Such colored dyes include, for example, chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), as well as paragraphs 0027 to 4 of JP-A No. 2014-42375. Dyes described in 0200 can also be used.
（着色剤）
　遮光膜は、黒色以外の色を有する着色剤を含んでもよい。黒色の色を有する黒色色材（上記黒色顔料を含む）と、１種以上の着色剤との両方を使用して、遮光膜の遮光特性を調整できる。また、例えば、遮光膜を光減衰膜として使用する場合に、広い波長成分を含む光に対して、各波長を均等に減衰しやすい。
　着色剤としては、例えば、黒色色材以外の顔料及び染料が挙げられる。
　着色剤として有彩色着色剤又は白色着色剤を含んでもよい。有彩色着色剤としては、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤、及び、オレンジ色着色剤が挙げられる。有彩色着色剤又は白色着色剤は、顔料であってもよく、染料であってもよい。顔料と染料とを併用してもよい。また、上記顔料は、無機顔料、有機顔料のいずれでもよい。また、上記顔料には、無機顔料又は有機－無機顔料の一部を有機発色団で置換した材料を用いることもできる。無機顔料や有機－無機顔料を有機発色団で置換することで、色相設計をしやすくできる。
　遮光膜が着色剤を含む場合、黒色色材と着色剤との合計含有量は、遮光膜の全質量に対して、１０～９０質量％が好ましく、３０～７０質量％がより好ましく、４０～６０質量％が更に好ましい。
　なお、遮光膜を光減衰膜として使用する場合、黒色色材と着色剤との合計含有量は、上記好適範囲より少ないことも好ましい。
　また、黒色色材の含有量に対する、着色剤の含有量との質量比（着色剤の含有量／黒色色材の含有量）は、０．１～９．０が好ましい。 (colorant)
The light-shielding film may contain a colorant having a color other than black. The light-shielding properties of the light-shielding film can be adjusted by using both a black colorant having a black color (including the black pigment described above) and one or more colorants. Further, for example, when a light shielding film is used as a light attenuation film, it is easy to attenuate each wavelength equally for light including a wide wavelength component.
Examples of the coloring agent include pigments and dyes other than black coloring materials.
A chromatic coloring agent or a white coloring agent may be included as a coloring agent. Examples of chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. The chromatic colorant or white colorant may be a pigment or a dye. Pigments and dyes may be used in combination. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or an organic-inorganic pigment partially substituted with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.
When the light shielding film contains a colorant, the total content of the black colorant and the colorant is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and more preferably 40 to 70% by mass, based on the total mass of the light shielding film. More preferably 60% by mass.
In addition, when using a light shielding film as a light attenuation film, it is also preferable that the total content of a black coloring material and a coloring agent is less than the said suitable range.
Further, the mass ratio of the colorant content to the black colorant content (colorant content/black colorant content) is preferably 0.1 to 9.0.
（赤外線吸収剤）
　遮光膜は、更に、赤外線吸収剤を含んでもよい。
　赤外線吸収剤は、赤外領域（好ましくは、波長６５０～１３００ｎｍ）の波長領域に吸収を有する化合物を意味する。赤外線吸収剤は、波長６７５～９００ｎｍの波長領域に極大吸収波長を有する化合物が好ましい。
　このような分光特性を有する着色剤としては、例えば、ピロロピロール化合物、銅化合物、シアニン化合物、フタロシアニン化合物、イミニウム化合物、チオール錯体系化合物、遷移金属酸化物系化合物、スクアリリウム化合物、ナフタロシアニン化合物、クオタリレン化合物、ジチオール金属錯体系化合物、及び、クロコニウム化合物等が挙げられる。
　フタロシアニン化合物、ナフタロシアニン化合物、イミニウム化合物、シアニン化合物、スクアリリウム化合物、及び、クロコニウム化合物は、特開２０１０－１１１７５０号公報の段落００１０～００８１に開示の化合物を使用してもよく、この内容は本明細書に組み込まれる。シアニン化合物は、例えば、「機能性色素、大河原信／松岡賢／北尾悌次郎／平嶋恒亮・著、講談社サイエンティフィック」を参酌でき、この内容は本明細書に組み込まれる。 (Infrared absorber)
The light shielding film may further contain an infrared absorber.
The infrared absorber refers to a compound having absorption in the infrared wavelength region (preferably a wavelength of 650 to 1300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm.
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, and quatarylene. compounds, dithiol metal complex compounds, croconium compounds, and the like.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, compounds disclosed in paragraphs 0010 to 0081 of JP-A No. 2010-111750 may be used, and the contents thereof are disclosed in this specification. incorporated into the book. Regarding the cyanine compound, for example, "Functional Pigment, Written by Makoto Okawara/Ken Matsuoka/Teijiro Kitao/Tsunesuke Hirashima, Kodansha Scientific" can be referred to, the contents of which are incorporated herein.
　上記分光特性を有する着色剤として、特開平０７－１６４７２９号公報の段落０００４～００１６に開示の化合物及び／又は特開２００２－１４６２５４号公報の段落００２７～００６２に開示の化合物、特開２０１１－１６４５８３号公報の段落００３４～００６７に開示のＣｕ及び／又はＰを含む酸化物の結晶子からなり数平均凝集粒子径が５～２００ｎｍである近赤外線吸収粒子を使用することもできる。 As the coloring agent having the above spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of JP-A No. 07-164729 and/or compounds disclosed in paragraphs 0027 to 0062 of JP-A 2002-146254, JP-A 2011-164583 It is also possible to use near-infrared absorbing particles which are made of oxide crystallites containing Cu and/or P and have a number average aggregate particle size of 5 to 200 nm, as disclosed in paragraphs 0034 to 0067 of the above publication.
　波長６７５～９００ｎｍの波長領域に極大吸収波長を有する化合物は、シアニン化合物、ピロロピロール化合物、スクアリリウム化合物、フタロシアニン化合物、及び、ナフタロシアニン化合物からなる群から選択される少なくとも１種が好ましい。
　また、赤外線吸収剤は、２５℃の水に１質量％以上溶解する化合物が好ましく、２５℃の水に１０質量％以上溶解する化合物がより好ましい。このような化合物を用いることで、耐溶剤性が良化する。
　ピロロピロール化合物は、特開２０１０－２２２５５７号公報の段落００４９～００６２を参酌でき、この内容は本明細書に組み込まれる。シアニン化合物及びスクアリリウム化合物は、国際公開２０１４／０８８０６３号公報の段落００２２～００６３、国際公開２０１４／０３０６２８号公報の段落００５３～０１１８、特開２０１４－５９５５０号公報の段落００２８～００７４、国際公開２０１２／１６９４４７号公報の段落００１３～００９１、特開２０１５－１７６０４６号公報の段落００１９～００３３、特開２０１４－６３１４４号公報の段落００５３～００９９、特開２０１４－５２４３１号公報の段落００８５～０１５０、特開２０１４－４４３０１号公報の段落００７６～０１２４、特開２０１２－８５３２号公報の段落００４５～００７８、特開２０１５－１７２１０２号公報の段落００２７～００６７、特開２０１５－１７２００４号公報の段落００２９～００６７、特開２０１５－４０８９５号公報の段落００２９～００８５、特開２０１４－１２６６４２号公報の段落００２２～００３６、特開２０１４－１４８５６７号公報の段落００１１～００１７、特開２０１５－１５７８９３号公報の段落００１０～００２５、特開２０１４－０９５００７号公報の段落００１３～００２６、特開２０１４－８０４８７号公報の段落００１３～００４７、及び、特開２０１３－２２７４０３号公報の段落０００７～００２８等を参酌でき、この内容は本明細書に組み込まれる。 The compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
Further, the infrared absorber is preferably a compound that dissolves in water at 25°C in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25°C in an amount of 10% by mass or more. By using such a compound, solvent resistance is improved.
Regarding the pyrrolopyrrole compound, paragraphs 0049 to 0062 of JP-A No. 2010-222557 can be referred to, the contents of which are incorporated herein. Cyanine compounds and squarylium compounds are described in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of JP2014-59550, and International Publication 2012/ Paragraphs 0013 to 0091 of JP 2015-176046, Paragraphs 0053 to 0099 of JP 2014-63144, Paragraphs 0085 to 0150 of JP 2014-52431, JP Paragraphs 0076 to 0124 of JP 2014-44301, Paragraphs 0045 to 0078 of JP 2012-8532, Paragraphs 0027 to 0067 of JP 2015-172102, Paragraphs 0029 to 0067 of JP 2015-172004, Paragraphs 0029 to 0085 of JP2015-40895, Paragraphs 0022 to 0036 of JP2014-126642, Paragraphs 0011 to 0017 of JP2014-148567, Paragraphs 0010 to 0010 of JP2015-157893 0025, paragraphs 0013 to 0026 of JP2014-095007, paragraphs 0013 to 0047 of JP2014-80487, and paragraphs 0007 to 0028 of JP2013-227403, etc. Incorporated herein.
＜樹脂＞
　遮光膜は、樹脂を含んでいてもよい。
　樹脂としては、例えば、後述する第１樹脂及び第２樹脂が挙げられる。なお、第１樹脂と第２樹脂とは異なる種類の樹脂である。
　遮光膜中、第１樹脂の含有量としては、遮光膜の全質量に対して、２～４０質量％が好ましく、５～３０質量％がより好ましく、１０～２５質量％が更に好ましい。
　また、遮光膜中、第２樹脂の含有量としては、遮光膜の全質量に対して、１～４０質量％が好ましく、２～３０質量％がより好ましく、５～２５質量％が更に好ましい。
　また、遮光膜中、第１樹脂と第２樹脂の含有量比（第１樹脂／第２樹脂）としては、０．３～０．８が好ましく、０．３～０．６がより好ましい。 <Resin>
The light shielding film may contain resin.
Examples of the resin include a first resin and a second resin described below. Note that the first resin and the second resin are different types of resin.
The content of the first resin in 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, based on the total mass of the light shielding film.
Further, the content of the second resin in 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, based on the total mass of the light shielding film.
Further, the content ratio of the first resin and the second resin (first resin/second resin) in the light shielding film is preferably 0.3 to 0.8, more preferably 0.3 to 0.6.
　遮光膜中、樹脂は、第１相及び第２相のいずれの相にも含まれているのが好ましく、第１相が後述する第１樹脂を含むのが好ましく、第２相が後述する第２樹脂を含むのが好ましい。以下において、第１樹脂と第２樹脂について各々説明する。 In the light-shielding film, the resin is preferably contained in both the first phase and the second phase, the first phase preferably containing the first resin described below, and the second phase containing the resin described later. It is preferable to include two resins. Below, the first resin and the second resin will be explained respectively.
（第１樹脂）
　第１樹脂の種類としては特に制限されず、例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、及びナフタレンスルホン酸ホルマリン縮合物等のいわゆる分散剤として汎用される樹脂；ポリオキシエチレンアルキルリン酸エステル；ポリオキシエチレンアルキルアミン；顔料誘導体等が挙げられる。 (First resin)
The type of the first resin is not particularly limited and includes, for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly(meth)acrylate, (meth) Examples include resins commonly used as dispersants such as acrylic copolymers and naphthalene sulfonic acid formalin condensates; polyoxyethylene alkyl phosphates; polyoxyethylene alkyl amines; pigment derivatives, and the like.
　後段部の遮光膜の製造手順の説明において示す通り、第１樹脂は、典型的には、遮光膜形成用組成物に導入される、黒色顔料を分散させた分散組成物中の分散剤そのものであるか又は上記分散剤由来の樹脂（重合性基を有する分散剤が重合してなる樹脂）が該当する。
　第１樹脂は、後述する分散剤が含んでいてもよいグラフト鎖を含む構造単位を含んでいてもよい。第１樹脂がグラフト鎖を含む構造単位（特に、後述する式（１）～（４）で表される構造単位）を含む場合、グラフト鎖を含む構造単位の含有量は、第１樹脂全質量に対して、２～９０質量％が好ましく、５～３０質量％がより好ましい。
　第１樹脂は、後述する分散剤が含んでいてもよい疎水性構造単位を含んでいてもよい。第１樹脂が疎水性構造単位を含む場合、疎水性構造単位の含有量は、第１樹脂全質量に対して、１０～９０質量％が好ましく、２０～８０質量％がより好ましい。
　第1樹脂は、後述する分散剤が含んでいてもよい顔料等と相互作用を形成し得る官能基を含む構造単位を含んでいてもよい。第１樹脂が顔料等と相互作用を形成し得る官能基を含む構造単位を含む場合、顔料等と相互作用を形成し得る官能基を含む構造単位の含有量は、第１樹脂全質量に対して、０．０５～９０質量％が好ましく、１．０～８０質量％がより好ましく、１０～７０質量％が更に好ましい。
　第１樹脂は、１種のみであってもよいし、２種以上であってもよい。 As shown in the explanation of the manufacturing procedure of the light-shielding film in the latter part, the first resin is typically the dispersant itself in the dispersion composition in which the black pigment is dispersed, which is introduced into the composition for forming the light-shielding film. Resins derived from the above-mentioned dispersants (resins obtained by polymerizing dispersants having polymerizable groups) fall under this category.
The first resin may include a structural unit containing a graft chain, which may also be included in a dispersant described below. When the first resin contains a structural unit containing a graft chain (particularly a structural unit represented by formulas (1) to (4) described below), the content of the structural unit containing a graft chain is the total mass of the first resin. It is preferably 2 to 90% by mass, more preferably 5 to 30% by mass.
The first resin may include a hydrophobic structural unit that may also be included in the dispersant described below. When the first resin contains a hydrophobic structural unit, the content of the hydrophobic structural unit is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the first resin.
The first resin may include a structural unit containing a functional group capable of forming an interaction with a pigment or the like that may be included in a dispersant described below. When the first resin includes a structural unit containing a functional group capable of forming an interaction with a pigment, etc., the content of the structural unit containing a functional group capable of forming an interaction with a pigment, etc. is determined based on the total mass of the first resin. The amount is preferably 0.05 to 90% by weight, more preferably 1.0 to 80% by weight, and even more preferably 10 to 70% by weight.
Only one type of first resin may be used, or two or more types may be used.
　第１樹脂の酸価としては、１０～２００ｍｇＫＯＨ／ｇが好ましく、２０～１５０ｍｇＫＯＨ／ｇがより好ましく、４０～１００ｍｇＫＯＨ／ｇが更に好ましく、４０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ未満が特に好ましい。
　なお、本明細書において、「酸価」は、例えば、化合物中における酸基の平均含有量から算出できる。また、樹脂の構成成分である酸基を含む構造単位の含有量を変化させれば所望の酸価を有する樹脂が得られる。
　第１樹脂の重量平均分子量としては、５，０００～１００，０００が好ましく、６，０００～８０，０００がより好ましく、１５，０００～４０，０００であるのが更に好ましく、２０，０００～４０，０００であるのが特に好ましく、２５，０００～４０，０００であるのが最も好ましい。
　第１樹脂のガラス転移温度としては、－２０～１００℃が好ましく、－２０～８０℃がより好ましく、－１０～６０℃が更に好ましい。
　ガラス転移温度は、ＤＳＣ　３５００　Ｓｉｒｉｕｓ（Ｎｅｔｚｓｃｈ社製）により測定できる。 The acid value of the first resin is preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, even more preferably 40 to 100 mgKOH/g, and particularly preferably 40 to 60 mgKOH/g.
In addition, in this specification, "acid value" can be calculated from the average content of acid groups in a compound, for example. Further, by changing the content of structural units containing acid groups, which are constituent components of the resin, a resin having a 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, even more preferably 15,000 to 40,000, and even more preferably 20,000 to 40. ,000 is particularly preferred, and 25,000 to 40,000 is most preferred.
The glass transition temperature of the first resin is preferably -20 to 100°C, more preferably -20 to 80°C, even more preferably -10 to 60°C.
The glass transition temperature can be measured using DSC 3500 Sirius (manufactured by Netzsch).
（第２樹脂）
　第２樹脂の種類としては特に制限されず、アルカリ可溶性樹脂が挙げられる。アルカリ可溶性樹脂は、典型的に、酸基を有する樹脂である。酸基としては、カルボキシル基、リン酸基、スルホ基及びフェノール性ヒドロキシ基等が挙げられる。
　第２樹脂が有する酸基は、１種のみであってもよいし、２種以上であってもよい。
　第２樹脂は、酸基を側鎖に有する繰り返し単位を含むのが好ましい。
　酸基を側鎖に有する繰り返し単位としては、例えば、後段にて示す遮光膜形成用組成物が含み得るアルカリ可溶性樹脂が有し得る、後述の式（２ＲＢ）で表される繰り返し単位が挙げられる。
　第２樹脂が酸基を側鎖に有する繰り返し単位を含む場合、その含有量としては、樹脂の全繰り返し単位に対して、１～４０質量％が好ましく、１～３０質量％がより好ましく、５～３０質量％が更に好ましい。 (Second resin)
The type of the second resin is not particularly limited, and examples include alkali-soluble resins. Alkali-soluble resins are typically resins that have acid groups. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups.
The second resin may have only one type of acid group, or may have two or more types of acid groups.
It is preferable that the second resin contains a repeating unit having an acid group in a side chain.
Examples of the repeating unit having an acid group in its side chain include a repeating unit represented by the below-mentioned formula (2RB) that may be included in the alkali-soluble resin that may be included in the composition for forming a light-shielding film shown below. .
When the second resin contains a repeating unit having an acid group in its side chain, the content thereof is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, based on the total repeating units of the resin. More preferably 30% by mass.
　また、第２樹脂は、ＣｌｏｇＰ値が１．０以上の化合物に由来する繰り返し単位を含んでいるのも好ましい。ＣｌｏｇＰ値が１．０以上の化合物に由来する繰り返し単位としては、（メタ）アクリレートに由来する繰り返し単位から選ばれるのが好ましい。なお、ＣｌｏｇＰ値の定義については後段部にて説明する。
　（メタ）アクリレートに由来する繰り返し単位としては、例えば、後段にて示す遮光膜形成用組成物が含み得るアルカリ可溶性樹脂が有し得る、後述の式（２ＲＡ）で表される繰り返し単位が挙げられる。また、（メタ）アクリレートに由来する繰り返し単位は、置換基として水酸基を有しているのも好ましい。
　第２樹脂が（メタ）アクリレートに由来する繰り返し単位を含む場合、その含有量としては、樹脂の全繰り返し単位に対して、３０質量％以上が好ましく、６０質量％以上がより好ましく、７０質量％以上が更に好ましく、８０質量％以上が特に好ましい。なお、上限値としては、例えば、９９質量％以下が好ましく、９５質量％以下がより好ましい。 Moreover, it is also preferable that the second resin contains a repeating unit derived from a compound having a ClogP value of 1.0 or more. The repeating unit derived from a compound having a ClogP value of 1.0 or more is preferably selected from repeating units derived from (meth)acrylate. Note that the definition of the ClogP value will be explained in the latter part.
Examples of the repeating unit derived from (meth)acrylate include a repeating unit represented by the below-mentioned formula (2RA) that may be included in the alkali-soluble resin that may be included in the composition for forming a light-shielding film shown below. . Moreover, it is also 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, the content thereof is preferably 30% by mass or more, more preferably 60% by mass or more, and 70% by mass based on the total repeating units of the resin. The above is more preferable, and 80% by mass or more is particularly preferable. In addition, as an upper limit, 99 mass % or less is preferable, and 95 mass % or less is more preferable, for example.
　第２樹脂の一態様としては、酸基を側鎖に有する繰り返し単位と、（メタ）アクリレートに由来する繰り返し単位と、を含み、（メタ）アクリレートに由来する繰り返し単位が樹脂の全繰り返し単位に対して６０質量％以上である樹脂が挙げられる。 One embodiment of the second resin includes a repeating unit having an acid group in a side chain and a repeating unit derived from (meth)acrylate, and the repeating unit derived from (meth)acrylate accounts for all repeating units of the resin. Examples include resins in which the amount is 60% by mass or more.
　後段部の遮光膜の製造手順の説明において示す通り、第２樹脂は、典型的には、遮光膜形成用組成物にバインダー成分として導入されるアルカリ可溶性樹脂そのものであるか又は上記アルカリ可溶性樹脂由来の樹脂が該当する。
　第２樹脂は、１種のみであってもよいし、２種以上であってもよい。 As shown in the explanation of the manufacturing procedure of the light-shielding film in the latter part, the second resin is typically the alkali-soluble resin itself that is introduced as a binder component into the composition for forming the light-shielding film, or is derived from the alkali-soluble resin mentioned above. This applies to the following resins.
The number of second resins may be one, or two or more.
　第２樹脂の酸価としては、０～１５０ｍｇＫＯＨ／ｇが好ましく、２０～１００ｍｇＫＯＨ／ｇがより好ましく、４０～９０ｍｇＫＯＨ／ｇが更に好ましく、６０～９０ｍｇＫＯＨ／ｇが最も好ましい。
　第２樹脂の重量平均分子量としては、５，０００～１００，０００が好ましく、８，０００～８０，０００がより好ましく、１５，０００～４０，０００が更に好ましく、１８，０００～２５，０００が特に好ましい。
　第２樹脂のガラス転移温度としては、－２０～１２０℃が好ましく、－２０～１１０℃が好ましく、－５～８０℃がより好ましく、０～７０℃が更に好ましい。
　ガラス転移温度は、ＤＳＣ　３５００　Ｓｉｒｉｕｓ（Ｎｅｔｚｓｃｈ社製）により測定できる。 The acid value of the second resin is preferably 0 to 150 mgKOH/g, more preferably 20 to 100 mgKOH/g, even more preferably 40 to 90 mgKOH/g, and most preferably 60 to 90 mgKOH/g.
The weight average molecular weight of the second resin is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, even more preferably 15,000 to 40,000, and even more preferably 18,000 to 25,000. Particularly preferred.
The glass transition temperature of the second resin is preferably -20 to 120°C, preferably -20 to 110°C, more preferably -5 to 80°C, and even more preferably 0 to 70°C.
The glass transition temperature can be measured using DSC 3500 Sirius (manufactured by Netzsch).
＜その他の任意成分＞
　遮光膜は、上述した成分以外のその他の任意成分を更に含有してもよい。
　例えば、黒色顔料以外の色材（顔料でも染料でもよい）、紫外線吸収剤、界面活性剤、可塑剤、基板表面への密着促進剤、及びその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、酸化防止剤、香料、表面張力調整剤及び連鎖移動剤等）等の公知の添加剤を必要に応じて含んでいてもよい。 <Other optional ingredients>
The light-shielding film may further contain other optional components other than the above-mentioned components.
For example, colorants other than black pigments (pigments or dyes may be used), ultraviolet absorbers, surfactants, plasticizers, adhesion promoters to the substrate surface, and other auxiliary agents (e.g., conductive particles, fillers, , antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be included as necessary.
［遮光膜の製造方法］
　本発明の遮光膜を製造方法する方法は特に制限されないが、黒色顔料を含む遮光膜形成用組成物を用いる方法が挙げられる。より具体的には、黒色顔料を含む遮光膜形成用組成物を支持体上に塗布して組成物層を形成する組成物層形成工程と、組成物層を露光する露光工程とを含む態様が好ましい。また、所定のパターン形状を有する遮光膜を製造する場合には、上述の組成物層形成工程を実施した後、組成物層を所定のマスクを介してパターン露光する露光工程と、露光後の組成物層を現像して遮光膜を形成する現像工程と、を更に含む態様がより好ましい。なお、現像処理は溶剤現像及びアルカリ現像のいずれでもよいが、アルカリ現像の方が好ましい。
　以下、遮光膜形成用組成物について説明する。 [Method for manufacturing light shielding film]
The method for manufacturing the light-shielding film of the present invention is not particularly limited, but examples include a method using a composition for forming a light-shielding film containing a black pigment. More specifically, an embodiment 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. preferable. In addition, when manufacturing a light-shielding film having a predetermined pattern shape, after implementing the above-mentioned composition layer forming step, an exposure step of exposing the composition layer to pattern light through a predetermined mask, and a composition layer after exposure are performed. More preferably, the method further includes a developing step of developing the material layer to form a light-shielding film. Note that the development treatment may be either solvent development or alkali development, but alkali development is preferable.
The composition for forming a light-shielding film will be explained below.
〔遮光膜形成用組成物〕
　遮光膜形成用組物（以下「組成物」ともいう。）は、黒色顔料、樹脂、及び重合性化合物を含むのが好ましい。
　以下、各成分について説明する。 [Composition for forming light-shielding film]
The composition for forming a light-shielding film (hereinafter also referred to as "composition") preferably contains a black pigment, a resin, and a polymerizable compound.
Each component will be explained below.
＜黒色顔料＞
　遮光膜形成用組成物は、黒色顔料を含む。
　黒色顔料としては、遮光膜が含む黒色顔料と同様のものが挙げられる。
　黒色顔料の含有量は、本発明の効果がより優れる点から、遮光膜の全固形分に対して、２０～９０質量％が好ましく、３０～７０質量％がより好ましく、３０～６０質量％が更に好ましい。
　２種以上の黒色顔料を使用する場合、その合計含有量が上記範囲内であるのが好ましい。なお、光減衰膜としての遮光膜においては、遮光膜中の黒色顔料の含有量は、上記好適範囲より少ないことも好ましい。 <Black pigment>
The composition for forming a light-shielding film contains a black pigment.
Examples of the black pigment include those similar to the black pigment contained in the light-shielding film.
The content of the black pigment is preferably 20 to 90% by mass, more preferably 30 to 70% by mass, and 30 to 60% by mass, based on the total solid content of the light shielding film, in order to obtain better effects of the present invention. More preferred.
When using two or more types of black pigments, it is preferable that the total content is within the above range. In addition, in the light-shielding film as a light-attenuating film, it is also preferable that the content of the black pigment in the light-shielding film is less than the above-mentioned preferred range.
＜重合性化合物＞
　組成物は、重合性化合物を含むのが好ましい。
　本明細書中において「重合性化合物」とは、後述する重合開始剤等の作用を受けて重合可能な有機化合物（例えば、エチレン性不飽和基を含む有機化合物）を意味する。
　組成物が溶媒を含む場合、重合性化合物は溶媒に溶解して存在するのが好ましい。 <Polymerizable compound>
Preferably, the composition includes a polymerizable compound.
As used herein, the term "polymerizable compound" refers to an organic compound (for example, an organic compound containing an ethylenically unsaturated group) that can be polymerized under the action of a polymerization initiator or the like described below.
When the composition contains a solvent, the polymerizable compound is preferably present dissolved in the solvent.
　重合性化合物は、低分子の重合性化合物であり、後述の樹脂とは別の成分である。
　組成物中における重合性化合物の含有量は、組成物の全固形分に対して、５～６０質量％が好ましく、７～３０質量％が好ましく、１０～３０質量％がより好ましい。
　組成物は重合性化合物を１種のみ含んでいてもよく、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
　重合性化合物の分子量（分子量分布を有する場合は重量平均分子量）は、特に制限されないが、２５００以下が好ましい。下限は、１００以上が好ましい。 The polymerizable compound is a low-molecular polymerizable compound, and is a separate component from the resin described below.
The content of the polymerizable compound in the composition is preferably 5 to 60% by mass, preferably 7 to 30% by mass, and more preferably 10 to 30% by mass, based on the total solid content of the composition.
The composition may contain only one kind of polymerizable compound, or may contain two or more kinds. When two or more types are included, it is preferable that their total amount falls within the above range.
The molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound is not particularly limited, but is preferably 2,500 or less. The lower limit is preferably 100 or more.
　重合性化合物は、エチレン性不飽和基（エチレン性不飽和結合を含む基）を含む化合物が好ましい。
　つまり、組成物は、エチレン性不飽和基を含む低分子化合物を、重合性化合物として含むのが好ましい。
　重合性化合物としては、エチレン性不飽和結合を１個以上含む化合物が好ましく、２個以上含む化合物がより好ましく、３個以上含む化合物が更に好ましく、４個以上含む化合物が特に好ましい。上限は、例えば、１５個以下である。エチレン性不飽和基としては、例えば、ビニル基、（メタ）アリル基及び（メタ）アクリロイル基が挙げられる。 The polymerizable compound is preferably a compound containing an ethylenically unsaturated group (a group containing an ethylenically unsaturated bond).
That is, the composition preferably contains a low molecular weight compound containing an ethylenically unsaturated group as a polymerizable compound.
The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more, still more preferably a compound containing three or more, and particularly preferably a compound containing four or more. The upper limit is, for example, 15 or less. Examples of the ethylenically unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.
　重合性化合物としては、例えば、特開２００８－２６０９２７号公報の段落［００５０］及び特開２０１５－０６８８９３号公報の段落［００４０］に記載されている化合物を援用でき、これらの内容は本明細書に組み込まれる。 As the polymerizable compound, for example, the compounds described in paragraph [0050] of JP-A No. 2008-260927 and paragraph [0040] of JP-A No. 2015-068893 can be cited, and the contents thereof are incorporated herein by reference. be incorporated into.
　重合性化合物は、例えば、モノマー、プレポリマー、オリゴマー及びこれらの混合物、並びに、これらの多量体等の化学的形態のいずれであってもよい。
　重合性化合物は、３～１５官能の（メタ）アクリレート化合物が好ましく、３～６官能の（メタ）アクリレート化合物がより好ましい。 The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a multimer thereof.
The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
　重合性化合物は、エチレン性不飽和基を１個以上含む、常圧下で１００℃以上の沸点を持つ化合物も好ましい。例えば、特開２０１３－０２９７６０号公報の段落［０２２７］及び特開２００８－２９２９７０号公報の段落［０２５４］～［０２５７］に記載の化合物を援用でき、これらの内容は本明細書に組み込まれる。 The polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher under normal pressure. For example, the compounds described in paragraph [0227] of JP-A No. 2013-029760 and paragraphs [0254] to [0257] of JP-A No. 2008-292970 can be cited, and the contents thereof are incorporated herein.
　重合性化合物は、ジペンタエリスリトールトリアクリレート（市販品としては、例えば、ＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬株式会社製）、ジペンタエリスリトールテトラアクリレート（市販品としては、例えば、ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬株式会社製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては、例えば、ＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬株式会社製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては、例えば、ＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬株式会社製、Ａ－ＤＰＨ－１２Ｅ；新中村化学株式会社製）及びこれらの（メタ）アクリロイル基がエチレングリコール残基又はプロピレングリコール残基を介している構造（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）が好ましい。これらのオリゴマータイプも使用できる。また、ＮＫエステルＡ－ＴＭＭＴ（ペンタエリスリトールテトラアクリレート、新中村化学株式会社製）、ＫＡＹＡＲＡＤ　ＲＰ－１０４０、ＫＡＹＡＲＡＤ　ＤＰＥＡ－１２ＬＴ、ＫＡＹＡＲＡＤ　ＤＰＨＡ　ＬＴ、ＫＡＹＡＲＡＤ　ＲＰ－３０６０及びＫＡＹＡＲＡＤ　ＤＰＥＡ－１２（いずれも商品名、日本化薬株式会社製）を使用してもよい。また、重合性化合物は、化合物中に（メタ）アクリロイル基とウレタン結合との両方を有する、ウレタン（メタ）アクリレート系化合物を使用してもよく、例えば、ＫＡＹＡＲＡＤ　ＤＰＨＡ－４０Ｈ（商品名、日本化薬株式会社製）を使用してもよい。
　以下に好ましい重合性化合物の態様を示す。 The polymerizable compounds include dipentaerythritol triacrylate (as a commercially available product, for example, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (as a commercially available product, for example, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). (manufactured by Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, for example, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product, For example, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin Nakamura Chemical Co., Ltd.) and structures in which these (meth)acryloyl groups are interposed via ethylene glycol residues or propylene glycol residues (for example, SR454, SR499) commercially available from Sartomer, Inc. are preferred. These oligomeric types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060 and KAYARAD DPEA-12 (all product names, (manufactured by Nippon Kayaku Co., Ltd.) may also be used. Further, as the polymerizable compound, a urethane (meth)acrylate compound having both a (meth)acryloyl group and a urethane bond may be used. For example, KAYARAD DPHA-40H (trade name, Nippon Chemical Co., Ltd. (manufactured by Yakuhin Co., Ltd.) may also be used.
Preferred embodiments of the polymerizable compound are shown below.
　重合性化合物は、カルボン酸基、スルホン酸基及びリン酸基等の酸基を有していてもよい。酸基を含む重合性化合物は、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応の水酸基に非芳香族カルボン酸無水物を反応させて酸基を持たせた重合性化合物がより好ましく、このエステルにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトール及び／又はジペンタエリスリトールである化合物が更に好ましい。市販品としては、例えば、東亞合成社製の、アロニックスＴＯ－２３４９、Ｍ－３０５、Ｍ－５１０及びＭ－５２０が挙げられる。 The polymerizable compound may have acid groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups. The polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. It is more preferable to use a polymerizable compound in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Commercially available products include, for example, Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei.
　酸基を含む重合性化合物の酸価は、０．１～４０ｍｇＫＯＨ／ｇが好ましく、５～３０ｍｇＫＯＨ／ｇがより好ましい。重合性化合物の酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像溶解特性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造及び／又は取扱い上、有利である。更には、光重合性能が良好で、硬化性に優れる。 The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, development and dissolution characteristics are good, and if it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, it has good photopolymerization performance and excellent curability.
　重合性化合物は、カプロラクトン構造を含む化合物も好ましい態様である。
　カプロラクトン構造を含む化合物としては、例えば、分子内にカプロラクトン構造を含む限り特に制限されないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール及びトリメチロールメラミン等の多価アルコールと、（メタ）アクリル酸及びε－カプロラクトンとをエステル化して得られる、ε－カプロラクトン変性多官能（メタ）アクリレートが挙げられる。中でも、下記式（Ｚ－１）で表されるカプロラクトン構造を含む化合物が好ましい。 A preferred embodiment of the polymerizable compound is a compound containing a caprolactone structure.
Compounds containing a caprolactone structure are not particularly limited as long as they contain a caprolactone structure in the molecule, but examples include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Examples include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerin, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among these, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferred.
　式（Ｚ－１）中、６個のＲは全てが下記式（Ｚ－２）で表される基であるか又は６個のＲのうち１～５個が下記式（Ｚ－２）で表される基であり、残余が下記式（Ｚ－３）で表される基である。 In formula (Z-1), all 6 R's are groups represented by the following formula (Z-2), or 1 to 5 of the 6 R's are represented by the following formula (Z-2). The remainder is a group represented by the following formula (Z-3).
　式（Ｚ－２）中、Ｒ１は水素原子又はメチル基を表し、ｍは１又は２の数を表し、＊は結合位置を表す。 In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and * represents a bonding position.
　式（Ｚ－３）中、Ｒ１は水素原子又はメチル基を表し、「＊」は結合位置を表す。 In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bonding position.
　カプロラクトン構造を含む重合性化合物は、例えば、日本化薬からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０（上記式（Ｚ－１）～（Ｚ－３）においてｍ＝１、式（Ｚ－２）で表される基の数＝２、Ｒ１が全て水素原子である化合物）、ＤＰＣＡ－３０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝３、Ｒ１が全て水素原子である化合物）、ＤＰＣＡ－６０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝６、Ｒ１が全て水素原子である化合物）及びＤＰＣＡ－１２０（同式においてｍ＝２、式（Ｚ－２）で表される基の数＝６、Ｒ１が全て水素原子である化合物）が挙げられる。また、カプロラクトン構造を含む重合性化合物の市販品としては、例えば、東亞合成株式会社製Ｍ－３５０（商品名）（トリメチロールプロパントリアクリレート）も挙げられる。 A polymerizable compound containing a caprolactone structure is, for example, commercially available from Nippon Kayaku as the KAYARAD DPCA series, and DPCA-20 (m=1 in the above formulas (Z-1) to (Z-3), formula (Z- 2), the number of groups represented by formula (Z-2) = 2, a compound in which all R 1 are hydrogen atoms), DPCA-30 (same formula, m = 1, number of groups represented by formula (Z-2) = 3, Compounds in which all R 1 are hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, compounds in which all R 1 are hydrogen atoms), and DPCA -120 (a compound in which m = 2, the number of groups represented by formula (Z-2) = 6, and all R 1 are hydrogen atoms). Further, as a commercially available product of a polymerizable compound containing a caprolactone structure, for example, M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd. may be mentioned.
　重合性化合物は、下記式（Ｚ－４）又は式（Ｚ－５）で表される化合物も使用できる。 As the polymerizable compound, a compound represented by the following formula (Z-4) or formula (Z-5) can also be used.
　式（Ｚ－４）及び式（Ｚ－５）中、Ｅは、－（（ＣＨ２）ｙＣＨ２Ｏ）－又は－（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－を表し、ｙは、０～１０の整数を表し、Ｘは、（メタ）アクリロイル基、水素原子又はカルボン酸基を表す。
　式（Ｚ－４）中、（メタ）アクリロイル基の合計は３個又は４個であり、ｍは０～１０の整数を表し、各ｍの合計は０～４０の整数である。
　式（Ｚ－５）中、（メタ）アクリロイル基の合計は５個又は６個であり、ｎは０～１０の整数を表し、各ｎの合計は０～６０の整数である。 In formula (Z-4) and formula (Z-5), E represents -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)-, and y represents an integer from 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom, or a 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 sum of each m is an integer of 0 to 40.
In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
　式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。
　また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が更に好ましい。
　式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。
　また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が更に好ましい。
　また、式（Ｚ－４）又は式（Ｚ－５）中の－（（ＣＨ２）ｙＣＨ２Ｏ）－又は－（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。 In formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
In formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
Further, the sum of each 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.
In addition, -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- in formula (Z-4) or formula (Z-5) is on the oxygen atom side. A form in which the terminal of is bonded to X is preferable.
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物は１種単独で用いてもよいし、２種以上併用してもよい。特に、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である形態、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である化合物と、６個のＸのうち、少なくとも１個が水素原子ある化合物との混合物である態様が好ましい。このような構成として、現像性をより向上できる。 The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in formula (Z-5), all six X are acryloyl groups, in formula (Z-5), all six X are acryloyl groups, and among the six X, A preferred embodiment is a mixture with a compound having at least one hydrogen atom. With such a configuration, the developability can be further improved.
　また、式（Ｚ－４）又は式（Ｚ－５）で表される化合物の重合性化合物中における全含有量は、２０質量％以上が好ましく、５０質量％以上がより好ましい。
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物の中でも、ペンタエリスリトール誘導体及び／又はジペンタエリスリトール誘導体がより好ましい。 Further, the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more.
Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.
　また、重合性化合物は、カルド骨格を含んでいてもよい。
　カルド骨格を含む重合性化合物は、９，９－ビスアリールフルオレン骨格を含む重合性化合物が好ましい。
　カルド骨格を含む重合性化合物としては、例えば、オンコートＥＸシリーズ（長瀬産業社製）及びオグソール（大阪ガスケミカル社製）が挙げられる。
　重合性化合物は、イソシアヌル酸骨格を中心核として含む化合物も好ましい。このような重合性化合物としては、例えば、ＮＫエステルＡ－９３００（新中村化学株式会社製）が挙げられる。
　重合性化合物のエチレン性不飽和基の含有量（重合性化合物中のエチレン性不飽和基の数を、重合性化合物の分子量（ｇ／ｍｏｌ）で除した値を意味する）は５．０ｍｍｏｌ／ｇ以上が好ましい。上限は、２０．０ｍｍｏｌ／ｇ以下が好ましい。 Moreover, the polymerizable compound may contain a cardo skeleton.
The polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton.
Examples of the polymerizable compound containing a cardo skeleton include Oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogusol (manufactured by Osaka Gas Chemical Co., Ltd.).
The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. An example of such a polymerizable compound is NK Ester A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.).
The content of ethylenically unsaturated groups in the polymerizable compound (meaning 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 5.0 mmol/ g or more is preferable. The upper limit is preferably 20.0 mmol/g or less.
＜樹脂＞
　組成物は樹脂を含む。
　樹脂としては、例えば、分散剤及びアルカリ可溶性樹脂等が挙げられる。
　本発明の遮光膜は、分散剤とアルカリ可溶性樹脂とが相分離することで形成していることが好ましい。本組成物を用いて後述する遮光膜の製造手順により本発明の遮光膜を形成した場合、遮光膜中には、黒色顔料と分散剤それ自体又は分散剤由来の樹脂（重合性基を有する分散剤が重合してなる樹脂）とから構成されたドメイン部（第１相に相当する）と、アルカリ可溶性樹脂そのものであるか又は上記アルカリ可溶性樹脂由来の樹脂（重合性基を有するアルカリ可溶性樹脂が重合してなる樹脂）から構成されたマトリックス部（第２相に相当する）が形成される。本組成物を用いて後述する遮光膜の製造手順により本発明の遮光膜を形成した場合、第１相と第２相の相分離構造としては、海島構造又は共連続構造となる場合が多い。 <Resin>
The composition includes a resin.
Examples of the resin include dispersants and alkali-soluble resins.
The light-shielding film of the present invention is preferably formed by phase separation of a dispersant and an alkali-soluble resin. When the light-shielding film of the present invention is formed using the composition according to the light-shielding film manufacturing procedure described below, the light-shielding film contains the black pigment and the dispersant itself, or a resin derived from the dispersant (a dispersion having a polymerizable group). A domain part (corresponding to the first phase) composed of a resin formed by polymerizing the agent and an alkali-soluble resin itself or a resin derived from the above-mentioned alkali-soluble resin (an alkali-soluble resin having a polymerizable group). A matrix portion (corresponding to the second phase) is formed from a polymerized resin. When the light-shielding film of the present invention is formed using the composition according to the light-shielding film production procedure described below, the phase-separated structure of the first phase and the second phase often becomes a sea-island structure or a co-continuous structure.
　樹脂の分子量は２，０００超であるのが好ましい。なお、樹脂の分子量が多分散である場合、重量平均分子量が２，０００超であるのが好ましい。
　以下、分散剤及びアルカリ可溶性樹脂について説明する。なお、本明細書において、分散剤とは、後述するアルカリ可溶性樹脂とは異なる化合物を意図する。 Preferably, the molecular weight of the resin is greater than 2,000. In addition, when the molecular weight of the resin is polydisperse, it is preferable that the weight average molecular weight is more than 2,000.
The dispersant and alkali-soluble resin will be explained below. In addition, in this specification, the dispersant intends a compound different from the alkali-soluble resin mentioned later.
（分散剤）
　組成物中における分散剤の含有量は特に制限されないが、組成物の全固形分に対して、２～４０質量％が好ましく、５～３０質量％がより好ましく、１０～２５質量％が更に好ましい。
　分散剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の分散剤を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 (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, based on the total solid content of the composition. .
The dispersants may be used alone or in combination of two or more. When two or more types of dispersants are used together, the total content is preferably within the above range.
　分散剤としては、例えば、公知の分散剤を適宜選択して使用できる。なかでも、高分子化合物が好ましい。
　分散剤としては、例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、及びナフタレンスルホン酸ホルマリン縮合物等のいわゆる分散樹脂として汎用の樹脂；ポリオキシエチレンアルキルリン酸エステル；ポリオキシエチレンアルキルアミン；顔料誘導体等が挙げられる。 As the dispersant, for example, known dispersants can be appropriately selected and used. Among these, polymer compounds are preferred.
Examples of dispersants include polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymers, and General-purpose resins such as so-called dispersion resins such as naphthalene sulfonic acid formalin condensates; polyoxyethylene alkyl phosphates; polyoxyethylene alkyl amines; pigment derivatives and the like can be mentioned.
　以下において、分散剤として機能し得る高分子化合物について説明する。 In the following, a polymer compound that can function as a dispersant will be explained.
・高分子化合物
　高分子化合物は、黒色顔料及び任意で組成物に含まれ得る各種顔料（以下、これらの顔料を総称して、単に「顔料」ともいう）等の被分散体の表面に吸着し、被分散体の再凝集を防止するように作用する。そのため、顔料表面へのアンカー部位を含む、末端変性型高分子、グラフト型（高分子鎖を含む）高分子、又はブロック型高分子が好ましい。 ・High molecular compound A high molecular compound is adsorbed onto the surface of a dispersion object such as a black pigment and various pigments that can optionally be included in the composition (hereinafter, these pigments are also collectively referred to simply as "pigments"). , acts to prevent re-agglomeration of the dispersed elements. Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, or a block-type polymer is preferable, which includes an anchor site to the pigment surface.
　上記高分子化合物は硬化性基を含んでいてもよい。
　硬化性基としては、例えば、エチレン性不飽和基（例えば、（メタ）アクリロイル基、ビニル基、及びスチリル基等）、及び環状エーテル基（例えば、エポキシ基及びオキセタニル基等）等が挙げられる。
　なかでも、ラジカル反応で重合制御が可能な点で、硬化性基としては、エチレン性不飽和基が好ましい。エチレン性不飽和基としては、（メタ）アクリロイル基が好ましい。 The above-mentioned polymer compound may contain a curable group.
Examples of the curable group include ethylenically unsaturated groups (eg, (meth)acryloyl group, vinyl group, styryl group, etc.), cyclic ether groups (eg, epoxy group, oxetanyl group, etc.), and the like.
Among these, ethylenically unsaturated groups are preferred as the curable group since polymerization can be controlled by radical reaction. As the ethylenically unsaturated group, a (meth)acryloyl group is preferable.
　硬化性基を含む高分子化合物は、ポリエステル構造及びポリエーテル構造からなる群から選ばれる１種以上を含むのが好ましい。この場合、主鎖にポリエステル構造及び／又はポリエーテル構造を含んでいてもよいし、後述するように、上記高分子化合物がグラフト鎖を含む構造単位を含む場合には、上記グラフト鎖がポリエステル構造及び／又はポリエーテル構造を含んでいてもよい。
　上記高分子化合物としては、上記グラフト鎖がポリエステル構造を含むのがより好ましい。 The polymer compound containing a curable group preferably contains one or more types selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and/or a polyether structure, or as described later, if the polymer compound contains a structural unit containing a graft chain, the graft chain may have a polyester structure. and/or may contain a polyether structure.
As for the above-mentioned polymer compound, it is more preferable that the above-mentioned graft chain contains a polyester structure.
　高分子化合物は、グラフト鎖を含む構造単位を含むのが好ましい。なお、本明細書において、「構造単位」とは「繰り返し単位」と同義である。
　このようなグラフト鎖を含む構造単位を含む高分子化合物は、グラフト鎖によって溶媒との親和性を有するために、顔料等の分散性、及び経時後の分散安定性に優れる。また、グラフト鎖の存在により、グラフト鎖を含む構造単位を含む高分子化合物は重合性化合物又はその他の併用可能な樹脂等との親和性を有する。結果として、アルカリ現像で残渣を生じにくくなる。
　グラフト鎖が長くなると立体反発効果が高くなり顔料等の分散性は向上する。一方、グラフト鎖が長すぎると顔料等への吸着力が低下して、顔料等の分散性は低下する傾向となる。このため、グラフト鎖中の水素原子を除いた原子数は、４０～１００００が好ましく、５０～２０００がより好ましく、６０～５００が更に好ましい。
　ここで、グラフト鎖とは、共重合体の主鎖の根元（主鎖から枝分かれしている基において主鎖に結合する原子）から、主鎖から枝分かれしている基の末端までを示す。 Preferably, the polymer compound contains a structural unit containing a graft chain. In addition, in this specification, a "structural unit" is synonymous with a "repeat unit."
A polymer compound containing a structural unit containing such a graft chain has affinity with a solvent due to the graft chain, and therefore has excellent dispersibility of pigments and the like and dispersion stability over time. Further, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity with the polymerizable compound or other resins that can be used in combination. As a result, residues are less likely to be produced during alkaline development.
As the graft chain becomes longer, the steric repulsion effect increases and the dispersibility of pigments and the like improves. On the other hand, if the graft chain is too long, the adsorption power to pigments etc. will decrease, and the dispersibility of pigments etc. will tend to decrease. Therefore, the number of atoms in the graft chain excluding hydrogen atoms is preferably 40 to 10,000, more preferably 50 to 2,000, even more preferably 60 to 500.
Here, the graft chain refers to the region from the root of the main chain of the copolymer (the atom bonded to the main chain in a group branching from the main chain) to the end of the group branching from the main chain.
　グラフト鎖は、ポリマー構造を含むのが好ましく、このようなポリマー構造としては、例えば、ポリ（メタ）アクリレート構造（例えば、ポリ（メタ）アクリル構造）、ポリエステル構造、ポリウレタン構造、ポリウレア構造、ポリアミド構造、及びポリエーテル構造等が挙げられる。
　グラフト鎖と溶媒との相互作用性を向上させ、それにより顔料等の分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造、及びポリ（メタ）アクリレート構造からなる群から選ばれる１種以上を含むグラフト鎖であるのが好ましく、ポリエステル構造及びポリエーテル構造の少なくともいずれかを含むグラフト鎖であるのがより好ましい。 Preferably, the graft chain comprises a polymeric structure, such as a poly(meth)acrylate structure (e.g. a poly(meth)acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure. , and a polyether structure.
In order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility of pigments, etc., the graft chain is one selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure. A graft chain containing at least one species is preferable, and a graft chain containing at least one of a polyester structure and a polyether structure is more preferable.
　このようなグラフト鎖を含むマクロモノマー（ポリマー構造を有し、共重合体の主鎖に結合してグラフト鎖を構成するモノマー）としては、特に制限されないが、反応性二重結合性基を含むマクロモノマーを好適に使用できる。 Macromonomers containing such graft chains (monomers that have a polymer structure and form graft chains by bonding to the main chain of the copolymer) are not particularly limited, but include reactive double bonding groups. Macromonomers can be suitably used.
　高分子化合物が含むグラフト鎖を含む構造単位に対応し、高分子化合物の合成に好適に用いられる市販のマクロモノマーとしては、ＡＡ－６（商品名、東亞合成社製）、ＡＡ－１０（商品名、東亞合成社製）、ＡＢ－６（商品名、東亞合成社製）、ＡＳ－６（商品名、東亞合成社製）、ＡＮ－６（商品名、東亞合成社製）、ＡＷ－６（商品名、東亞合成社製）、ＡＡ－７１４（商品名、東亞合成社製）、ＡＹ－７０７（商品名、東亞合成社製）、ＡＹ－７１４（商品名、東亞合成社製）、ＡＫ－５（商品名、東亞合成社製）、ＡＫ－３０（商品名、東亞合成社製）、ＡＫ－３２（商品名、東亞合成社製）、ブレンマーＰＰ－１００（商品名、日油社製）、ブレンマーＰＰ－５００（商品名、日油社製）、ブレンマーＰＰ－８００（商品名、日油社製）、ブレンマーＰＰ－１０００（商品名、日油社製）、ブレンマー５５－ＰＥＴ－８００（商品名、日油社製）、ブレンマーＰＭＥ－４０００（商品名、日油社製）、ブレンマーＰＳＥ－４００（商品名、日油社製）、ブレンマーＰＳＥ－１３００（商品名、日油社製）、又はブレンマー４３ＰＡＰＥ－６００Ｂ（商品名、日油社製）等が用いられる。このなかでも、ＡＡ－６（商品名、東亞合成社製）、ＡＡ－１０（商品名、東亞合成社製）、ＡＢ－６（商品名、東亞合成社製）、ＡＳ－６（商品名、東亞合成社製）、ＡＮ－６（商品名、東亞合成社製）、又はブレンマーＰＭＥ－４０００（商品名、日油社製）が好ましい。 Commercially available macromonomers that correspond to structural units containing graft chains contained in polymeric compounds and are suitably used in the synthesis of polymeric compounds include AA-6 (trade name, manufactured by Toagosei Co., Ltd.) and AA-10 (trade name). AB-6 (product name, manufactured by Toagosei Co., Ltd.), AS-6 (product name, manufactured by Toagosei Co., Ltd.), AN-6 (product name, manufactured by Toagosei Co., Ltd.), AW-6 (Product name, manufactured by Toagosei Co., Ltd.), AA-714 (Product name, manufactured by Toagosei Co., Ltd.), AY-707 (Product name, manufactured by Toagosei Co., Ltd.), AY-714 (Product name, manufactured by Toagosei Co., Ltd.), AK -5 (product name, manufactured by Toagosei Co., Ltd.), AK-30 (product name, manufactured by Toagosei Co., Ltd.), AK-32 (product name, manufactured by Toagosei Co., Ltd.), Blenmar PP-100 (product name, manufactured by NOF Corporation) ), Blenmar PP-500 (trade name, manufactured by NOF Corporation), Blenmar PP-800 (trade name, manufactured by NOF Corporation), Blenmar PP-1000 (trade name, manufactured by NOF Corporation), Blenmar 55-PET-800 (Product name, manufactured by NOF Corporation), Blenmar PME-4000 (Product name, manufactured by NOF Corporation), Blenmar PSE-400 (Product name, manufactured by NOF Corporation), Blenmar PSE-1300 (Product name, manufactured by NOF Corporation) ), or Blenmar 43PAPE-600B (trade name, manufactured by NOF Corporation), etc. are used. Among these, AA-6 (product name, manufactured by Toagosei Co., Ltd.), AA-10 (product name, manufactured by Toagosei Co., Ltd.), AB-6 (product name, manufactured by Toagosei Co., Ltd.), AS-6 (product name, (manufactured by Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), or Blenmar PME-4000 (trade name, manufactured by NOF Corporation) are preferred.
　上記分散剤は、ポリアクリル酸メチル、ポリメタクリル酸メチル、及び環状又は鎖状のポリエステルからなる群から選ばれる１種以上の構造を含むのが好ましく、ポリアクリル酸メチル、ポリメタクリル酸メチル、及び鎖状のポリエステルからなる群から選ばれる１種以上の構造を含むのがより好ましく、ポリアクリル酸メチル構造、ポリメタクリル酸メチル構造、ポリカプロラクトン構造、及びポリバレロラクトン構造からなる群から選ばれる１種以上の構造を含むのが更に好ましい。分散剤は、一の分散剤中に上記構造を単独で含む分散剤であってもよいし、一の分散剤中にこれらの構造を複数含む分散剤であってもよい。
　ここで、ポリカプロラクトン構造とは、ε－カプロラクトンを開環した構造を繰り返し単位として含む構造をいう。ポリバレロラクトン構造とは、δ－バレロラクトンを開環した構造を繰り返し単位として含む構造をいう。
　ポリカプロラクトン構造を含む分散剤の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが５である分散剤が挙げられる。また、ポリバレロラクトン構造を含む分散剤の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが４である分散剤が挙げられる。
　ポリアクリル酸メチル構造を含む分散剤の具体例としては、下記式（４）におけるＸ５が水素原子であり、Ｒ４がメチル基である分散剤が挙げられる。また、ポリメタクリル酸メチル構造を含む分散剤の具体例としては、下記式（４）におけるＸ５がメチル基であり、Ｒ４がメチル基である分散剤が挙げられる。 The dispersant preferably contains one or more structures selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester, and includes polymethyl acrylate, polymethyl methacrylate, and More preferably, it contains one or more structures selected from the group consisting of chain polyesters, and one selected from the group consisting of polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure, and polyvalerolactone structure. It is even more preferable to include more than one type of structure. The dispersant may be a dispersant containing only one of the above structures in one dispersant, or may be a dispersant containing a plurality of these structures in one dispersant.
Here, the polycaprolactone structure refers to a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opened structure of δ-valerolactone as a repeating unit.
Specific examples of dispersants containing a polycaprolactone structure include dispersants in which j and k are 5 in the following formulas (1) and (2). Further, specific examples of dispersants containing a polyvalerolactone structure include dispersants in which j and k are 4 in the following formulas (1) and (2).
A specific example of a dispersant containing a polymethyl acrylate structure includes a dispersant in which X 5 is a hydrogen atom and R 4 is a methyl group in the following formula (4). Further, a specific example of a dispersant containing a polymethyl methacrylate structure includes a dispersant in which X 5 is a methyl group and R 4 is a methyl group in the following formula (4).
・グラフト鎖を含む構造単位
　グラフト鎖を含む構造単位としては、下記式（１）～式（４）のいずれかで表される構造単位が好ましい。 - Structural unit containing a graft chain The structural unit containing a graft chain is preferably a structural unit represented by any of the following formulas (1) to (4).
　式（１）～（４）において、Ｗ１、Ｗ２、Ｗ３、及びＷ４は、それぞれ独立に、酸素原子又はＮＨを表す。Ｗ１、Ｗ２、Ｗ３、及びＷ４としては、酸素原子が好ましい。
　式（１）～（４）において、Ｘ１、Ｘ２、Ｘ３、Ｘ４、及びＸ５は、それぞれ独立に、水素原子又は１価の有機基を表す。Ｘ１、Ｘ２、Ｘ３、Ｘ４、及びＸ５としては、合成上の制約の観点からは、それぞれ独立に、水素原子又は炭素数（炭素原子数）１～１２のアルキル基が好ましく、それぞれ独立に、水素原子又はメチル基がより好ましく、メチル基が更に好ましい。 In formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH. As W 1 , W 2 , W 3 , and W 4 , oxygen atoms are preferable.
In formulas (1) to (4), X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthetic constraints, each of X 1 , X 2 , X 3 , X 4 and X 5 is preferably independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Each independently, a hydrogen atom or a methyl group is more preferable, and a methyl group is even more preferable.
　式（１）～（４）において、Ｙ１、Ｙ２、Ｙ３、及びＹ４は、それぞれ独立に、２価の連結基を表し、連結基は特に構造上制約されない。Ｙ１、Ｙ２、Ｙ３、及びＹ４で表される２価の連結基として、具体的には、下記の（Ｙ－１）～（Ｙ－２１）の連結基等が例として挙げられる。下記に示した構造において、Ａ、Ｂはそれぞれ、式（１）～（４）における左末端基、右末端基との結合部位を意味する。下記に示した構造のうち、合成の簡便性から、（Ｙ－２）又は（Ｙ－１３）であるのがより好ましい。 In formulas (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly structurally restricted. Specific examples of the divalent linking groups represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following linking groups (Y-1) to (Y-21). . In the structures shown below, A and B mean the bonding site with the left end group and the right end group in formulas (1) to (4), respectively. Among the structures shown below, (Y-2) or (Y-13) is more preferred for ease of synthesis.
　式（１）～（４）において、Ｚ１、Ｚ２、Ｚ３、及びＺ４は、それぞれ独立に、水酸基、アミノ基、又は１価の有機基を表す。有機基の構造としては特に制限されないが、具体的には、アルキル基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、及びヘテロアリールチオエーテル基等が挙げられる。
　Ｚ１、Ｚ２、Ｚ３、及びＺ４で表される有機基としては、なかでも、特に分散性向上の観点から、立体反発効果を含む基が好ましく、炭素数５～２４のアルキル基又はアルコキシ基がより好ましく、炭素数５～２４の分岐アルキル基、炭素数５～２４の環状アルキル基、又は炭素数５～２４のアルコキシ基が更に好ましい。
　なお、アルコキシ基中に含まれるアルキル基は、直鎖状、分岐鎖状、及び環状のいずれでもよい。また、アルコキシ基におけるメチレン基は、－Ｏ－で置換されていてもよい。
　また、上記各基は、置換基（例えば、水酸基及び（メタ）アクリロイルオキシ基等のエチレン性不飽和基等）を有していてもよい。 In formulas (1) to (4), Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a hydroxyl group, an amino group, or a monovalent organic group. Although the structure of the organic group is not particularly limited, specific examples include an alkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
Among the organic groups represented by Z 1 , Z 2 , Z 3 , and Z 4 , groups having a steric repulsion effect are preferred, particularly from the viewpoint of improving dispersibility, and alkyl groups having 5 to 24 carbon atoms or An alkoxy group is more preferred, and a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is even more preferred.
Note that the alkyl group contained in the alkoxy group may be linear, branched, or cyclic. Furthermore, the methylene group in the alkoxy group may be substituted with -O-.
Moreover, each of the above groups may have a substituent (for example, a hydroxyl group, an ethylenically unsaturated group such as a (meth)acryloyloxy group, etc.).
　なお、式（１）において、Ｚ１が水酸基である場合、式中の－ＣＯＺ１で表される部位は、アニオン化（－ＣＯＯ－）していてもよい。この場合、カウンターカチオンとしては、４級アンモニウム塩が挙げられ、なかでも式（ＴＹ）で表される構造であるのが好ましい。 In addition, in the formula (1), when Z 1 is a hydroxyl group, the moiety represented by -COZ 1 in the formula may be anionized (-COO - ). In this case, examples of the counter cation include quaternary ammonium salts, and a structure represented by formula (TY) is particularly preferred.
　式（ＴＹ）において、Ｒ１ｆ及びＲ１ｇは、各々独立に、水素原子又はアルキル基を表す。Ｒ１ｆ及びＲ１ｇで表されるアルキル基としては、直鎖状又は分岐鎖状であるのが好ましい。また、炭素数としては、１～１０であるのが好ましく、１～４であるのがより好ましく、１又は２が更に好ましい。
　式（ＴＹ）において、Ｒ１ｅは、アルキル基を表す。Ｒ１ｅで表されるアルキル基としては、直鎖状であるのが好ましい。また、炭素数としては、１０～２４であるのが好ましく、１０～２０であるのがより好ましい。
　式（ＴＹ）において、Ｌ２は、アルキレン基を表す。Ｌ２で表されるアルキレン基としては、直鎖状又は分岐鎖状であるのが好ましく、直鎖状であるのがより好ましい。炭素数としては、１～２０が好ましく、１～１２がより好ましい。また、アルキレン基は置換基（例えば、水酸基）を有していてもよい。また、アルキレン基におけるメチレン基は、－Ｏ－で置換されていてもよい。
　式（ＴＹ）において、Ｒ１ｈは、水素原子又は（メタ）アクリロイルオキシ基等のエチレン性不飽和基を表す。 In formula (TY), R 1f and R 1g each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R 1f and R 1g is preferably linear or branched. Further, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
In formula (TY), R 1e represents an alkyl group. The alkyl group represented by R 1e is preferably linear. Further, the number of carbon atoms is preferably 10 to 24, more preferably 10 to 20.
In formula (TY), L 2 represents an alkylene group. The alkylene group represented by L 2 is preferably linear or branched, more preferably linear. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 12. Further, the alkylene group may have a substituent (for example, a hydroxyl group). Furthermore, the methylene group in the alkylene group may be substituted with -O-.
In formula (TY), R 1h represents a hydrogen atom or an ethylenically unsaturated group such as a (meth)acryloyloxy group.
　式（１）～（４）において、ｎ、ｍ、ｐ、及びｑは、それぞれ独立に、１～５００の整数を表す。
　また、式（１）及び（２）において、ｊ及びｋは、それぞれ独立に、２～８の整数を表す。式（１）及び（２）におけるｊ及びｋとしては、組成物の経時粘度安定性及び現像性の観点から、４～６の整数が好ましく、５がより好ましい。
　また、式（１）及び（２）において、ｎ及びｍとしては、５以上の整数が好ましく、８以上の整数がより好ましく、１０以上の整数が更に好ましい。また、分散剤が、ポリカプロラクトン構造、及びポリバレロラクトン構造を含む場合、ポリカプロラクトン構造の繰り返し数と、ポリバレロラクトンの繰返し数の和としては、１０以上の整数が好ましく、２０以上の整数がより好ましい。 In formulas (1) to (4), n, m, p, and q each independently represent an integer of 1 to 500.
Furthermore, in formulas (1) and (2), j and k each independently represent an integer from 2 to 8. j and k in formulas (1) and (2) are preferably integers of 4 to 6, more preferably 5, from the viewpoint of the viscosity stability over time and developability of the composition.
Further, in formulas (1) and (2), n and m are preferably integers of 5 or more, more preferably 8 or more, and even more preferably 10 or more. In addition, when the dispersant includes a polycaprolactone structure and a polyvalerolactone structure, the sum of the number of repeats of the polycaprolactone structure and the number of repeats of polyvalerolactone is preferably an integer of 10 or more, and an integer of 20 or more is preferable. More preferred.
　式（３）中、Ｒ３は分岐鎖状又は直鎖状のアルキレン基を表し、炭素数１～１０のアルキレン基が好ましく、炭素数２又は３のアルキレン基がより好ましい。ｐが２～５００のとき、複数存在するＲ３は互いに同じであっても異なっていてもよい。
　式（４）中、Ｒ４は水素原子又は１価の有機基を表し、この１価の有機基としては特に構造上制限はされない。Ｒ４としては、水素原子、アルキル基、アリール基、又はヘテロアリール基が好ましく、水素原子又はアルキル基がより好ましい。Ｒ４がアルキル基である場合、アルキル基としては、炭素数１～２０の直鎖状アルキル基、炭素数３～２０の分岐鎖状アルキル基、又は炭素数５～２０の環状アルキル基が好ましく、炭素数１～２０の直鎖状アルキル基がより好ましく、炭素数１～６の直鎖状アルキル基が更に好ましい。式（４）において、ｑが２～５００のとき、グラフト共重合体中に複数存在するＸ５及びＲ４は互いに同じであっても異なっていてもよい。 In formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 's may be the same or different.
In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and this monovalent organic group is not particularly limited in terms of structure. R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R 4 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, a plurality of X 5 and R 4 present in the graft copolymer may be the same or different.
　また、高分子化合物は、２種以上の構造が異なる、グラフト鎖を含む構造単位を含むことができる。即ち、高分子化合物の分子中に、互いに構造の異なる式（１）～（４）で示される構造単位を含んでいてもよく、また、式（１）～（４）においてｎ、ｍ、ｐ、及びｑがそれぞれ２以上の整数を表す場合、式（１）及び（２）においては、側鎖中にｊ及びｋが互いに異なる構造を含んでいてもよく、式（３）及び（４）においては、分子内に複数存在するＲ３、Ｒ４、及びＸ５は互いに同じであっても異なっていてもよい。 Furthermore, the polymer compound can include two or more structural units that have different structures and include graft chains. That is, the molecules of the polymer compound may contain structural units represented by formulas (1) to (4) that have mutually different structures, and in formulas (1) to (4), n, m, p , and q each represent an integer of 2 or more, in formulas (1) and (2), j and k may include structures different from each other in the side chain, and formulas (3) and (4) In , a plurality of R 3 , R 4 , and X 5 present in the molecule may be the same or different.
　高分子化合物において、グラフト鎖を有する構造単位（特に、上記式（１）～（４）で表される構造単位）の含有量としては、質量換算で、高分子化合物の総質量に対して、２～９０質量％であるのが好ましく、５～３０質量％であるのがより好ましい。グラフト鎖を有する構造単位（特に、上記式（１）～（４）で表される構造単位）の含有量が５質量％以上である場合、顔料の分散性が高く、本発明の効果がより優れる。 In a polymer compound, the content of structural units having a graft chain (particularly structural units represented by formulas (1) to (4) above) is, in terms of mass, relative to the total mass of the polymer compound. It is preferably 2 to 90% by weight, more preferably 5 to 30% by weight. When the content of structural units having graft chains (particularly structural units represented by formulas (1) to (4) above) is 5% by mass or more, the dispersibility of the pigment is high and the effects of the present invention are enhanced. Excellent.
・疎水性構造単位
　また、高分子化合物は、グラフト鎖を含む構造単位とは異なる（すなわち、グラフト鎖を含む構造単位には相当しない）疎水性構造単位を含むのが好ましい。ただし、本明細書において、疎水性構造単位は、酸基（例えば、カルボン酸基、スルホン酸基、リン酸基、フェノール性水酸基等）を有さない構造単位である。 -Hydrophobic Structural Unit The polymer compound preferably contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the graft chain). However, in this specification, a hydrophobic structural unit is a structural unit that does not have an acid group (eg, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).
　疎水性構造単位は、ＣｌｏｇＰ値が１．２以上の化合物（モノマー）に由来する（対応する）構造単位であるのが好ましく、ＣｌｏｇＰ値が１．２～８の化合物に由来する構造単位であるのがより好ましい。これにより、本発明の効果をより確実に発現できる。 The hydrophobic structural unit is preferably a structural unit (corresponding to) derived from a compound (monomer) having a ClogP value of 1.2 or more, and is a structural unit derived from a compound having a ClogP value of 1.2 to 8. is more preferable. Thereby, the effects of the present invention can be more reliably expressed.
　本明細書において、ＣｌｏｇＰ値は、Ｄａｙｌｉｇｈｔ　Ｃｈｅｍｉｃａｌ　Ｉｎｆｏｒｍａｔｉｏｎ　Ｓｙｓｔｅｍ，　Ｉｎｃ．から入手できるプログラム“ＣＬＯＧＰ”で計算された値である。このプログラムは、Ｈａｎｓｃｈ，　Ｌｅｏのフラグメントアプローチ（下記文献参照）により算出される“計算ｌｏｇＰ”の値を提供する。フラグメントアプローチは化合物の化学構造に基づいており、化学構造を部分構造（フラグメント）に分割し、そのフラグメントに対して割り当てられたｌｏｇＰ寄与分を合計して化合物のｌｏｇＰ値を推算している。その詳細は以下の文献に記載されている。本明細書では、プログラムＣＬＯＧＰ　ｖ４．８２により計算したＣｌｏｇＰ値を用いる。
　Ａ．　Ｊ．　Ｌｅｏ，　Ｃｏｍｐｒｅｈｅｎｓｉｖｅ　Ｍｅｄｉｃｉｎａｌ　Ｃｈｅｍｉｓｔｒｙ，　Ｖｏｌ．４，　Ｃ．　Ｈａｎｓｃｈ，　Ｐ．　Ｇ．　Ｓａｍｍｎｅｎｓ，　Ｊ．　Ｂ．　Ｔａｙｌｏｒ　ａｎｄ　Ｃ．　Ａ．　Ｒａｍｓｄｅｎ，　Ｅｄｓ．，　ｐ．２９５，　Ｐｅｒｇａｍｏｎ　Ｐｒｅｓｓ，　１９９０　Ｃ．　Ｈａｎｓｃｈ　＆　Ａ．　Ｊ．　Ｌｅｏ．　ＳＵｂｓｔｉｔｕｅｎｔ　Ｃｏｎｓｔａｎｔｓ　Ｆｏｒ　Ｃｏｒｒｅｌａｔｉｏｎ　Ａｎａｌｙｓｉｓ　ｉｎ　Ｃｈｅｍｉｓｔｒｙ　ａｎｄ　Ｂｉｏｌｏｇｙ．　Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ．　Ａ．Ｊ．　Ｌｅｏ．　Ｃａｌｃｕｌａｔｉｎｇ　ｌｏｇＰｏｃｔ　ｆｒｏｍ　ｓｔｒｕｃｔｕｒｅ．　Ｃｈｅｍ．　Ｒｅｖ．，　９３，　１２８１－１３０６，　１９９３． As used herein, ClogP values are determined by Daylight Chemical Information System, Inc. This value was calculated using the program “CLOGP” available from This program provides the value of "computed logP" calculated by the fragment approach of Hansch, Leo (see below). The fragment approach is based on the chemical structure of a compound and estimates the logP value of the compound by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments. The details are described in the following documents. In this specification, ClogP values calculated by the program CLOGP v4.82 are used.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds. , p. 295, Pergamon Press, 1990 C. Hansch &A. J. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev. , 93, 1281-1306, 1993.
　ｌｏｇＰは、分配係数Ｐ（Ｐａｒｔｉｔｉｏｎ　Ｃｏｅｆｆｉｃｉｅｎｔ）の常用対数を意味し、ある有機化合物が油（一般的には１－オクタノール）と水の２相系の平衡でどのように分配されるかを定量的な数値として表す物性値であり、以下の式で示される。
　　ｌｏｇＰ＝ｌｏｇ（Ｃｏｉｌ／Ｃｗａｔｅｒ）
　式中、Ｃｏｉｌは油相中の化合物のモル濃度を、Ｃｗａｔｅｒは水相中の化合物のモル濃度を表す。
　ｌｏｇＰの値が０をはさんでプラスに大きくなると油溶性が増し、マイナスで絶対値が大きくなると水溶性が増し、有機化合物の水溶性と負の相関があり、有機化合物の親疎水性を見積るパラメータとして広く利用されている。 logP means the common logarithm of the partition coefficient P (Partition Coefficient), which quantitatively describes how a certain organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, 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 Water represents the molar concentration of the compound in the aqueous phase.
When the value of logP increases in the positive direction across 0, the oil solubility increases, and as the absolute value increases in the negative direction, the water solubility increases.There is a negative correlation with the water solubility of organic compounds, and it is a parameter for estimating the hydrophilicity and hydrophobicity of organic compounds. It is widely used as
　高分子化合物において、疎水性構造単位は、質量換算で、高分子化合物の総質量に対して、１０～９０％の範囲で含まれるのが好ましく、２０～８０％の範囲で含まれるのがより好ましい。含有量が上記範囲において十分なパターン形成が得られる。 In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably 20 to 80%, based on the total mass of the polymer compound. preferable. Sufficient pattern formation can be obtained when the content is within the above range.
・顔料等と相互作用を形成しうる官能基
　高分子化合物は、顔料等（例えば、遮光顔料）と相互作用を形成しうる官能基を導入できる。ここで、高分子化合物は、顔料等と相互作用を形成しうる官能基を含む構造単位を更に含むのが好ましい。
　この顔料等と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、及び反応性を有する官能基等が挙げられる。
　高分子化合物が、酸基、塩基性基、配位性基、又は反応性を有する官能基を含む場合、それぞれ、酸基を含む構造単位、塩基性基を含む構造単位、配位性基を含む構造単位、又は反応性を有する構造単位を含むのが好ましい。
　特に、高分子化合物が、更に、酸基として、カルボン酸基等のアルカリ可溶性基を含有すれば、高分子化合物に、アルカリ現像によるパターン形成のための現像性を付与できる。
　すなわち、高分子化合物にアルカリ可溶性基を導入すれば、上記組成物は、顔料等の分散に寄与する分散剤としての高分子化合物がアルカリ可溶性を含むことになる。このような高分子化合物を含む組成物は、露光して形成される遮光膜の遮光性に優れ、かつ、未露光部のアルカリ現像性が向上される。
　また、高分子化合物が酸基を含む構造単位を含めば、高分子化合物が溶媒となじみやすくなり、塗布性も向上する傾向となる。
　これは、酸基を含む構造単位における酸基が顔料等と相互作用しやすく、高分子化合物が顔料等を安定的に分散すると共に、顔料等を分散する高分子化合物の粘度が低くなっており、高分子化合物自体も安定的に分散されやすいためであると推測される。 -Functional group capable of forming an interaction with a pigment, etc. A functional group capable of forming an interaction with a pigment, etc. (for example, a light-shielding pigment) can be introduced into the polymer compound. Here, it is preferable that the polymer compound further includes a structural unit containing a functional group capable of forming an interaction with a pigment or the like.
Examples of the functional group capable of forming an interaction with the pigment include an acid group, a basic group, a coordinating group, and a reactive functional group.
When a polymer compound contains an acid group, a basic group, a coordinating group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, or a coordinating group is It is preferable to include a structural unit that contains or a structural unit that has reactivity.
In particular, if the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be given developability for pattern formation by alkali development.
That is, if an alkali-soluble group is introduced into the polymer compound, in the composition, the polymer compound serving as a dispersant that contributes to the dispersion of pigments and the like contains alkali-solubility. A composition containing such a polymer compound has excellent light-shielding properties of a light-shielding film formed by exposure, and the alkali developability of unexposed areas is improved.
Furthermore, if the polymer compound contains a structural unit containing an acid group, the polymer compound will be more compatible with the solvent, and its coating properties will tend to be improved.
This is because acid groups in structural units containing acid groups easily interact with pigments, etc., and the polymer compound stably disperses the pigment, etc., and the viscosity of the polymer compound that disperses the pigment, etc. is low. This is presumably because the polymer compound itself is easily dispersed stably.
　ただし、酸基としてのアルカリ可溶性基を含む構造単位は、上記のグラフト鎖を含む構造単位と同一の構造単位であっても、異なる構造単位であってもよいが、酸基としてのアルカリ可溶性基を含む構造単位は、上記の疎水性構造単位とは異なる構造単位である（すなわち、上記の疎水性構造単位には相当しない）。 However, the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the above-mentioned structural unit containing a graft chain, or may be a different structural unit; The structural unit containing is a structural unit different from the above-mentioned hydrophobic structural unit (that is, it does not correspond to the above-mentioned hydrophobic structural unit).
　顔料等と相互作用を形成しうる官能基である酸基としては、例えば、カルボン酸基、スルホン酸基、リン酸基、及びフェノール性水酸基等があり、カルボン酸基、スルホン酸基、及びリン酸基からなる群から選ばれる１種以上であるのが好ましく、カルボン酸基がより好ましい。カルボン酸基は、顔料等への吸着力が良好で、かつ、分散性が高い。
　すなわち、高分子化合物は、カルボン酸基、スルホン酸基、及びリン酸基からなる群から選ばれる１種以上を含む構造単位を含むのが好ましい。 Examples of acid groups that are functional groups that can interact with pigments include carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups. It is preferable that it is one or more types selected from the group consisting of acid groups, and carboxylic acid groups are more preferable. Carboxylic acid groups have good adsorption power to pigments and the like, and have high dispersibility.
That is, the polymer compound preferably contains a structural unit containing one or more types selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
　高分子化合物は、酸基を含む構造単位を１種又は２種以上有してもよい。
　高分子化合物は、酸基を含む構造単位を含んでいなくてもよいが、含む場合、酸基を含む構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、５～８０質量％が好ましく、アルカリ現像による画像強度のダメージ抑制という観点から、１０～６０質量％がより好ましい。 The polymer compound may have one or more types of structural units containing acid groups.
The polymer compound does not need to contain a structural unit containing an acid group, but if it does, the content of the structural unit containing an acid group is 5% relative to the total mass of the polymer compound in terms of mass. The amount is preferably from 10 to 80% by mass, and more preferably from 10 to 60% by mass from the viewpoint of suppressing damage to image strength due to alkaline development.
　顔料等と相互作用を形成しうる官能基である塩基性基としては、例えば、第１級アミノ基、第２級アミノ基、第３級アミノ基、Ｎ原子を含むヘテロ環、及びアミド基等があり、好ましい塩基性基は、顔料等への吸着力が良好で、かつ、分散性が高い点で、第３級アミノ基である。高分子化合物は、これらの塩基性基を１種又は２種以上、含んでいてもよい。
　高分子化合物は、塩基性基を含む構造単位を含んでいなくてもよいが、含む場合、塩基性基を含む構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、０．０１～５０質量％が好ましく、現像性阻害抑制という観点から、０．０１～３０質量％がより好ましい。 Examples of basic groups that are functional groups that can interact with pigments include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, and amide groups. A preferred basic group is a tertiary amino group because it has good adsorption power to pigments and the like and high dispersibility. The polymer compound may contain one or more of these basic groups.
The polymer compound does not need to contain a structural unit containing a basic group, but if it does, the content of the structural unit containing a basic group is calculated based on the total mass of the polymer compound. , is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass from the viewpoint of suppressing development inhibition.
　顔料等と相互作用を形成しうる官能基である配位性基、及び反応性を有する官能基としては、例えば、アセチルアセトキシ基、トリアルコキシシリル基、イソシアネート基、酸無水物、及び酸塩化物等が挙げられる。好ましい官能基は、顔料等への吸着力が良好で、顔料等の分散性が高い点で、アセチルアセトキシ基である。高分子化合物は、これらの基を１種又は２種以上有してもよい。
　高分子化合物は、配位性基を含む構造単位、又は反応性を有する官能基を含む構造単位を含んでいなくてもよいが、含む場合、これらの構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、１０～８０質量％が好ましく、現像性阻害抑制という観点から、２０～６０質量％がより好ましい。 Coordinating groups that are functional groups that can interact with pigments, etc., and reactive functional groups include, for example, acetylacetoxy groups, trialkoxysilyl groups, isocyanate groups, acid anhydrides, and acid chlorides. etc. A preferred functional group is an acetylacetoxy group because it has good adsorption power to pigments and the like and has high dispersibility of pigments and the like. The polymer compound may have one or more of these groups.
The polymer compound does not need to contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it does, the content of these structural units in terms of mass is , based on the total weight of the polymer compound, is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass from the viewpoint of suppressing development inhibition.
　顔料等と相互作用を形成しうる官能基を含む構造単位の含有量は、顔料等との相互作用、経時粘度安定性、及び現像液への浸透性の観点から、高分子化合物の全質量に対して、０．０５～９０質量％が好ましく、１．０～８０質量％がより好ましく、１０～７０質量％が更に好ましい。 The content of structural units containing functional groups that can interact with pigments, etc. is determined based on the total mass of the polymer compound, from the viewpoints of interaction with pigments, viscosity stability over time, and permeability to the developer. On the other hand, it is preferably 0.05 to 90% by weight, more preferably 1.0 to 80% by weight, and even more preferably 10 to 70% by weight.
・その他の構造単位
　更に、高分子化合物は、画像強度等の諸性能を向上する目的で、本発明の効果を損なわない限りにおいて、グラフト鎖を含む構造単位、疎水性構造単位、及び顔料等と相互作用を形成しうる官能基を含む構造単位とは異なる、種々の機能を有する他の構造単位（例えば、後述する溶媒との親和性を有する官能基等を含む構造単位）を更に有していてもよい。
　このような、他の構造単位としては、例えば、アクリロニトリル類、及びメタクリロニトリル類等から選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。 ・Other structural units Furthermore, for the purpose of improving various performances such as image strength, the polymer compound may contain structural units containing graft chains, hydrophobic structural units, pigments, etc., as long as the effects of the present invention are not impaired. It further has other structural units that have various functions (for example, structural units that include a functional group that has affinity with a solvent as described below), which is different from the structural unit that includes a functional group that can form an interaction. It's okay.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
　高分子化合物は、これらの他の構造単位を１種又は２種以上使用でき、その含有量は、質量換算で、高分子化合物の総質量に対して、０～８０質量％が好ましく、１０～６０質量％がより好ましい。含有量が上記範囲において、十分なパターン形成性が維持される。 The polymer compound can use one or more of these other structural units, and the content thereof is preferably 0 to 80% by mass, and 10 to 80% by mass, based on the total mass of the polymer compound. 60% by mass is more preferred. When the content is within the above range, sufficient pattern formability is maintained.
・高分子化合物の物性
　高分子化合物の酸価は、０～２００ｍｇＫＯＨ／ｇが好ましく、２０～１５０ｍｇＫＯＨ／ｇがより好ましく、４０～１００ｍｇＫＯＨ／ｇが更に好ましく、４０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ未満が特に好ましい。
　高分子化合物の酸価が２００ｍｇＫＯＨ／ｇ以下であれば、露光後の組成物層を現像する際におけるパターン剥離がより効果的に抑えられる。また、高分子化合物の酸価が１０ｍｇＫＯＨ／ｇ以上であればアルカリ現像性がより良好となる。
　高分子化合物の重量平均分子量としては、５，０００～１００，０００が好ましく、６，０００～８０，０００がより好ましく、１５，０００～４０，０００であるのが更に好ましく、２０，０００～４０，０００であるのが特に好ましく、２５，０００～４０，０００であるのが最も好ましい。
　高分子化合物のガラス転移温度としては、－２０～１００℃が好ましく、－２０～８０℃がより好ましく、－１０～６０℃が更に好ましい。
　ガラス転移温度は、ＤＳＣ　３５００　Ｓｉｒｉｕｓ（Ｎｅｔｚｓｃｈ社製）により測定できる。
　高分子化合物は、公知の方法に基づいて合成できる。 ・Physical properties of the polymer compound The acid value of the polymer compound is preferably 0 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, even more preferably 40 to 100 mgKOH/g, particularly 40 mgKOH/g or more and less than 60 mgKOH/g. preferable.
If the acid value of the polymer compound is 200 mgKOH/g or less, pattern peeling during development of the exposed composition layer can be more effectively suppressed. Further, if the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability will be better.
The weight average molecular weight of the polymer compound is preferably 5,000 to 100,000, more preferably 6,000 to 80,000, even more preferably 15,000 to 40,000, and even more preferably 20,000 to 40. ,000 is particularly preferred, and 25,000 to 40,000 is most preferred.
The glass transition temperature of the polymer compound is preferably -20 to 100°C, more preferably -20 to 80°C, even more preferably -10 to 60°C.
The glass transition temperature can be measured using DSC 3500 Sirius (manufactured by Netzsch).
A polymer compound can be synthesized based on a known method.
　高分子化合物としては、例えば、楠本化成社製「ＤＡ－７３０１」、ＢＹＫＣｈｅｍｉｅ社製「Ｄｉｓｐｅｒｂｙｋ－１０１（ポリアミドアミン燐酸塩）、１０７（カルボン酸エステル）、１１０（酸基を含む共重合体）、１１１（リン酸系分散剤）、１３０（ポリアミド）、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１７０、１９０（高分子共重合体）」、「ＢＹＫ－Ｐ１０４、Ｐ１０５（高分子量不飽和ポリカルボン酸）」、ＥＦＫＡ社製「ＥＦＫＡ４０４７、４０５０～４０１０～４１６５（ポリウレタン系）、ＥＦＫＡ４３３０～４３４０（ブロック共重合体）、４４００～４４０２（変性ポリアクリレート）、５０１０（ポリエステルアミド）、５７６５（高分子量ポリカルボン酸塩）、６２２０（脂肪酸ポリエステル）、６７５０（アゾ顔料誘導体）」、味の素ファインテクノ社製「アジスパーＰＢ８２１、ＰＢ８２２、ＰＢ８８０、ＰＢ８８１」、共栄社化学社製「フローレンＴＧ－７１０（ウレタンオリゴマー）」、「ポリフローＮｏ．５０Ｅ、Ｎｏ．３００（アクリル系共重合体）」、楠本化成社製「ディスパロンＫＳ－８６０、８７３ＳＮ、８７４、＃２１５０（脂肪族多価カルボン酸）、＃７００４（ポリエーテルエステル）、ＤＡ－７０３－５０、ＤＡ－７０５、ＤＡ－７２５」、花王社製「デモールＲＮ、Ｎ（ナフタレンスルホン酸ホルマリン重縮合物）、ＭＳ、Ｃ、ＳＮ－Ｂ（芳香族スルホン酸ホルマリン重縮合物）」、「ホモゲノールＬ－１８（高分子ポリカルボン酸）」、「エマルゲン９２０、９３０、９３５、９８５（ポリオキシエチレンノニルフェニルエーテル）」、「アセタミン８６（ステアリルアミンアセテート）」、日本ルブリゾール社製「２２０００（アゾ顔料誘導体）、１３２４０（ポリエステルアミン）、３０００、１２０００、１７０００、２００００、２７０００（末端部に機能部を含む高分子）、２４０００、２８０００、３２０００、３８５００（グラフト共重合体）」、日光ケミカル社製「ニッコールＴ１０６（ポリオキシエチレンソルビタンモノオレート）、ＭＹＳ－ＩＥＸ（ポリオキシエチレンモノステアレート）」、川研ファインケミカル製　ヒノアクトＴ－８０００Ｅ等、信越化学工業製、オルガノシロキサンポリマーＫＰ３４１、裕商製「Ｗ００１：カチオン系界面活性剤」、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル等のノニオン系界面活性剤、「Ｗ００４、Ｗ００５、Ｗ０１７」等のアニオン系界面活性剤、森下産業製「ＥＦＫＡ－４６、ＥＦＫＡ－４７、ＥＦＫＡ－４７ＥＡ、ＥＦＫＡポリマー１００、ＥＦＫＡポリマー４００、ＥＦＫＡポリマー４０１、ＥＦＫＡポリマー４５０」、サンノプコ製「ディスパースエイド６、ディスパースエイド８、ディスパースエイド１５、ディスパースエイド９１００」等の高分子分散剤、ＡＤＥＫＡ製「アデカプルロニック（登録商標）Ｌ３１、Ｆ３８、Ｌ４２、Ｌ４４、Ｌ６１、Ｌ６４、Ｆ６８、Ｌ７２、Ｐ９５、Ｆ７７、Ｐ８４、Ｆ８７、Ｐ９４、Ｌ１０１、Ｐ１０３、Ｆ１０８、Ｌ１２１、Ｐ－１２３」、及び三洋化成製「イオネット（商品名）Ｓ－２０」等が挙げられる。また、アクリベースＦＦＳ－６７５２、アクリベースＦＦＳ－１８７も使用できる。 Examples of the polymer compound include "DA-7301" manufactured by Kusumoto Kasei Co., Ltd., "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid group)" manufactured by BYK Chemie, 111 (phosphoric acid dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 167, 170, 190 (polymer copolymer), BYK-P104, P105 (polymer copolymer) EFKA 4047, 4050-4010-4165 (polyurethane type), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (manufactured by EFKA) 6220 (fatty acid polyester), 6750 (azo pigment derivative), Ajisper PB821, PB822, PB880, PB881 manufactured by Ajinomoto Fine Techno, Florene TG-710 (urethane oligomer manufactured by Kyoeisha Chemical Co., Ltd.) )", "Polyflow No. 50E, No. 300 (acrylic copolymer)", Kusumoto Kasei Co., Ltd. "Disparon KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyhydric copolymer)" ether ester), DA-703-50, DA-705, DA-725", Kao Corporation's "Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin "Polycondensate)", "Homogenol L-18 (high molecular weight polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", Japan Manufactured by Lubrizol "22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer containing a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) )”, “Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)” manufactured by Nikko Chemical Co., Ltd., Hinoact T-8000E manufactured by Kawaken Fine Chemicals, organosiloxane polymer manufactured by Shin-Etsu Chemical Co., Ltd. KP341, "W001: Cationic surfactant" manufactured by Yusho, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate , polyethylene glycol distearate, nonionic surfactants such as sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", Morishita Sangyo "EFKA-46, EFKA-47, EFKA-47EA, EFKA" Polymer dispersants such as "Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" made by San Nopco, "ADEKA" made by 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's "Ionet" (Product name) S-20''. Additionally, Acrybase FFS-6752 and Acrybase FFS-187 can also be used.
　また、酸基及び塩基性基を含む両性樹脂も好ましい。両性樹脂としては、酸価が５ｍｇＫＯＨ／ｇ以上で、かつ、アミン価が５ｍｇＫＯＨ／ｇ以上である樹脂が好ましい。
　両性樹脂の市販品としては、例えば、ビックケミー社製のＤＩＳＰＥＲＢＹＫ－１３０、ＤＩＳＰＥＲＢＹＫ－１４０、ＤＩＳＰＥＲＢＹＫ－１４２、ＤＩＳＰＥＲＢＹＫ－１４５、ＤＩＳＰＥＲＢＹＫ－１８０、ＤＩＳＰＥＲＢＹＫ－１８７、ＤＩＳＰＥＲＢＹＫ－１９１、ＤＩＳＰＥＲＢＹＫ－２００１、ＤＩＳＰＥＲＢＹＫ－２０１０、ＤＩＳＰＥＲＢＹＫ－２０１２、ＤＩＳＰＥＲＢＹＫ－２０２５、ＢＹＫ－９０７６、味の素ファインテクノ社製のアジスパーＰＢ８２１、アジスパーＰＢ８２２、及びアジスパーＰＢ８８１等が挙げられる。
　これらの高分子化合物は、１種を単独で用いても、２種以上を併用してもよい。 Also preferred are amphoteric resins containing acid groups and basic groups. As the amphoteric resin, a resin having an acid value of 5 mgKOH/g or more and an amine value of 5 mgKOH/g or more is preferable.
Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, and DISPER manufactured by BYK Chemie. BYK-2001, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajisper PB821, Ajisper PB822, and Ajisper PB881 manufactured by Ajinomoto Fine Techno.
These polymer compounds may be used alone or in combination of two or more.
　なお、高分子化合物としては、例えば、特開２０１３－２４９４１７号公報の段落０１２７～０１２９に記載の高分子化合物を参照でき、これらの内容は本明細書に組み込まれる。 Note that as the polymer compound, for example, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A-2013-249417, the contents of which are incorporated herein.
　また、分散剤としては、上記の高分子化合物以外に、特開２０１０－１０６２６８号公報の段落００３７～０１１５（対応するＵＳ２０１１／０１２４８２４の段落００７５～０１３３欄）のグラフト共重合体が挙げられ、これらの内容は援用でき、本明細書に組み込まれる。
　また、上記以外にも、特開２０１１－１５３２８３号公報の段落００２８～００８４（対応するＵＳ２０１１／０２７９７５９の段落００７５～０１３３欄）の酸基が連結基を介して結合してなる側鎖構造を含む構成成分を含む高分子化合物が挙げられ、これらの内容は援用でき、本明細書に組み込まれる。 In addition to the above-mentioned polymer compounds, examples of dispersants include graft copolymers described in paragraphs 0037 to 0115 of JP-A No. 2010-106268 (corresponding columns 0075 to 0133 of US 2011/0124824). The contents of the following are incorporated herein by reference.
In addition to the above, it also includes a side chain structure in which acid groups are bonded via a linking group as described in paragraphs 0028 to 0084 of JP 2011-153283 (corresponding columns 0075 to 0133 of US 2011/0279759). Examples include polymeric compounds containing constituent components, the contents of which are incorporated herein by reference.
　また、分散剤としては、特開２０１６－１０９７６３号公報の段落００３３～００４９に記載された樹脂も挙げられ、この内容は本明細書に組み込まれる。 Further, examples of the dispersant include resins described in paragraphs 0033 to 0049 of JP-A No. 2016-109763, the content of which is incorporated herein.
（アルカリ可溶性樹脂）
　本明細書において、アルカリ可溶性樹脂とは、アルカリ可溶性を促進する基（以下、単に「アルカリ可溶性基」ともいう。例えば、カルボン酸基などの酸基が挙げられる。）を含む樹脂を意図し、既に説明した分散剤とは異なる樹脂を意図する。
　酸基としては、カルボキシル基、リン酸基、スルホ基及びフェノール性ヒドロキシ基等が挙げられる。
　アルカリ可溶性樹脂は、酸基を側鎖に有する繰り返し単位を含むのが好ましい。
　酸基を側鎖に有する繰り返し単位としては、例えば、後述の式（２ＲＢ）で表される繰り返し単位が挙げられる。
　第２樹脂が酸基を側鎖に有する繰り返し単位を含む場合、その含有量としては、樹脂の全繰り返し単位に対して、１～４０質量％が好ましく、１～３０質量％がより好ましく、５～３０質量％が更に好ましい。 (Alkali-soluble resin)
In the present specification, the alkali-soluble resin refers to a resin containing a group that promotes alkali solubility (hereinafter also simply referred to as an "alkali-soluble group"; for example, an acid group such as a carboxylic acid group), Different resins than the dispersants already described are contemplated.
Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups.
The alkali-soluble resin preferably contains a repeating unit having an acid group in its side chain.
Examples of the repeating unit having an acid group in its side chain include a repeating unit represented by the below-mentioned formula (2RB).
When the second resin contains a repeating unit having an acid group in its side chain, the content thereof is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, based on the total repeating units of the resin. More preferably 30% by mass.
　アルカリ可溶性樹脂としては、例えば、ポリヒドロキシスチレン樹脂、ポリシロキサン樹脂、（メタ）アクリル樹脂、（メタ）アクリルアミド樹脂、（メタ）アクリル／（メタ）アクリルアミド共重合体樹脂、エポキシ系樹脂、及びポリイミド樹脂等が挙げられる。 Examples of alkali-soluble resins include polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic/(meth)acrylamide copolymer resins, epoxy resins, and polyimide resins. etc.
　アルカリ可溶性樹脂としては、例えば、不飽和カルボン酸とエチレン性不飽和化合物の共重合体が挙げられる。
　不飽和カルボン酸としては特に制限されないが、（メタ）アクリル酸、クロトン酸、及びビニル酢酸等のモノカルボン酸類；イタコン酸、マレイン酸、及びフマル酸等のジカルボン酸、又はその酸無水物；並びに、フタル酸モノ（２－（メタ）アクリロイロキシエチル）等の多価カルボン酸モノエステル類；等が挙げられる。 Examples of the alkali-soluble resin include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
Unsaturated carboxylic acids are not particularly limited, but include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinyl acetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or their acid anhydrides; , polyhydric carboxylic acid monoesters such as mono(2-(meth)acryloyloxyethyl) phthalate; and the like.
　共重合可能なエチレン性不飽和化合物としては、（メタ）アクリル酸メチル等が挙げられる。また、特開２０１０－０９７２１０号公報の段落００２７、及び特開２０１５－０６８８９３号公報の段落００３６～００３７に記載の化合物も使用でき、上記の内容は本明細書に組み込まれる。 Examples of copolymerizable ethylenically unsaturated compounds include methyl (meth)acrylate and the like. Further, compounds described in paragraph 0027 of JP-A No. 2010-097210 and paragraphs 0036 to 0037 of JP-A No. 2015-068893 can also be used, and the above content is incorporated into the present specification.
　アルカリ可溶性樹脂としては、本発明の効果がより優れる点で、硬化性基を含むアルカリ可溶性樹脂も好ましい。
　上記硬化性基としては、上述の高分子化合物が含んでいてもよい硬化性基が同様に挙げられ、好ましい範囲も同様である。
　硬化性基を含むアルカリ可溶性樹脂の一態様としては、側鎖にエチレン性不飽和基を含むアクリル樹脂が挙げられる。側鎖にエチレン性不飽和基を含むアクリル樹脂は、例えば、カルボン酸基を含むアクリル樹脂のカルボン酸基に、グリシジル基又は脂環式エポキシ基を含むエチレン性不飽和化合物を付加反応させて得られる。
　硬化性基を含むアルカリ可溶性樹脂としては、硬化性基を側鎖に有するアルカリ可溶性樹脂等が好ましい。 As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferable since the effects of the present invention are more excellent.
Examples of the curable group include the curable groups that the above-mentioned polymer compound may contain, and the preferred ranges are also the same.
One embodiment of the alkali-soluble resin containing a curable group includes an acrylic resin containing an ethylenically unsaturated group in the side chain. An acrylic resin containing an ethylenically unsaturated group in the side chain can be obtained by, for example, adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to the carboxylic acid group of an acrylic resin containing a carboxylic acid group. It will be done.
As the alkali-soluble resin containing a curable group, an alkali-soluble resin having a curable group in a side chain is preferable.
　アルカリ可溶性樹脂は、ＣｌｏｇＰ値が１．０以上の化合物に由来する繰り返し単位を含んでいるのも好ましい。
　上記ＣｌｏｇＰ値としては、なかでも、１．０～８．０であるのが好ましい。ＣｌｏｇＰ値の定義については、既述のとおりである。 It is also preferable that the alkali-soluble resin contains a repeating unit derived from a compound having a ClogP value of 1.0 or more.
The above ClogP value is preferably 1.0 to 8.0. The definition of the ClogP value is as described above.
　ＣｌｏｇＰ値が１．０以上の化合物に由来する繰り返しとしては、（メタ）アクリレートに由来する繰り返し単位が好ましい。
　（メタ）アクリレートに由来する繰り返し単位としては、例えば、後述の式（２ＲＡ）で表される繰り返し単位が挙げられる。また、（メタ）アクリレートに由来する繰り返し単位は、置換基として水酸基を有しているのも好ましい。
　アルカリ可溶性樹脂が（メタ）アクリレートに由来する繰り返し単位を含む場合、その含有量としては、樹脂の全繰り返し単位に対して、３０質量％以上が好ましく、６０質量％以上がより好ましく、７０質量％以上が更に好ましく、８０質量％以上が特に好ましい。なお、上限値としては、例えば、９９質量％以下が好ましく、９５質量％以下がより好ましい。 As the repeating unit derived from a compound having a ClogP value of 1.0 or more, a repeating unit derived from (meth)acrylate is preferable.
Examples of the repeating unit derived from (meth)acrylate include a repeating unit represented by formula (2RA) described below. Moreover, it is also preferable that the repeating unit derived from (meth)acrylate has a hydroxyl group as a substituent.
When the alkali-soluble resin contains repeating units derived from (meth)acrylate, the content thereof is preferably 30% by mass or more, more preferably 60% by mass or more, and 70% by mass based on the total repeating units of the resin. The above is more preferable, and 80% by mass or more is particularly preferable. In addition, as an upper limit, 99 mass % or less is preferable, and 95 mass % or less is more preferable, for example.
　アルカリ可溶性樹脂としては、本発明の遮光膜が形成され易い点で、下記式（２ＲＡ）で表される繰り返し単位及び下記式（２ＲＢ）で表される繰り返し単位を含み、且つ、式（２ＲＡ）で表される繰り返し単位の含有量が、樹脂の全繰り返し単位に対して３０質量％以上（好ましくは６０質量％以上、より好ましくは７０質量％以上、更に好ましくは８０質量％以上）である樹脂が好ましい。 The alkali-soluble resin contains a repeating unit represented by the following formula (2RA) and a repeating unit represented by the following formula (2RB), and has the formula (2RA) in that the light-shielding film of the present invention is easily formed. A resin in which the content of repeating units represented by is 30% by mass or more (preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more) based on the total repeating units of the resin. is preferred.
　式（２ＲＡ）中、Ｒ１ａは、水素原子又はメチル基を表す。
　Ｒ２ａは、置換基を有していてもよい炭素数１～１２の直鎖状若しくは分岐鎖状のアルキル基又は置換基を有していてもよい炭素数７～１８のアラルキル基を表す。
　Ｒ２ａで表されるアルキル基の炭素数としては、１～８が好ましく、２～６がより好ましく、３～４が更に好ましい。また、直鎖状のアルキル基が好ましい。
　Ｒ２ａで表されるアラルキル基の炭素数としては、７～１８が好ましく、７～１２がより好ましく、７～１０が更に好ましい。
　また、Ｒ２ａで表されるアルキル基及びアラルキル基が有していてもよい置換基としては特に制限されないが、例えば、水酸基が挙げられる。 In formula (2RA), R 1a represents a hydrogen atom or a methyl group.
R 2a represents a linear or branched alkyl group having 1 to 12 carbon atoms which may have a substituent or an aralkyl group having 7 to 18 carbon atoms which may have a substituent.
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. Moreover, a linear alkyl group is preferable.
The number of carbon atoms in the aralkyl group represented by R 2a is preferably 7 to 18, more preferably 7 to 12, and even more preferably 7 to 10.
Furthermore, the substituents that the alkyl group and aralkyl group represented by R 2a may have are not particularly limited, and include, for example, a hydroxyl group.
　式（２ＲＢ）中、Ｒ１ｂは、水素原子又はメチル基を表す。
　Ｌｂは、単結合又は２価の連結基を表す。
　２価の連結基の種類は特に制限されず、例えば、２価の炭化水素基（２価の飽和炭化水素基であっても、２価の芳香族炭化水素基であってもよい。２価の飽和炭化水素基は、直鎖状、分岐鎖状、及び環状のいずれであってもよく、炭素数１～１０が好ましく、例えば、アルキレン基が挙げられる。また、２価の芳香族炭化水素基は、炭素数５～１０が好ましく、例えば、フェニレン基が挙げられる。それ以外にも、アルケニレン基及びアルキニレン基であってもよい。）、２価の複素環基、－Ｏ－、－Ｓ－、－ＳＯ２－、－ＮＲＡ－、－ＣＯ－（－Ｃ（＝Ｏ）－）、－ＣＯＯ－（－Ｃ（＝Ｏ）Ｏ－）、－ＮＲＡ－ＣＯ－、－ＳＯ３－、－ＳＯ２ＮＲＡ－、及び、これらを２種以上組み合わせた基が挙げられる。ここで、ＲＡは、水素原子又はアルキル基（好ましくは炭素数１～１０）を表す。 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 the divalent linking group is not particularly limited, and for example, a divalent hydrocarbon group (which may be a divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group). The saturated hydrocarbon group may be linear, branched, or cyclic, and preferably has 1 to 10 carbon atoms, such as an alkylene group.Also, divalent aromatic hydrocarbon The group preferably has 5 to 10 carbon atoms, and includes, for example, a phenylene group.Alkenylene groups and alkynylene groups may also be used), divalent heterocyclic groups, -O-, -S -, -SO 2 -, -NR A -, -CO- (-C(=O)-), -COO- (-C(=O)O-), -NR A -CO-, -SO 3 - , -SO 2 NR A -, and a combination of two or more thereof. Here, R A represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
　式（２ＲＡ）で表される繰り返し単位の含有量は、樹脂の全繰り返し単位に対して、３０質量％以上が好ましく、６０質量％以上がより好ましく、７０質量％以上が更に好ましく、８０質量％以上が特に好ましい。上限は特に制限されないが、９９質量％以下が好ましく、９０質量％以下がより好ましい。
　式（２ＲＢ）で表される繰り返し単位の含有量は、樹脂の全繰り返し単位に対して、１～４０質量％が好ましく、１～３０質量％がより好ましく、５～３０質量％が更に好まく、５～２５質量％が特に好ましい。 The content of the repeating unit represented by formula (2RA) is preferably 30% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and 80% by mass, based on the total repeating units of the resin. The above is particularly preferable. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less.
The content of the repeating unit represented by formula (2RB) is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 30% by mass, based on the total repeating units of the resin. , 5 to 25% by weight is particularly preferred.
　式（２ＲＡ）で表される繰り返し単位及び式（２ＲＢ）で表される繰り返し単位を含むアルカリ可溶性樹脂は、上記以外の他の繰り返し単位を含んでいてもよい。
　他の繰り返し単位としては、硬化性基を有する繰り返し単位が挙げられる。
　上記硬化性基としては、上述の高分子化合物が含んでいてもよい硬化性基が同様に挙げられ、好ましい範囲も同様である。
　アルカリ可溶性樹脂が硬化性基を有する繰り返し単位を含む場合、その含有量としては、樹脂の全繰り返し単位に対して、３～４０質量％が好ましく、５～３０質量％がより好ましい。 The alkali-soluble resin containing the repeating unit represented by the formula (2RA) and the repeating unit represented by the formula (2RB) may contain other repeating units other than the above.
Other repeating units include repeating units having a curable group.
Examples of the curable group include the curable groups that the above-mentioned polymer compound may contain, and the preferred ranges are also the same.
When the alkali-soluble resin contains a repeating unit having a curable group, the content thereof is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, based on the total repeating units of the resin.
　また、アルカリ可溶性樹脂は、式（２ＲＡ）で表される繰り返し単位として、式（２ＲＡ－１）で表される繰り返し単位と式（２ＲＡ－２）で表される繰り返し単位とを含む構成であるのも好ましい。
　式（２ＲＡ－１）で表される繰り返し単位とは、上記式（２ＲＡ）で表される繰り返し単位において、Ｒ２ａが無置換の炭素数１～１２の直鎖状若しくは分岐鎖状のアルキル基を表す態様である。
　また、式（２ＲＡ－２）で表される繰り返し単位とは、上記式（２ＲＡ）で表される繰り返し単位において、Ｒ２ａが水酸基を含む置換基を有する、炭素数１～１２の直鎖状若しくは分岐鎖状のアルキル基を表すか、又は、置換基を有していてもよい炭素数７～１８のアラルキル基を表す態様である。
　アルカリ可溶性樹脂が式（２ＲＡ－１）で表される繰り返し単位と式（２ＲＡ－２）で表される繰り返し単位とを含む構成である場合、式（２ＲＡ－１）で表される繰り返し単位の含有量としては、樹脂の全繰り返し単位に対して、６０～９０質量％であるのが好ましく、式（２ＲＡ－２）で表される繰り返し単位の含有量としては、樹脂の全繰り返し単位に対して、２～１５質量％であるのが好ましい。 Furthermore, the alkali-soluble resin has a structure including a repeating unit represented by formula (2RA-1) and a repeating unit represented by formula (2RA-2) as the repeating unit represented by formula (2RA). is also preferable.
The repeating unit represented by formula (2RA-1) is a repeating unit represented by formula (2RA) above, in which R 2a is an unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms. This is an aspect that represents.
Furthermore, the repeating unit represented by formula (2RA-2) is a linear unit having 1 to 12 carbon atoms in which R 2a has a substituent containing a hydroxyl group in the repeating unit represented by formula (2RA) above. or a branched alkyl group, or an aralkyl group having 7 to 18 carbon atoms which may have a substituent.
When the alkali-soluble resin has a structure including a repeating unit represented by formula (2RA-1) and a repeating unit represented by formula (2RA-2), the repeating unit represented by formula (2RA-1) is The content is preferably 60 to 90% by mass based on the total repeating units of the resin, and the content of the repeating unit represented by formula (2RA-2) is preferably 60 to 90% by mass based on the total repeating units of the resin. The amount is preferably 2 to 15% by mass.
　アルカリ可溶性樹脂の具体例としては、例えば、以下に示す樹脂が挙げられるが、これに制限されない。
　下記表１中の「共重合成分種」は、ポリマーに含まれる繰り返し単位の種類を表す。「共重合成分比（質量％）」は、ポリマーの全繰り返し単位に対する、各繰り返し単位の含有量（質量％）を表す。 Specific examples of the alkali-soluble resin include, but are not limited to, the following resins.
"Copolymerization component" in Table 1 below represents the type of repeating unit contained in the polymer. "Copolymerization component ratio (mass%)" represents the content (mass%) of each repeating unit with respect to all repeating units of the polymer.
　以下に、表１中に示される各ポリマーを構成する繰り返し単位の原料モノマーを示す。 The raw material monomers of the repeating units constituting each polymer shown in Table 1 are shown below.
　アルカリ可溶性樹脂の酸価としては、０～１５０ｍｇＫＯＨ／ｇが好ましく、２０～１００ｍｇＫＯＨ／ｇがより好ましく、４０～９０ｍｇＫＯＨ／ｇが更に好ましく、６０～９０ｍｇＫＯＨ／ｇが最も好ましい。
　アルカリ可溶性樹脂の重量平均分子量としては、５，０００～１００，０００が好ましく、８，０００～８０，０００がより好ましく、１５，０００～４０，０００が更に好ましく、１８，０００～２５，０００が特に好ましい。
　アルカリ可溶性樹脂のガラス転移温度としては、－２０～１２０℃が好ましく、－２０～１１０℃が好ましく、－５～８０℃がより好ましく、０～７０℃が更に好ましい。
　ガラス転移温度は、ＤＳＣ　３５００　Ｓｉｒｉｕｓ（Ｎｅｔｚｓｃｈ社製）により測定できる。 The acid value of the alkali-soluble resin is preferably 0 to 150 mgKOH/g, more preferably 20 to 100 mgKOH/g, even more preferably 40 to 90 mgKOH/g, and most preferably 60 to 90 mgKOH/g.
The weight average molecular weight of the alkali-soluble resin is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, even more preferably 15,000 to 40,000, and even more preferably 18,000 to 25,000. Particularly preferred.
The glass transition temperature of the alkali-soluble resin is preferably -20 to 120°C, preferably -20 to 110°C, more preferably -5 to 80°C, and even more preferably 0 to 70°C.
The glass transition temperature can be measured using DSC 3500 Sirius (manufactured by Netzsch).
　組成物中におけるアルカリ可溶性樹脂の含有量としては特に制限されないが、組成物の全固形分に対して、１～４０質量％が好ましく、２～３０質量％がより好ましく、５～２５質量％が更に好ましい。
　アルカリ可溶性樹脂は１種を単独で用いても、２種以上を併用してもよい。２種以上のアルカリ可溶性樹脂を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 The content of the alkali-soluble resin in the composition is not particularly limited, but is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and 5 to 25% by mass based on the total solid content of the composition. More preferred.
One type of alkali-soluble resin may be used alone, or two or more types may be used in combination. When two or more types of alkali-soluble resins are used together, the total content is preferably within the above range.
　なお、組成物中における樹脂（アルカリ可溶性樹脂及び分散剤を含む。）の含有量としては、特に制限されないが、例えば、３～７０質量％が好ましく、９～５０質量％がより好ましく、１０～４０質量％が更に好ましい。 The content of the resin (including an alkali-soluble resin and a dispersant) in the composition is not particularly limited, but is preferably 3 to 70% by mass, more preferably 9 to 50% by mass, and 10 to 50% by mass. 40% by mass is more preferred.
＜重合開始剤＞
　組成物は、重合開始剤を含んでもよい。
　重合開始剤は特に制限されず、公知の重合開始剤を使用できる。重合開始剤としては、例えば、光重合開始剤及び熱重合開始剤等が挙げられ、光重合開始剤が好ましい。なお、重合開始剤としては、いわゆるラジカル重合開始剤が好ましい。 <Polymerization initiator>
The composition may also include a polymerization initiator.
The polymerization initiator is not particularly limited, and any known polymerization initiator can be used. Examples of the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, with photopolymerization initiators being preferred. In addition, as the polymerization initiator, a so-called radical polymerization initiator is preferable.
　熱重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）、３－カルボキシプロピオニトリル、アゾビスマレノニトリル、及びジメチル－（２，２’）－アゾビス（２－メチルプロピオネート）［Ｖ－６０１］等のアゾ化合物、並びに、過酸化ベンゾイル、過酸化ラウロイル、及び過硫酸カリウム等の有機過酸化物が挙げられる。
　重合開始剤の具体例としては、例えば、加藤清視著「紫外線硬化システム」（株式会社総合技術センター発行：平成元年）の第６５～１４８頁に記載されている重合開始剤等を挙げられる。 Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismarenonitrile, and dimethyl-(2,2')-azobis(2- Examples include azo compounds such as methyl propionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
Specific examples of the polymerization initiator include those described on pages 65 to 148 of "Ultraviolet Curing System" by Kiyoshi Kato (Published by Sogo Gijutsu Center Co., Ltd., 1989). .
　光重合開始剤としては、重合性化合物の重合を開始できれば特に制限されず、公知の光重合開始剤を使用できる。光重合開始剤としては、例えば、紫外線領域から可視光領域に対して感光性を有する光重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよく、重合性化合物の種類に応じてカチオン重合を開始させるような開始剤であってもよい。 The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and any known photopolymerization initiator can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from the ultraviolet region to the visible light region is preferable. Further, the activator may be an activator that generates active radicals by having some effect with the photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of polymerizable compound.
　光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を含む化合物、オキサジアゾール骨格を含む化合物、等）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、アミノアセトフェノン化合物、及びヒドロキシアセトフェノン等が挙げられる。
　光重合開始剤の具体例としては、例えば、特開２０１３－０２９７６０号公報の段落０２６５～０２６８を参酌でき、この内容は本明細書に組み込まれる。 Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Examples include oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.
As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A No. 2013-029760 can be referred to, the contents of which are incorporated herein.
　光重合開始剤としては、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、及び特許第４２２５８９８号公報に記載のアシルホスフィン系開始剤が挙げられる。
　ヒドロキシアセトフェノン化合物としては、例えば、Ｏｍｎｉｒａｄ－１８４、Ｏｍｎｉｒａｄ－１１７３、Ｏｍｎｉｒａｄ－５００、Ｏｍｎｉｒａｄ－２９５９、及びＯｍｎｉｒａｄ－１２７（商品名：いずれもＩＧＭ　ＲＥＳＩＮＳ　Ｂ．Ｖ．製）が挙げられる。
　アミノアセトフェノン化合物としては、例えば、市販品であるＯｍｎｉｒａｄ－９０７、Ｏｍｎｉｒａｄ－３６９、又はＯｍｎｉｒａｄ－３７９ＥＧ（商品名：いずれもＩＧＭ　ＲＥＳＩＮＳ　Ｂ．Ｖ．製）が挙げられる。アミノアセトフェノン化合物としては、波長３６５ｎｍ又は波長４０５ｎｍ等の長波光源に吸収波長がマッチングされた特開２００９－１９１１７９公報に記載の化合物も挙げられる。
　アシルホスフィン化合物としては、市販品であるＯｍｎｉｒａｄ－８１９、又はＯｍｎｉｒａｄ－ＴＰＯ（商品名：いずれもＩＧＭ　ＲＥＳＩＮＳ　Ｂ．Ｖ．製）が挙げられる。 Examples of the photopolymerization initiator include the aminoacetophenone initiator described in JP-A-10-291969 and the acylphosphine initiator 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 the aminoacetophenone compound include commercially available products Omnirad-907, Omnirad-369, and Omnirad-379EG (trade names: all manufactured by IGM RESINS BV). Examples of the aminoacetophenone compound include compounds described in JP-A No. 2009-191179 whose absorption wavelength is matched to a long-wave light source such as a wavelength of 365 nm or 405 nm.
Examples of the acylphosphine compound include commercially available Omnirad-819 and Omnirad-TPO (trade names: both manufactured by IGM RESINS BV).
（オキシム化合物）
　光重合開始剤として、オキシムエステル系重合開始剤（オキシム化合物）が好ましい。特にオキシム化合物は高感度で重合効率が高く、組成物中における遮光顔料の含有量を高く設計しやすいため好ましい。
　オキシム化合物としては、例えば、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、又は特開２００６－３４２１６６号公報に記載の化合物が挙げられる。
　オキシム化合物としては、例えば、３－ベンゾイロキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイロキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オン等が挙げられる。
　また、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１６５３－１６６０、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１５６－１６２、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年）ｐｐ．２０２－２３２、特開２０００－０６６３８５号公報に記載の化合物、特開２０００－０８００６８号公報、特表２００４－５３４７９７号公報、及び特開２００６－３４２１６６号公報の各公報に記載の化合物等も挙げられる。
　市販品ではＩＲＧＡＣＵＲＥ－ＯＸＥ０１（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３（ＢＡＳＦ社製）、及びＩＲＧＡＣＵＲＥ－ＯＸＥ０４（ＢＡＳＦ社製）も挙げられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－７３０、アデカアークルズＮＣＩ－８３１、アデカアークルズＮＣＩ－９３０（ＡＤＥＫＡ社製）、及びＮ－１９１９（カルバゾール・オキシムエステル骨格含有光開始剤（ＡＤＥＫＡ社製））も挙げられる。また、Ｏｍｎｉｒａｄ１３１６（ＩＧＭ社）も挙げられる。 (oxime compound)
As the photopolymerization initiator, an oxime ester polymerization initiator (oxime compound) is preferable. In particular, oxime compounds are preferred because they have high sensitivity and high polymerization efficiency, and it is easy to design a high content of light-shielding pigment in the composition.
Examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166.
Examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Examples include oxyimino-1-phenylpropan-1-one.
Also, J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP 2000-066385, JP 2000-080068, JP 2004-534797, and JP 2006-342166, etc. It will be done.
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). In addition, TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), ADEKA ARCLES NCI-730, ADEKA ARCLES NCI-831, ADEKA ARCLES NCI-930 (manufactured by ADEKA), and N-1919 (carbazole・An oxime ester skeleton-containing photoinitiator (manufactured by ADEKA) can also be mentioned. Another example is Omnirad 1316 (IGM).
　また上記以外のオキシム化合物としては、カルバゾールＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物；ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号公報に記載の化合物；色素部位にニトロ基が導入された特開２０１０－０１５０２５号公報及び米国特許公開２００９－２９２０３９号記載の化合物；国際公開第２００９－１３１１８９号公報に記載のケトオキシム化合物；及びトリアジン骨格とオキシム骨格を同一分子内に含む米国特許７５５６９１０号公報に記載の化合物；４０５ｎｍに吸収極大を有しｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報記載の化合物；等が挙げられる。
　例えば、特開２０１３－０２９７６０号公報の段落０２７４～０２７５を参酌でき、この内容は本明細書に組み込まれる。
　具体的には、オキシム化合物としては、下記式（ＯＸ－１）で表される化合物が好ましい。なお、オキシム化合物のＮ－Ｏ結合が（Ｅ）体のオキシム化合物であっても、（Ｚ）体のオキシム化合物であっても、（Ｅ）体と（Ｚ）体との混合物であってもよい。 In addition, examples of oxime compounds other than the above include compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced at the benzophenone moiety; Compounds described in JP-A No. 2010-015025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety; Ketoxime compounds described in International Publication No. 2009-131189; and compounds in which the triazine skeleton and the oxime skeleton are the same Examples include the compound described in US Pat. No. 7,556,910, which is contained in the molecule; the compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-line light source; and the like.
For example, paragraphs 0274 to 0275 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. In addition, even if the N-O bond of the oxime compound is an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form, good.
　式（ＯＸ－１）中、Ｒ及びＢはそれぞれ独立に１価の置換基を表し、Ａは２価の有機基を表し、Ａｒはアリール基を表す。
　式（ＯＸ－１）中、Ｒで表される１価の置換基としては、１価の非金属原子団が好ましい。
　１価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、及びアリールチオカルボニル基等が挙げられる。また、これらの基は、１以上の置換基を有していてもよい。また、前述した置換基は、更に他の置換基で置換されていてもよい。
　置換基としては、ハロゲン原子、アリールオキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、及びアリール基等が挙げられる。
　式（ＯＸ－１）中、Ｂで表される１価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は複素環カルボニル基が好ましく、アリール基、又は複素環基がより好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
　式（ＯＸ－１）中、Ａで表される２価の有機基としては、炭素数１～１２のアルキレン基、シクロアルキレン基、又はアルキニレン基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。 In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the above-mentioned substituents may be further substituted with other substituents.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group, and more preferably an aryl group or a heterocyclic group. . These groups may have one or more substituents. Examples of the substituent include the substituents described above.
In formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
　光重合開始剤としては、フッ素原子を含むオキシム化合物も挙げられる。フッ素原子を含むオキシム化合物としては、例えば、特開２０１０－２６２０２８号公報に記載の化合物；特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０；及び特開２０１３－１６４４７１号公報記載の化合物（Ｃ－３）；等が挙げられる。この内容は本明細書に組み込まれる。 Examples of photopolymerization initiators include oxime compounds containing fluorine atoms. Examples of oxime compounds containing a fluorine atom include compounds described in JP-A No. 2010-262028; compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852; and compounds described in JP-A No. 2013-164471. Compound (C-3); and the like. This content is incorporated herein.
　重合開始剤として、下記式（１）～（４）で表される化合物も挙げられる。 Examples of the polymerization initiator include compounds represented by the following formulas (1) to (4).
　式（１）において、Ｒ１及びＲ２は、それぞれ独立に、炭素数１～２０のアルキル基、炭素数４～２０の脂環式炭化水素基、炭素数６～３０のアリール基、又は炭素数７～３０のアリールアルキル基を表し、Ｒ１及びＲ２がフェニル基の場合、フェニル基同士が結合してフルオレン基を形成してもよく、Ｒ３及びＲ４は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を示す。 In formula (1), R 1 and R 2 are each independently 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 a carbon represents an arylalkyl group of 7 to 30, and when R 1 and R 2 are phenyl groups, the phenyl groups may combine with each other to form a fluorene group, and R 3 and R 4 each independently represent hydrogen. represents an atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond or a carbonyl group. shows.
　式（２）において、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、式（１）におけるＲ１、Ｒ２、Ｒ３、及びＲ４と同義であり、Ｒ５は、－Ｒ６、－ＯＲ６、－ＳＲ６、－ＣＯＲ６、－ＣＯＮＲ６Ｒ６、－ＮＲ６ＣＯＲ６、－ＯＣＯＲ６、－ＣＯＯＲ６、－ＳＣＯＲ６、－ＯＣＳＲ６、－ＣＯＳＲ６、－ＣＳＯＲ６、－ＣＮ、ハロゲン原子、又は水酸基を表し、Ｒ６は、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基、又は炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を表し、ａは０～４の整数を表す。 In formula (2), R 1 , R 2 , R 3 , and R 4 are synonymous with R 1 , R 2 , R 3 , and R 4 in formula (1), and R 5 is -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN , a halogen atom, or a hydroxyl group, and R 6 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocycle having 4 to 20 carbon atoms. represents a group, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
　式（３）において、Ｒ１は、炭素数１～２０のアルキル基、炭素数４～２０の脂環式炭化水素基、炭素数６～３０のアリール基、又は炭素数７～３０のアリールアルキル基を表し、Ｒ３及びＲ４は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基、又は炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を示す。 In formula (3), R 1 is 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 arylalkyl group having 7 to 30 carbon atoms. R 3 and R 4 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 arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 4 carbon atoms. ~20 heterocyclic groups, and X represents a direct bond or a carbonyl group.
　式（４）において、Ｒ１、Ｒ３、及びＲ４は、式（３）におけるＲ１、Ｒ３、及びＲ４と同義であり、Ｒ５は、－Ｒ６、－ＯＲ６、－ＳＲ６、－ＣＯＲ６、－ＣＯＮＲ６Ｒ６、－ＮＲ６ＣＯＲ６、－ＯＣＯＲ６、－ＣＯＯＲ６、－ＳＣＯＲ６、－ＯＣＳＲ６、－ＣＯＳＲ６、－ＣＳＯＲ６、－ＣＮ、ハロゲン原子、又は水酸基を表し、Ｒ６は、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基、又は炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を表し、ａは０～４の整数を表す。 In formula (4), R 1 , R 3 , and R 4 are synonymous with R 1 , R 3 , and R 4 in formula (3), and R 5 is -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, halogen atom, or hydroxyl group , R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X is , represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
　式（１）及び式（２）で表される化合物としては、例えば、特開２０１４－１３７４６６号公報の段落００７６～００７９に記載された化合物が挙げられる。この内容は本明細書に組み込まれる。 Examples of the compounds represented by formula (1) and formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein.
　また、重合開始剤としては、下記式（１）で表される化合物も好ましい。 Furthermore, as the polymerization initiator, a compound represented by the following formula (1) is also preferable.
　式（１）中、Ｒは、以下の式（１ａ）で表される基を表す。 In formula (1), R represents a group represented by the following formula (1a).
　式（１ａ）中、ｎは、１～５の整数を表す。ｍは、１～６の整数を表す。＊は、結合位置を表す。 In formula (1a), n represents an integer from 1 to 5. m represents an integer from 1 to 6. * represents the bonding position.
　ｍとしては、３又は４が好ましい。
　式（１）で表される化合物は、例えば、特開２０１２－５１９１９１号公報に記載の合成方法に準じて合成できる。 As m, 3 or 4 is preferable.
The compound represented by formula (1) can be synthesized, for example, according to the synthesis method described in JP-A-2012-519191.
　上記組成物に好ましく使用されるオキシム化合物の具体例を以下に示す。
　また、オキシム化合物としては、国際公開第２０１５－０３６９１０号のＴａｂｌｅ１に記載の化合物も挙げられ、上記の内容は本明細書に組み込まれる。 Specific examples of oxime compounds preferably used in the above composition are shown below.
Further, examples of the oxime compound include the compounds described in Table 1 of International Publication No. 2015-036910, the contents of which are incorporated herein.

　オキシム化合物は、３５０～５００ｎｍの波長領域に極大吸収波長を有するのが好ましく、３６０～４８０ｎｍの波長領域に極大吸収波長を有するのがより好ましく、３６５ｎｍ及び４０５ｎｍの波長の吸光度が高いのが更に好ましい。
　オキシム化合物の３６５ｎｍ又は４０５ｎｍにおけるモル吸光係数は、感度の観点から、１，０００～３００，０００が好ましく、２，０００～３００，０００がより好ましく、５，０００～２００，０００が更に好ましい。
　化合物のモル吸光係数は、公知の方法を使用でき、例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチルを用い、０．０１ｇ／Ｌの濃度で測定するのが好ましい。
　光重合開始剤は、必要に応じて２種以上を組み合わせて使用してもよい。 The oxime compound preferably has a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably has a maximum absorption wavelength in a wavelength range of 360 to 480 nm, and even more preferably has high absorbance at wavelengths of 365 nm and 405 nm. .
From the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000.
The molar absorption coefficient of a compound can be determined using a known method. For example, it can be measured using ethyl acetate at a concentration of 0.01 g/L using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian). preferable.
Photopolymerization initiators may be used in combination of two or more types, if necessary.
　また、光重合開始剤としては、特開２００８－２６０９２７号公報の段落００５２、特開２０１０－０９７２１０号公報の段落００３３～００３７、特開２０１５－０６８８９３号公報の段落００４４に記載の化合物も使用でき、上記の内容は本明細書に組み込まれる。 Furthermore, as a photopolymerization initiator, compounds described in paragraph 0052 of JP-A No. 2008-260927, paragraphs 0033 to 0037 of JP-A No. 2010-097210, and paragraph 0044 of JP-A No. 2015-068893 can also be used. , the contents of which are incorporated herein by reference.
　重合開始剤としては、本発明の効果がより優れる点で、オキシムエステル系重合開始剤が好ましく、上述の式（１）で表される化合物がより好ましい。 As the polymerization initiator, an oxime ester polymerization initiator is preferable, and a compound represented by the above formula (1) is more preferable, since the effects of the present invention are more excellent.
　組成物中における重合開始剤の含有量は特に制限されないが、本発明の効果がより優れる点で、組成物の全固形分に対して、０．５～２０質量％が好ましく、１．０～１０質量％がより好ましく、１．５～８質量％が更に好ましい。
　重合開始剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の重合開始剤を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 The content of the polymerization initiator in the composition is not particularly limited, but it is preferably 0.5 to 20% by mass, and 1.0 to 20% by mass, based on the total solid content of the composition, in order to achieve better effects of the present invention. The content is more preferably 10% by weight, and even more preferably 1.5 to 8% by weight.
The polymerization initiators may be used alone or in combination of two or more. When two or more types of polymerization initiators are used together, it is preferable that the total content is within the above range.
＜界面活性剤＞
　組成物は、界面活性剤を含んでいてもよい。界面活性剤は、組成物の塗布性向上に寄与する。
　界面活性剤としては、例えば、シリコーン系界面活性剤、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、及びアニオン系界面活性剤等が挙げられる。
　なかでも、本発明の効果がより優れる点で、シリコーン系界面活性剤が好ましい。 <Surfactant>
The composition may also include a surfactant. The surfactant contributes to improving the coating properties of the composition.
Examples of the surfactant include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.
Among these, silicone surfactants are preferred because they provide better effects of the present invention.
　シリコーン系界面活性剤としては、例えば、シロキサン結合からなる直鎖状ポリマー、並びに、側鎖及び／又は末端に有機基を導入した変性シロキサンポリマー等が挙げられる。 Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into side chains and/or terminals, and the like.
　シリコーン系界面活性剤としては、例えば、ＤＯＷＳＩＬ（登録商標）シリーズのＤＣ３ＰＡ、ＳＨ７ＰＡ、ＤＣ１１ＰＡ、ＳＨ２１ＰＡ、ＳＨ２８ＰＡ、ＳＨ２９ＰＡ、ＳＨ３０ＰＡ、及びＳＨ８４００（以上、東レ・ダウコーニング社製）；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、及び、ＫＦ－６００２（以上、信越シリコーン社製）；Ｆ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、及び、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）；ＢＹＫ３０７、ＢＹＫ３２３、及び、ＢＹＫ３３０（以上、ビックケミー社製）が挙げられる。
　シリコーン系界面活性剤の好適な一態様としては、本発明の効果がより優れる点で、芳香族基変性型シリコーン系界面活性剤（芳香族基を有するシリコーン系界面活性剤）が好ましく、フェニル変性型シリコーン系界面活性剤（フェニル基を有するシリコーン系界面活性剤）がより好ましい。 Examples of silicone surfactants include DOWSIL (registered trademark) series DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (all manufactured by Dow Corning Toray); X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, KF-6000, KF-6004, KP-323, KP-341, KF-6001, and KF-6002 (manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (manufactured by Momentive Performance Materials); BYK307, BYK323, and BYK330 (manufactured by BYK Chemie).
A preferred embodiment of the silicone surfactant is an aromatic group-modified silicone surfactant (a silicone surfactant having an aromatic group), and a phenyl-modified silicone surfactant, since the effects of the present invention are more excellent. type silicone surfactants (silicone surfactants having a phenyl group) are more preferred.
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、及び、同Ｆ７８０（以上、ＤＩＣ（株）製）；フロラードＦＣ４３０、同ＦＣ４３１、及び、同ＦＣ１７１（以上、住友スリーエム（株）製）；サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、及び、同ＫＨ－４０（以上、旭硝子（株）製）；並びに、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、及び、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。
　フッ素系界面活性剤としてブロックポリマーも使用でき、例えば、特開第２０１１－０８９０９０号公報に記載された化合物が挙げられる。 Examples of the fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, F482, F554, and F780 (manufactured by DIC Corporation); Florado FC430, FC431, and FC171 (manufactured by Sumitomo 3M Corporation); Surflon S-382, SC-101 , SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.); and Examples include PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA).
Block polymers can also be used as the fluorosurfactant, and examples thereof include compounds described in JP-A No. 2011-089090.
　組成物が界面活性剤を含む場合、組成物中における界面活性剤の含有量は特に制限されないが、本発明の効果がより優れる点で、組成物の全固形分に対して、０．００１～２．０質量％が好ましく、０．００５～０．５質量％がより好ましく、０．０１～０．１質量％が更に好ましい。
　界面活性剤は、１種を単独で用いても、２種以上を併用してもよい。界面活性剤を２種以上併用する場合は、合計量が上記範囲内であるのが好ましい。 When the composition contains a surfactant, the content of the surfactant in the composition is not particularly limited, but the content of the surfactant in the composition is not particularly limited. It is preferably 2.0% by weight, more preferably 0.005 to 0.5% by weight, and even more preferably 0.01 to 0.1% by weight.
The surfactants 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.
＜溶媒＞
　組成物は、溶媒を含んでいてもよい。
　溶媒は特に制限されず、公知の溶媒を使用でき、例えば、有機溶媒、及び、水が挙げられる。
　組成物中、固形分の含有量は、組成物の全質量に対して、１０～９０質量％が好ましく、１０～５０質量％がより好ましく、１５～５０質量％が更に好ましい。つまり、組成物中における溶媒の含有量としては特に制限されないが、組成物の固形分が上記含有量となるように調整されるのが好ましい。
　溶媒は１種を単独で用いても、２種以上を併用してもよい。２種以上の溶媒を併用する場合には、組成物の全固形分が上記範囲内となるように調整されるのが好ましい。 <Solvent>
The composition may also include a solvent.
The solvent is not particularly limited, and any known solvent can be used, such as organic solvents and water.
The content of solids in the composition is preferably 10 to 90% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 50% by mass, based on the total mass of the composition. That is, although the content of the solvent in the composition is not particularly limited, it is preferable that the solid content of the composition is adjusted to the above content.
One type of solvent may be used alone or two or more types may be used in combination. When two or more types of solvents are used together, it is preferable that the total solid content of the composition is adjusted to fall within the above range.
　有機溶媒としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、３－メトキシプロパノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、３－メトキシプロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、γ－ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸メチル、Ｎ－メチル－２－ピロリドン、及び乳酸エチル等が挙げられるが、これらに制限されない。 Examples of organic solvents include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and acetylacetone. , cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, 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, ethyl acetate, butyl acetate, methyl lactate, N- Examples include, but are not limited to, methyl-2-pyrrolidone and ethyl lactate.
＜エポキシ基を含む化合物（密着剤）＞
　組成物は、エポキシ基を含む化合物を含んでいてもよい。
　エポキシ基を含む化合物は、エポキシ基を１個以上有する化合物が挙げられ、エポキシ基を２個以上有する化合物が好ましい。エポキシ基は１～１００個有するのが好ましい。上限は、例えば、１０個以下でもよく、５個以下でもよい。下限は、２個以上が好ましい。
　なお、エポキシ基を含む化合物は、上述の、分散剤、アルカリ可溶性樹脂、及び重合性化合物とは異なる成分を意図する。 <Compound containing epoxy group (adhesive)>
The composition may include a compound containing an epoxy group.
Examples of the compound containing an epoxy group include compounds having one or more epoxy groups, and preferably compounds having two or more epoxy groups. It is preferable to have 1 to 100 epoxy groups. The upper limit may be, for example, 10 or less, or 5 or less. The lower limit is preferably two or more.
Note that the compound containing an epoxy group is intended to be a component different from the above-mentioned dispersant, alkali-soluble resin, and polymerizable compound.
　エポキシ基を含む化合物のエポキシ当量（＝エポキシ基を含む化合物の分子量／エポキシ基の数）は、５００ｇ／当量以下が好ましく、１００～４００ｇ／当量がより好ましく、１００～３００ｇ／当量が更に好ましい。 The epoxy equivalent of the compound containing an epoxy group (=molecular weight of the compound containing an epoxy group/number of epoxy groups) is preferably 500 g/equivalent or less, more preferably 100 to 400 g/equivalent, and even more preferably 100 to 300 g/equivalent.
　エポキシ基を含む化合物は、低分子化合物（例えば、分子量２０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量２０００以上、ポリマーの場合は、重量平均分子量が２０００以上）でもよい。エポキシ基を含む化合物の重量平均分子量は、２００～１０００００が好ましく、５００～５００００がより好ましい。重量平均分子量の上限は、１００００以下がより好ましく、５０００以下が更に好ましく、３０００以下が特に好ましい。 The compound containing an epoxy group may be a low-molecular compound (e.g., molecular weight less than 2000) or a macromolecule (e.g., molecular weight 2000 or more, in the case of a polymer, the weight average molecular weight is 2000 or more). The weight average molecular weight of the compound containing an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less.
　エポキシ基を含む化合物は、市販品を用いてもよい。例えば、ＥＨＰＥ３１５０（ダイセル製）及びＥＰＩＣＬＯＮ　Ｎ－６９５（ＤＩＣ製）等が挙げられる。また、エポキシ基を含む化合物は、特開２０１３－０１１８６９号公報の段落００３４～００３６、特開２０１４－０４３５５６号公報の段落０１４７～０１５６、及び特開２０１４－０８９４０８号公報の段落００８５～００９２に記載された化合物が挙げられる。これらの内容は、本明細書に組み込まれる。 A commercially available compound may be used as the compound containing an epoxy group. Examples include EHPE3150 (manufactured by Daicel) and EPICLON N-695 (manufactured by DIC). Compounds containing epoxy groups are described in paragraphs 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0092 of JP2014-089408. Examples include compounds that have been Their contents are incorporated herein.
　組成物がエポキシ基を含む化合物を含む場合、組成物中におけるエポキシ基を含む化合物の含有量は、組成物中の全固形分に対して、０．００１～１０質量％が好ましく、０．０１～８質量％がより好ましく、０．０１～６質量％が更に好ましい。
　エポキシ基を含む化合物は、１種を単独で用いても、２種以上を使用してもよい。上記組成物が、エポキシ基を含む化合物を２種類以上含む場合、その合計含有量が上記範囲となるのが好ましい。 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, and 0.01% by mass based on the total solid content in the composition. It is more preferably 8% by mass, and even more preferably 0.01% by mass to 6% by mass.
The compounds containing epoxy groups may be used alone or in combination of two or more. When the composition contains two or more types of compounds containing epoxy groups, the total content thereof is preferably within the above range.
＜シランカップリング剤（密着剤）＞
　組成物はシランカップリング剤を含んでいてもよい。
　シランカップリング剤は、基板上に遮光膜を形成する際に、基板と遮光膜間の密着性を向上させる密着剤として機能する。
　シランカップリング剤とは、分子中に加水分解性基とそれ以外の官能基とを含む化合物である。なお、アルコキシ基等の加水分解性基は、珪素原子に結合している。
　加水分解性基とは、珪素原子に直結し、加水分解反応及び／又は縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基、及びアルケニルオキシ基が挙げられる。加水分解性基が炭素原子を含む場合、その炭素数は６以下が好ましく、４以下がより好ましい。特に、炭素数４以下のアルコキシ基又は炭素数４以下のアルケニルオキシ基が好ましい。
　また、基板上に遮光膜を形成する場合に、シランカップリング剤は基板と遮光膜間の密着性を向上させるため、フッ素原子及び珪素原子（ただし、加水分解性基が結合した珪素原子は除く）を含まないのが好ましく、フッ素原子、珪素原子（ただし、加水分解性基が結合した珪素原子は除く）、珪素原子で置換されたアルキレン基、炭素数８以上の直鎖状アルキル基、及び炭素数３以上の分岐鎖状アルキル基は含まないのが望ましい。
　シランカップリング剤は、（メタ）アクリロイル基等のエチレン性不飽和基を含んでいてもよい。エチレン性不飽和基を含む場合、その数は１～１０個が好ましく、４～８個がより好ましい。なお、エチレン性不飽和基を含むシランカップリング剤（例えば、加水分解性基とエチレン性不飽和基とを含む、分子量２０００以下の化合物）は、上述の重合性化合物に該当しない。 <Silane coupling agent (adhesive agent)>
The composition may also include a silane coupling agent.
The silane coupling agent functions as an adhesive that improves the adhesion between the substrate and the light-shielding film when forming the light-shielding film on the substrate.
A silane coupling agent is a compound containing a hydrolyzable group and other functional groups in its molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
A hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through a hydrolysis reaction and/or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group contains carbon atoms, the number of carbon atoms is preferably 6 or less, 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 is preferred.
In addition, when forming a light-shielding film on a substrate, the silane coupling agent is used to improve the adhesion between the substrate and the light-shielding film. ), and preferably does not contain fluorine atoms, silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and It is preferable not to include a branched alkyl group having 3 or more carbon atoms.
The silane coupling agent may contain an ethylenically unsaturated group such as a (meth)acryloyl group. When containing ethylenically unsaturated groups, the number is preferably 1 to 10, more preferably 4 to 8. Note that a silane coupling agent containing an ethylenically unsaturated group (for example, a compound containing a hydrolyzable group and an ethylenically unsaturated group and having a molecular weight of 2000 or less) does not correspond to the above-mentioned polymerizable compound.
　シランカップリング剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、ビニルトリメトキシシラン、及びビニルトリエトキシシラン等が挙げられる。 Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Examples include vinyltrimethoxysilane and vinyltriethoxysilane.
　組成物がシランカップリング剤を含む場合、組成物中におけるシランカップリング剤の含有量は、組成物中の全固形分に対して、０．１～１０質量％が好ましく、０．５～８質量％がより好ましく、１．０～６質量％が更に好ましい。
　上記組成物は、シランカップリング剤を１種単独で含んでいてもよく、２種以上を含んでいてもよい。組成物がシランカップリング剤を２種以上含む場合は、その合計が上記範囲内であればよい。 When the composition contains a silane coupling agent, the content of the silane coupling agent in the composition is preferably 0.1 to 10% by mass, and 0.5 to 8% by mass, based on the total solid content in the composition. The amount is more preferably 1.0 to 6% by weight, and even more preferably 1.0 to 6% by weight.
The composition may contain one type of silane coupling agent alone, or may contain two or more types of silane coupling agents. When the composition contains two or more types of silane coupling agents, the total may be within the above range.
＜紫外線吸収剤＞
　組成物は、紫外線吸収剤を含んでいてもよい。これにより、露光して形成される遮光膜のパターンの形状をより優れた（精細な）形状にできる。
　紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、及びトリアジン系の紫外線吸収剤が挙げられる。また、特開２０１２－０６８４１８号公報の段落０１３７～０１４２（対応するＵＳ２０１２／００６８２９２の段落０２５１～０２５４）の化合物も挙げられ、これらの内容が援用でき、本明細書に組み込まれる。
　他にジエチルアミノ－フェニルスルホニル系紫外線吸収剤（大東化学社製、商品名：ＵＶ－５０３）等も挙げられる。
　紫外線吸収剤としては、特開２０１２－０３２５５６号公報の段落０１３４～０１４８に例示される化合物も挙げられる。
　組成物が紫外線吸収剤を含む場合、紫外線吸収剤の含有量は、組成物の全固形分に対して、０．００１～１５質量％が好ましく、０．０１～１０質量％がより好ましく、０．１～５質量％が更に好ましい。 <Ultraviolet absorber>
The composition may also include a UV absorber. Thereby, the shape of the pattern of the light-shielding film formed by exposure can be made into a more excellent (fine) shape.
Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. Further, compounds in paragraphs 0137 to 0142 of JP2012-068418 (corresponding paragraphs 0251 to 0254 of US2012/0068292) are also mentioned, and the contents thereof can be cited and incorporated herein.
Other examples include diethylamino-phenylsulfonyl ultraviolet absorbers (manufactured by Daito Kagaku Co., Ltd., trade name: UV-503).
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP-A No. 2012-032556.
When the composition contains a UV absorber, the content of the UV absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, based on the total solid content of the composition. .1 to 5% by mass is more preferred.
＜その他の着色剤＞
　組成物は、任意の着色剤を含んでいてもよく、顔料、染料又は赤外線吸収剤等から選択できる。但し、上述したカーボンブラック、硫酸バリウム、及び、金属含有粒子以外の着色剤である。 <Other colorants>
The composition may include optional colorants, which can be selected from pigments, dyes, infrared absorbers, and the like. However, the colorant is other than the above-mentioned carbon black, barium sulfate, and metal-containing particles.
＜その他の任意成分＞
　組成物は、上述した成分以外のその他の任意成分を更に含んでいてもよい。例えば、重合禁止剤、増感剤、共増感剤、架橋剤、硬化促進剤、フィラー、熱硬化促進剤、可塑剤、希釈剤、及び感脂化剤等が挙げられ、更に、基板表面への密着促進剤及びその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、酸化防止剤、香料、表面張力調整剤、及び連鎖移動剤等）等の公知の添加剤を必要に応じて加えてもよい。
　これらの成分は、例えば、特開２０１２－００３２２５号公報の段落０１８３～０２２８（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落０２３７～０３０９）、特開２００８－２５００７４号公報の段落０１０１～０１０２、段落０１０３～０１０４、段落０１０７～０１０９、及び特開２０１３－１９５４８０号公報の段落０１５９～０１８４等の記載を参酌でき、これらの内容は本明細書に組み込まれる。 <Other optional ingredients>
The composition may further contain other optional components other than those mentioned above. Examples include polymerization inhibitors, sensitizers, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and sensitizing agents. adhesion promoters and other auxiliary agents (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling promoters, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc.) ) may be added as necessary.
These components are described, for example, in paragraphs 0183 to 0228 of JP2012-003225A (corresponding paragraphs 0237 to 0309 of US Patent Application Publication No. 2013/0034812), and paragraph 0101 of JP2008-250074A. -0102, paragraphs 0103-0104, paragraphs 0107-0109, and paragraphs 0159-0184 of JP-A-2013-195480, etc., can be referred to, and the contents thereof are incorporated into the present specification.
〔組成物の製造方法〕
　組成物は、まず、黒色顔料を分散させた分散組成物を製造し、得られた分散組成物を更にその他の成分と混合して組成物とするのが好ましい。
　分散組成物は、黒色顔料、樹脂（分散樹脂）、及び溶媒を混合して調製するのが好ましい。また、分散組成物に重合禁止剤を導入するのも好ましい。
　上記分散組成物は、上記の各成分を公知の混合方法（例えば、撹拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機、又は湿式分散機等を用いた混合方法）により混合して調製できる。
　分散組成物の調製後、上記分散組成物、樹脂（アルカリ可溶性樹脂）、重合性化合物、重合開始剤、及び溶媒を混合して調製できる。
　組成物の調製に際しては、各成分を一括配合してもよいし、各成分をそれぞれ、溶媒に溶解又は分散した後に逐次配合してもよい。また、配合する際の投入順序及び作業条件は特に制限されない。 [Method for producing composition]
It is preferable that the composition is first prepared by producing a dispersion composition in which a black pigment is dispersed, and then the obtained dispersion composition is further mixed with other components to form a composition.
The dispersion composition is preferably prepared by mixing a black pigment, a resin (dispersion resin), and a solvent. It is also preferable to introduce a polymerization inhibitor into the dispersion composition.
The above-mentioned dispersion composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, etc.).
After preparing the dispersion composition, it can be prepared by mixing the dispersion composition, resin (alkali-soluble resin), polymerizable compound, polymerization initiator, and solvent.
When preparing the composition, each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then blended sequentially. Furthermore, the order of addition and working conditions during blending are not particularly limited.
　組成物は、異物の除去及び欠陥の低減等の目的で、フィルタでろ過することが好ましい。フィルタとしては、例えば、従来からろ過用途等に用いられているフィルタであれば特に制限されずに使用できる。例えば、ＰＴＦＥ（ポリテトラフルオロエチレン）等のフッ素樹脂、ナイロン等のポリアミド系樹脂、並びに、ポリエチレン及びポリプロピレン（ＰＰ）等のポリオレフィン系樹脂（高密度、超高分子量を含む）等によるフィルタが挙げられる。中でも、ポリプロピレン（高密度ポリプロピレンを含む）又はナイロンが好ましい。
　フィルタの孔径は、０．１～７．０μｍが好ましく、０．２～２．５μｍがより好ましく、０．２～１．５μｍが更に好ましく、０．３～０．７μｍが特に好ましい。この範囲とすれば、顔料（黒色顔料を含む）のろ過詰まりを抑えつつ、顔料に含まれる不純物及び凝集物等、微細な異物を確実に除去できるようになる。
　組成物は、金属、ハロゲンを含む金属塩、酸、アルカリ等の不純物を含まないことが好ましい。これら材料に含まれる不純物の含有量は、１質量ｐｐｍ以下が好ましく、１質量ｐｐｂ以下がより好ましく、１００質量ｐｐｔ以下が更に好ましく、１０質量ｐｐｔ以下が特に好ましく、実質的に含まないこと（測定装置の検出限界以下であること）が最も好ましい。
　なお、上記不純物は、誘導結合プラズマ質量分析装置（横河アナリティカルシステムズ製、Ａｇｉｌｅｎｔ　７５００ｃｓ型）により測定できる。 The composition is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. As the filter, for example, any filter that has been conventionally used for filtration purposes can be used without particular restriction. Examples include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). . Among these, polypropylene (including high-density polypropylene) or nylon is preferred.
The pore diameter of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, even more preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. Within this range, fine foreign substances such as impurities and aggregates contained in the pigments can be reliably removed while suppressing the clogging of the filtration of pigments (including black pigments).
The composition preferably does not contain impurities such as metals, metal salts containing halogens, acids, and alkalis. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and substantially free of impurities (measured). most preferably below the detection limit of the device).
Note that the above impurities can be measured using an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
［遮光膜の製造方法］
　遮光膜は、硬化膜であるのが好ましい。
　本明細書において「硬化膜」とは、組成物を用いて形成される組成物層に対して露光処理等の硬化処理が施されて形成される膜である。
　以下、遮光膜が硬化膜である場合における、遮光膜（硬化膜）の製造方法について説明する。
　遮光膜の製造方法は、以下の工程を含むのが好ましい。上記工程を経ることで、例えば、パターン状の遮光膜が形成できる。なお、遮光膜をパターン状としない場合、現像工程は実施しなくてもよい。
　以下、各工程について説明する。 [Method for manufacturing light shielding film]
It is preferable that the light shielding film is a cured film.
In this specification, a "cured film" is a film formed by subjecting a composition layer formed using a composition to a curing treatment such as an exposure treatment.
Hereinafter, a method for manufacturing a light-shielding film (cured film) in the case where the light-shielding film is a cured film will be described.
The method for manufacturing a light shielding film preferably includes the following steps. By going through the above steps, for example, a patterned light shielding film can be formed. Note that if the light-shielding film is not patterned, the development step may not be performed.
Each step will be explained below.
〔組成物層形成工程〕
　組成物層形成工程においては、露光に先立ち、支持体等の上に、組成物を付与して組成物の層（組成物層）を形成する。支持体としては、例えば、基板（例えば、シリコン基板）上にＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）又はＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ－Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）等の撮像素子（受光素子）が設けられた固体撮像素子用基板を使用できる。また、支持体上には、必要により、上部の層との密着改良、物質の拡散防止及び基板表面の平坦化等のために下塗り層を設けてもよい。 [Composition layer forming process]
In the composition layer forming step, prior to exposure, a composition is applied onto a support or the like to form a composition layer (composition layer). As the support, for example, a substrate for a solid-state image sensor in which an image sensor (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate) is used. can. Further, an undercoat layer may be provided on the support, if necessary, for improving adhesion with the upper layer, preventing substance diffusion, flattening the substrate surface, and the like.
　支持体上への組成物の適用方法としては、スリット塗布法、インクジェット法、回転塗布法、流延塗布法、ロール塗布法、及びスクリーン印刷法等の各種の塗布方法が挙げられる。組成物層の膜厚は、０．１～１０μｍが好ましく、０．２～５μｍがより好ましく、０．２～３μｍが更に好ましい。支持体上に塗布された組成物層の乾燥（プリベーク）は、ホットプレート及びオーブン等で５０～１４０℃の温度で１０～３００秒で行える。 Examples of methods for applying the composition onto the support include various coating methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, and screen printing. The thickness of the composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.2 to 3 μm. Drying (prebaking) of the composition layer coated on the support can be performed at a temperature of 50 to 140° C. for 10 to 300 seconds using a hot plate, oven, or the like.
〔露光工程〕
　露光工程は、活性光線又は放射線を照射して、組成物層形成工程において形成された組成物層を露光する工程である。露光工程は、具体的には、組成物層形成工程において形成された組成物層に活性光線又は放射線を照射して露光し、組成物層の光照射領域を硬化させる工程である。
　光照射の方法としては特に制限されないが、パターン状の開口部を有するフォトマスクを介して光照射するのが好ましい。
　露光は放射線の照射により行うのが好ましく、露光に際して使用できる放射線としては、特に、ｇ線、ｈ線、及びｉ線等の紫外線が好ましく、光源としては高圧水銀灯が好まれる。照射強度は５～１５００ｍＪ／ｃｍ２が好ましく、１０～１０００ｍＪ／ｃｍ２がより好ましい。
　なお、組成物が、熱重合開始剤を含む場合、上記露光工程において、組成物層を加熱するのも好ましい。加熱の温度として特に制限されないが、８０～２５０℃が好ましい。また、加熱の時間としては特に制限されないが、３０～３００秒が好ましい。
　なお、露光工程において、組成物層を加熱する場合、後述する後加熱工程を兼ねてもよい。言い換えれば、露光工程において、組成物層を加熱する場合、遮光膜の製造方法は後加熱工程を含んでいなくてもよい。 [Exposure process]
The exposure step is a step of exposing the composition layer formed in the composition layer forming step by irradiating actinic rays or radiation. Specifically, the exposure step is a step of irradiating and exposing the composition layer formed in the composition layer forming step with actinic rays or radiation, and curing the light irradiated area of the composition layer.
Although the method of light irradiation is not particularly limited, it is preferable to irradiate light through a photomask having patterned openings.
Exposure is preferably carried out by irradiation with radiation, and the radiation that can be used for exposure is particularly preferably ultraviolet rays such as G-line, H-line, and I-line, and a high-pressure mercury lamp is preferable as the light source. The irradiation intensity is preferably 5 to 1500 mJ/cm 2 , more preferably 10 to 1000 mJ/cm 2 .
In addition, when a composition contains a thermal polymerization initiator, it is also preferable to heat a composition layer in the said exposure process. The heating temperature is not particularly limited, but is preferably 80 to 250°C. Further, the heating time is not particularly limited, but is preferably 30 to 300 seconds.
In addition, in the exposure process, when heating the composition layer, it may also serve as a post-heating process described below. In other words, when heating the composition layer in the exposure step, the method for producing a light shielding film does not need to include a post-heating step.
〔現像工程〕
　現像工程は、露光後の組成物層に対して現像処理を施す工程である。本工程により、露光工程における光露光領域の組成物層が溶出し、光硬化した部分だけが残る。例えば、露光工程においてパターン状の開口部を有するフォトマスクを介して光照射を実施した場合には、パターン状の遮光膜が得られる。
　現像工程で使用される現像液の種類は特に制限されないが、下地の撮像素子及び回路等にダメージを起さない、アルカリ現像液が望ましい。
　現像温度としては、例えば、２０～３０℃である。
　現像時間は、例えば、２０～９０秒である。より残渣を除去するため、近年では１２０～１８０秒実施する場合もある。更には、より残渣除去性を向上するため、現像液を６０秒ごとに振り切り、更に新たに現像液を供給する工程を数回繰り返す場合もある。 [Development process]
The developing step is a step of subjecting the exposed composition layer to a developing treatment. Through this step, the composition layer in the photoexposed area in the exposure step is eluted, leaving only the photocured portion. For example, when light is irradiated through a photomask having patterned openings in the exposure process, a patterned light shielding film is obtained.
The type of developer used in the developing step is not particularly limited, but an alkaline developer is preferable because it does not cause damage to the underlying image sensor, circuits, etc.
The developing temperature is, for example, 20 to 30°C.
The developing time is, for example, 20 to 90 seconds. In order to remove more residue, in recent years, it is sometimes carried out for 120 to 180 seconds. Furthermore, in order to further improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying new developer may be repeated several times.
　アルカリ現像液は、アルカリ性化合物を濃度が０．００１～１０質量％（好ましくは０．０１～５質量％）となるように水に溶解して調製されたアルカリ性水溶液が好ましい。
　アルカリ性化合物は、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム，硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシ、ベンジルトリメチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン及び１，８－ジアザビシクロ［５．４．０］－７－ウンデセンが挙げられる（このうち、有機アルカリが好ましい。）。
　なお、アルカリ現像液として用いた場合は、一般に現像後に水で洗浄処理が施される。 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 alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropyl. Examples include ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among these, organic alkalis are preferred). .
In addition, when used as an alkaline developer, washing treatment with water is generally performed after development.
〔ポストベーク〕
　露光工程の後、加熱処理（ポストベーク）を行うことが好ましい。ポストベークは、硬化を完全にするための現像後の加熱処理である。その加熱温度は、２４０℃以下が好ましく、２２０℃以下がより好ましい。下限は特にないが、効率的かつ効果的な処理を考慮すると、５０℃以上が好ましく、１００℃以上がより好ましい。
　ポストベークは、ホットプレート、コンベクションオーブン（熱風循環式乾燥機）及び高周波加熱機等の加熱手段を用いて、連続式又はバッチ式で行える。 [Post bake]
It is preferable to perform a heat treatment (post-bake) after the exposure step. Post-bake is a heat treatment after development to complete curing. The heating temperature is preferably 240°C or lower, more preferably 220°C or lower. Although there is no particular lower limit, in consideration of efficient and effective treatment, the temperature is preferably 50°C or higher, more preferably 100°C or higher.
Post-baking can be performed in a continuous or batch manner using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater.
　上記のポストベークは、低酸素濃度の雰囲気下で行うのが好ましい。その酸素濃度は、１９体積％以下が好ましく、１５体積％以下がより好ましく、１０体積％以下が更に好ましく、７体積％以下が特に好ましく、３体積％以下が最も好ましい。下限は特にないが、１０体積ｐｐｍ以上が実際的である。 The above post-bake is preferably performed in an atmosphere with a low oxygen concentration. The oxygen concentration is preferably 19 vol% or less, more preferably 15 vol% or less, even more preferably 10 vol% or less, particularly preferably 7 vol% or less, and most preferably 3 vol% or less. Although there is no particular lower limit, 10 volume ppm or more is practical.
　また、上記の加熱によるポストベークに変え、ＵＶ（紫外線）照射によって硬化を完全にしてもよい。
　この場合、上述した組成物は、更にＵＶ硬化剤を含むのが好ましい。ＵＶ硬化剤は、通常のｉ線露光によるリソグラフィー工程のために添加する重合開始剤の露光波長である３６５ｎｍより短波の波長で硬化できるＵＶ硬化剤が好ましい。ＵＶ硬化剤としては、例えば、チバ　イルガキュア　２９５９（商品名）が挙げられる。ＵＶ照射を行う場合においては、組成物層が波長３４０ｎｍ以下で硬化する材料であることが好ましい。波長の下限値は特にないが、２２０ｎｍ以上であることが一般的である。また、ＵＶ照射の露光量は、１００～５０００ｍＪが好ましく、３００～４０００ｍＪがより好ましく、８００～３５００ｍＪが更に好ましい。このＵＶ硬化工程は、リソグラフィー工程の後に行うのが、低温硬化をより効果的に行うために、好ましい。露光光源はオゾンレス水銀ランプを使用するのが好ましい。 Further, instead of the above-mentioned post-baking by heating, curing may be completed by UV (ultraviolet) irradiation.
In this case, the composition described above preferably further contains a UV curing agent. The UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of a polymerization initiator added for a lithography process using normal i-line exposure. Examples of the UV curing agent include Ciba Irgacure 2959 (trade name). When UV irradiation is performed, the composition layer is preferably made of a material that hardens at a wavelength of 340 nm or less. Although there is no particular lower limit for the wavelength, it is generally 220 nm or more. Further, the exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and still more preferably 800 to 3500 mJ. This UV curing step is preferably performed after the lithography step in order to more effectively perform low temperature curing. It is preferable to use an ozone-free mercury lamp as the exposure light source.
［遮光膜の物性及び遮光膜の用途］
〔遮光膜の物性〕
　遮光膜は、優れた遮光性を有する点で、４００～１１００ｎｍの波長領域における膜厚５．０μｍあたりの光学濃度（ＯＤ：Optical Density）が、３．０以上が好ましく、３．５以上がより好ましい。なお、上限値は特に制限されないが、一般に１０以下が好ましい。
　また、本明細書において、４００～１１００ｎｍの波長領域における膜厚５．０μｍあたりの光学濃度が、３．０以上とは、波長４００～１１００ｎｍの全域において、膜厚５．０μｍあたりの光学濃度が３．０以上であることを意図する。
　なお、本明細書において、遮光膜の光学濃度の測定方法としては、まず、ガラス基板上遮光膜を形成して、分光光度計（例えば、日立ハイテクノロジーズ社製のＵ－４１００等）を用いて測定する。
　遮光膜の膜厚は、例えば、０．１～６．０μｍが好ましく、１．０～５．０μｍがより好ましく、１．０～２．５μｍが更に好ましい。また、遮光膜は、用途にあわせてこの範囲よりも薄膜としてもよいし、厚膜としてもよい。
　また、遮光膜は、優れた低反射性を有する点で、３５０～１２００ｎｍの波長領域における膜厚５．０μｍあたりの最大反射率（入射角５°）が、５％未満が好ましく、３％未満がより好ましい。なお、下限値は特に制限されないが、一般に０％以上である。
　なお、本明細書において、遮光膜の最大反射率の測定方法としては、まず、ガラス基板上に遮光膜を形成して、分光器（例えば、日本分光社製の分光器Ｖ７２００のＶＡＲユニット等）を用いて入射角５°に対する反射率スペクトルを得て、３５０～１２００ｎｍの波長領域において最大反射率を示した波長の光の反射率を求める。 [Physical properties of light-shielding film and uses of light-shielding film]
[Physical properties of light shielding film]
The light-shielding film has an excellent light-shielding property, and the optical density (OD) per film thickness of 5.0 μm in the wavelength region of 400 to 1100 nm is preferably 3.0 or more, more preferably 3.5 or more. preferable. Note that the upper limit is not particularly limited, but is generally preferably 10 or less.
In addition, in this specification, the optical density per 5.0 μm of film thickness in the wavelength region of 400 to 1100 nm is 3.0 or more means that the optical density per 5.0 μm of film thickness in the wavelength range of 400 to 1100 nm is 3.0 or more. It is intended to be 3.0 or higher.
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 then the optical density is measured using a spectrophotometer (for example, U-4100 manufactured by Hitachi High-Technologies, Inc.). Measure.
The thickness of the light shielding film is, for example, preferably 0.1 to 6.0 μm, more preferably 1.0 to 5.0 μm, and even more preferably 1.0 to 2.5 μm. Further, the light shielding film may be made thinner or thicker than this range depending on the purpose.
In addition, the light-shielding film has excellent low reflectivity, and the maximum reflectance (at an incident angle of 5°) per film thickness of 5.0 μm in the wavelength range of 350 to 1200 nm is preferably less than 5%, and preferably less than 3%. is more preferable. Note that the lower limit is not particularly limited, but is generally 0% or more.
In this specification, as a method for measuring the maximum reflectance of a light shielding film, first, a light shielding film is formed on a glass substrate, and a spectrometer (for example, a VAR unit of a spectrometer V7200 manufactured by JASCO Corporation) is used. A reflectance spectrum for an incident angle of 5° is obtained using the method, and the reflectance of light having a maximum reflectance in the wavelength range of 350 to 1200 nm is determined.
　また、上記遮光膜は、パーソナルコンピュータ、タブレット、携帯電話、スマートフォン、及びデジタルカメラ等のポータブル機器；プリンタ複合機、及びスキャナ等のＯＡ（Ｏｆｆｉｃｅ　Ａｕｔｏｍａｔｉｏｎ）機器；監視カメラ、バーコードリーダ、現金自動預け払い機（ＡＴＭ：ａｕｔｏｍａｔｅｄ　ｔｅｌｌｅｒ　ｍａｃｈｉｎｅ）、ハイスピードカメラ、及び顔画像認証を使用した本人認証機能を有する機器等の産業用機器；車載用カメラ機器；内視鏡、カプセル内視鏡、及びカテーテル等の医療用カメラ機器；並びに、生体センサ、バイオセンサー、軍事偵察用カメラ、立体地図用カメラ、気象及び海洋観測カメラ、陸地資源探査カメラ、及び宇宙の天文及び深宇宙ターゲット用の探査カメラ等の宇宙用機器；等に使用される光学フィルタ及びモジュールの遮光部材及び遮光膜、更には反射防止部材及び反射防止膜に好適である。 In addition, the light-shielding film can be applied to portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multifunction printers and scanners; surveillance cameras, barcode readers, and automated teller machines. Industrial equipment such as automated teller machines (ATMs), high-speed cameras, and devices with personal authentication functions using facial image authentication; vehicle-mounted camera equipment; endoscopes, capsule endoscopes, catheters, etc. medical camera equipment; and space applications such as biosensors, biosensors, military reconnaissance cameras, stereo mapping cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomical and deep space targets. It is suitable for light-shielding members and light-shielding films of optical filters and modules used in industrial equipment, etc., as well as anti-reflection members and anti-reflection films.
　遮光膜は、マイクロＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）及びマイクロＯＬＥＤ（Ｏｒｇａｎｉｃ　Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）等の用途にも使用できる。遮光膜は、マイクロＬＥＤ及びマイクロＯＬＥＤに使用される光学フィルタ及び光学フィルムのほか、遮光機能又は反射防止機能を付与する部材に対して好適である。
　マイクロＬＥＤ及びマイクロＯＬＥＤの例としては、特表２０１５－５００５６２号公報及び特表２０１４－５３３８９０号公報に記載された例が挙げられる。 The light shielding film can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). The light-shielding film is suitable for optical filters and optical films used in micro-LEDs and micro-OLEDs, as well as members that provide a light-shielding function or an antireflection function.
Examples of micro LEDs and micro OLEDs include those described in Japanese Translated Patent Publication No. 2015-500562 and Japanese Translated Patent Publication No. 2014-533890.
　遮光膜は、量子ドットセンサー及び量子ドット固体撮像素子に使用される光学及び光学フィルムとしても好適である。また、遮光機能及び反射防止機能を付与する部材として好適である。量子ドットセンサー及び量子ドット固体撮像素子の例としては、米国特許出願公開第２０１２／３７７８９号及び国際公開第２００８／１３１３１３号パンフレットに記載された例等が挙げられる。 The light-shielding film is also suitable as an optical film used in quantum dot sensors and quantum dot solid-state imaging devices. Further, it is suitable as a member that provides a light shielding function and an antireflection function. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313 pamphlet.
〔固体撮像素子及び固体撮像装置〕
　遮光膜は、固体撮像素子に使用するのも好ましい。
　換言すると、本発明の固体撮像素子は、本発明の遮光膜を有する固体撮像素子である。
　固体撮像素子が遮光膜を含む形態としては特に制限されず、例えば、基板上に、固体撮像素子（ＣＣＤイメージセンサ、ＣＭＯＳイメージセンサ等）の受光エリアを構成する複数のフォトダイオード及びポリシリコン等からなる受光素子を有し、支持体の受光素子形成面側（例えば、受光部以外の部分及び／又は色調整用画素等）又は形成面の反対側に遮光膜を有する形態が挙げられる。
　また、遮光膜を光減衰膜として使用する場合、例えば、一部の光が光減衰膜を通過した上で受光素子に入射するように、光減衰膜を配置すれば、固体撮像素子のダイナミックレンジを改善できる。
　固体撮像装置は、上記固体撮像素子を含む。 [Solid-state imaging device and solid-state imaging device]
It is also preferable to use the light-shielding film in a solid-state image sensor.
In other words, the solid-state image sensor of the present invention is a solid-state image sensor that has the light-shielding film of the present invention.
The form in which the solid-state image sensor includes a light-shielding film is not particularly limited, and for example, it may include a plurality of photodiodes, polysilicon, etc. that constitute the light receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on the substrate. Examples include a configuration in which the support has a light-receiving element and a light-shielding film on the side of the support where the light-receiving element is formed (for example, a portion other than the light-receiving part and/or a color adjustment pixel, etc.) or on the opposite side of the formation surface.
In addition, when using a light-shielding film as a light-attenuating film, for example, if the light-attenuating film is arranged so that some light passes through the light-attenuating film and then enters the light-receiving element, the dynamic range of the solid-state image sensor can be improved. can be improved.
The solid-state imaging device includes the solid-state imaging device described above.
〔画像表示装置〕
　遮光膜は、画像表示装置に適用されるのも好ましい。
　換言すると、本発明の画像表示装置は、本発明の遮光膜を有する画像表示装置である。
　画像表示装置が遮光膜を有する形態としては、例えば、遮光膜を含むブラックマトリクスを備えたカラーフィルタが画像表示装置に適用される形態が挙げられる。
　次に、ブラックマトリクス及びブラックマトリクスを含むカラーフィルタについて説明し、更に、画像表示装置の具体例として、このようなカラーフィルタを含む液晶表示装置について説明する。 [Image display device]
The light shielding film is also preferably applied to an image display device.
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.
An example of a mode in which the image display device has a light-shielding film is a mode in which a color filter including a black matrix including a light-shielding film is applied to the image display device.
Next, a black matrix and a color filter including a black matrix will be explained, and further, a liquid crystal display device including such a color filter will be explained as a specific example of an image display device.
＜ブラックマトリクス＞
　遮光膜は、ブラックマトリクスに含まれるのも好ましい。ブラックマトリクスは、カラーフィルタ、固体撮像素子、及び液晶表示装置等の画像表示装置に含まれる場合がある。
　ブラックマトリクスとしては、上記で既に説明したもの；液晶表示装置等の画像表示装置の周縁部に設けられた黒色の縁；赤、青、及び緑の画素間の格子状、及び／又はストライプ状の黒色の部分；ＴＦＴ（ｔｈｉｎ　ｆｉｌｍ　ｔｒａｎｓｉｓｔｏｒ）遮光のためのドット状、及び／又は線状の黒色パターン；等が挙げられる。このブラックマトリクスの定義については、例えば、菅野泰平著、「液晶ディスプレイ製造装置用語辞典」、第２版、日刊工業新聞社、１９９６年、ｐ．６４に記載がある。
　ブラックマトリクスは表示コントラストを向上させるため、また薄膜トランジスタ（ＴＦＴ）を用いたアクティブマトリックス駆動方式の液晶表示装置の場合には光の電流リークによる画質低下を防止するため、高い遮光性（光学濃度ＯＤで３以上）を有するのが好ましい。 <Black Matrix>
It is also preferable that the light shielding film is included in the black matrix. A black matrix may be included in a color filter, a solid-state image sensor, and an image display device such as a liquid crystal display device.
Examples of the black matrix include those already explained above; a black edge provided at the periphery of an image display device such as a liquid crystal display; a lattice-like and/or stripe-like matrix between red, blue, and green pixels; Examples include black portions; dot-like and/or linear black patterns for TFT (thin film transistor) light shielding; and the like. For the definition of this black matrix, see, for example, Taihei Kanno, "Liquid Crystal Display Manufacturing Equipment Terminology Dictionary," 2nd edition, Nikkan Kogyo Shimbun, 1996, p. It is described in 64.
The black matrix is used to improve display contrast, and in the case of active matrix drive type liquid crystal display devices using thin film transistors (TFTs), to prevent image quality from deteriorating due to light current leakage. 3 or more).
　ブラックマトリクスの製造方法としては特に制限されないが、上述の遮光膜の製造方法と同様の方法により製造できる。具体的には、基板に組成物を塗布して、組成物層を形成し、露光、及び現像してパターン状の遮光膜（ブラックマトリクス）を製造できる。なお、遮光膜（ブラックマトリクス）の膜厚としては、０．１～４．０μｍが好ましい。 The method for producing the black matrix is not particularly limited, but it can be produced by a method similar to the method for producing the light-shielding film described above. Specifically, a patterned light-shielding film (black matrix) can be manufactured by applying a composition to a substrate to form a composition layer, exposing it to light, and developing it. Note that the thickness of the light shielding film (black matrix) is preferably 0.1 to 4.0 μm.
　上記基板は特に制限されないが、可視光（波長４００～８００ｎｍ）に対して８０％以上の透過率を有するのが好ましい。このような基材の材料としては、例えば、ソーダライムガラス、無アルカリガラス、石英ガラス、及びホウケイ酸ガラス等のガラス；ポリエステル系樹脂及びポリオレフィン系樹脂等のプラスチック等が挙げられ、耐薬品性及び耐熱性の観点から、無アルカリガラス又は石英ガラス等が好ましい。 The above substrate is not particularly limited, but preferably has a transmittance of 80% or more for visible light (wavelength 400 to 800 nm). Examples of such base materials include glasses such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; From the viewpoint of heat resistance, alkali-free glass or quartz glass is preferable.
＜カラーフィルタ＞
　遮光膜は、カラーフィルタに含まれるのも好ましい。
　カラーフィルタが遮光膜を含む形態としては、特に制限されないが、基板と、上記ブラックマトリクスと、を備えるカラーフィルタが挙げられる。すなわち、基板上に形成された上記ブラックマトリクスの開口部に形成された赤色、緑色、及び青色の着色画素と、を備えるカラーフィルタが例示できる。 <Color filter>
It is also preferable that the light shielding film is included in the color filter.
Examples of forms in which the color filter includes a light-shielding film include, but are not particularly limited to, a color filter including a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
　ブラックマトリクスを含むカラーフィルタは、例えば、以下の方法により製造できる。
　まず、基板上に形成されたパターン状のブラックマトリクスの開口部に、カラーフィルタの各着色画素に対応する顔料を含む組成物の塗膜（組成物層）を形成する。なお、各色用組成物は特に制限されず、公知の組成物を使用できるが、本明細書で説明した組成物において、黒色顔料を各画素に対応した着色剤に置き換えた組成物を使用するのが好ましい。
　次に、組成物層に対して、ブラックマトリクスの開口部に対応したパターンを有するフォトマスクを介して露光する。次いで、現像処理により未露光部を除去した後、ベークしてブラックマトリクスの開口部に着色画素を形成できる。一連の操作を、例えば、赤色、緑色、及び青色顔料を含む各色用組成物を用いて行えば、赤色、緑色、及び青色画素を有するカラーフィルタを製造できる。 A color filter containing a black matrix can be manufactured, for example, by the following method.
First, a coating film (composition layer) of a composition containing a pigment corresponding to each colored pixel of a color filter is formed in the openings of a patterned black matrix formed on a substrate. Note that the composition for each color is not particularly limited and any known composition can be used; however, in the composition described in this specification, a composition in which the black pigment is replaced with a coloring agent corresponding to each pixel may be used. is preferred.
Next, the composition layer is exposed to light through a photomask having a pattern corresponding to the openings in the black matrix. Next, after removing the unexposed areas through a development process, it is baked to form colored pixels in the openings of the black matrix. For example, by performing a series of operations using compositions for each color containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be manufactured.
＜液晶表示装置＞
　遮光膜は、液晶表示装置に含まれるのも好ましい。液晶表示装置が遮光膜を含む形態としては特に制限されないが、すでに説明したブラックマトリクス（遮光膜）を含むカラーフィルタを含む形態が挙げられる。 <Liquid crystal display device>
It is also preferable that the light shielding film is included in the liquid crystal display device. The form in which the liquid crystal display device includes a light shielding film is not particularly limited, but may include a form including a color filter including the black matrix (light shielding film) described above.
　液晶表示装置としては、例えば、対向して配置された一対の基板と、それらの基板の間に封入されている液晶化合物とを備える形態が挙げられる。上記基板としては、ブラックマトリクス用の基板として既に説明したとおりである。 An example of a liquid crystal display device is one that includes a pair of substrates placed opposite to each other and a liquid crystal compound sealed between the substrates. The above-mentioned substrate is as already explained as a black matrix substrate.
　上記液晶表示装置の具体的な形態としては、例えば、使用者側から、偏光板／基板／カラーフィルタ／透明電極層／配向膜／液晶層／配向膜／透明電極層／ＴＦＴ（Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）素子／基板／偏光板／バックライトユニットをこの順に含む積層体が挙げられる。 As a specific form of the liquid crystal display device, for example, from the user side, polarizing plate/substrate/color filter/transparent electrode layer/alignment film/liquid crystal layer/alignment film/transparent electrode layer/TFT (Thin Film Transistor) Examples include a laminate including an element/substrate/polarizing plate/backlight unit in this order.
　なお、液晶表示装置としては、上記に制限されず、例えば「電子ディスプレイデバイス（佐々木　昭夫著、（株）工業調査会　１９９０年発行）」、「ディスプレイデバイス（伊吹　順章著、産業図書（株）平成元年発行）」等に記載されている液晶表示装置が挙げられる。また、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、（株）工業調査会　１９９４年発行）」に記載されている液晶表示装置が挙げられる。 Note that liquid crystal display devices are not limited to those mentioned above, and include, for example, "Electronic Display Device (written by Akio Sasaki, published by Industrial Research Association Co., Ltd. in 1990)" and "Display Device (authored by Junaki Ibuki, published by Sangyo Tosho Co., Ltd.)". An example of this is the liquid crystal display device described in ``1989 (Published in 1989)''. Another example is the liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd. in 1994)".
〔赤外線センサ〕
　遮光膜は、赤外線センサに含まれるのも好ましい。
　次に、上記赤外線センサを適用した固体撮像装置について説明する。
　上記固体撮像装置は、レンズ光学系と、固体撮像素子と、赤外発光ダイオード等を含む。なお、固体撮像装置の各構成については、特開２０１１－２３３９８３号公報の段落００３２～００３６を参酌でき、この内容は本明細書に組み込まれる。 [Infrared sensor]
It is also preferable that the light shielding film is included in the infrared sensor.
Next, a solid-state imaging device to which the above infrared sensor is applied will be described.
The solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light emitting diode, and the like. For each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP-A No. 2011-233983 can be referred to, and the contents thereof are incorporated into the present specification.
　以下に実施例に基づいて本発明をさらに詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。 The present invention will be described in more detail below based on Examples. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the Examples shown below.
［遮光膜形成用組成物の調製に用いる各種成分］
　以下、遮光膜形成用組成物の調製に用いる成分について詳述する。 [Various components used for preparing the composition for forming a light-shielding film]
Hereinafter, the components used for preparing the composition for forming a light-shielding film will be described in detail.
〔バインダ樹脂〕
　表３に示すバインダ樹脂（樹脂Ｂ－１～Ｂ－１２）としては以下の樹脂を用いた。 [Binder resin]
The following resins were used as the binder resins (resins B-1 to B-12) shown in Table 3.
＜樹脂Ｂ－１～Ｂ－１０＞
　表２に樹脂Ｂ－１～Ｂ－１０の構造を示す。樹脂Ｂ－１～Ｂ－１０としては、合成したものを使用した。以下に、樹脂Ｂ－１の合成例を一例として示す。なお、樹脂Ｂ－２～Ｂ－１０については、原料モノマーの種類及び配合比を変更した点以外は、樹脂Ｂ－１の合成例と同様の手順で合成した。 <Resin B-1 to B-10>
Table 2 shows the structures of resins B-1 to B-10. Resins B-1 to B-10 were synthesized. A synthesis example of resin B-1 is shown below as an example. Note that Resins B-2 to B-10 were synthesized in the same manner as in the synthesis example of Resin B-1, except that the types and blending ratios of raw material monomers were changed.
（樹脂Ｂ－１の合成例）
　ブチルメタクリレート１７３．７ｇ、メタクリル酸２０．０ｇ、２－ヒドロキシエチルメタクリレート６．３ｇを混合し、原料モノマー溶液を調製した。また、上記原料モノマーの合計質量に対して２ｍｏｌ％の熱重合開始剤（和光純薬工業（株）製Ｖ－６０１）と、上記原料モノマーの合計質量に対して１１１質量％の１－メトキシ－２－プロパノールとを混合した混合液Ａを調製した。次に、上記原料モノマー混合液と上記原料モノマーの合計質量に対して７４質量％の１－メトキシ－２－プロパノールとの混合液Ｂを調製して８０℃に加熱した後、この混合液Ｂに対して混合液Ａを２時間かけて滴下し（滴下重合）、滴下後に８０℃で２時間、更に９０℃で３時間加熱することで、樹脂Ｂ－１を合成した。 (Synthesis example of resin B-1)
173.7 g of butyl methacrylate, 20.0 g of methacrylic acid, and 6.3 g of 2-hydroxyethyl methacrylate were mixed to prepare a raw material monomer solution. In addition, 2 mol% of a thermal polymerization initiator (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) based on the total mass of the raw material monomers, and 111% by mass of 1-methoxy- A mixed solution A was prepared by mixing with 2-propanol. Next, a mixture B of the raw material monomer mixture and 1-methoxy-2-propanol in an amount of 74% by mass based on the total mass of the raw material monomers was prepared and heated to 80°C. Resin B-1 was synthesized by adding mixture A dropwise over 2 hours (drop polymerization), and heating at 80° C. for 2 hours after the dropwise addition, and then at 90° C. for 3 hours.
　以下において、表２中に示される各繰り返し単位（Ｘ－１、Ｘ－２、Ｙ－１、Ｚ－１、及びＺ－２）を示す。 Below, each repeating unit (X-1, X-2, Y-1, Z-1, and Z-2) shown in Table 2 is shown.
＜樹脂Ｂ－１１～Ｂ－１２＞
　以下に、樹脂Ｂ－１１～Ｂ－１２の構造を示す。
　なお、樹脂Ｂ－１１は、特開２０１４－１７７６１４号公報記載の方法により合成した。 <Resin B-11 to B-12>
The structures of resins B-11 and B-12 are shown below.
Note that resin B-11 was synthesized by the method described in JP-A-2014-177614.
（樹脂Ｂ－１１）
(Resin B-11)
（樹脂Ｂ－１２）
(Resin B-12)
〔顔料分散液〕
　表３に示す顔料分散液としては、分散液１～２を用いた。以下、分散液１及び分散液２の調製方法について説明する。 [Pigment dispersion]
As the pigment dispersions shown in Table 3, Dispersions 1 and 2 were used. Hereinafter, methods for preparing dispersion liquid 1 and dispersion liquid 2 will be explained.
＜分散液１の調製＞
（チタンブラック（Ａ－１）の調製）
　ＢＥＴ比表面積１１０ｍ２／ｇの酸化チタンＴＴＯ－５１Ｎ（商品名：石原産業製）を１２０ｇ、ＢＥＴ表面積３００ｍ２／ｇのシリカ粒子ＡＥＲＯＳＩＬ３００（登録商標）３００／３０（エボニック製）を２５ｇ、及び、分散剤Ｄｉｓｐｅｒｂｙｋ１９０（商品名：ビックケミー社製）を１００ｇ秤量し、イオン電気交換水７１ｇを加えてＫＵＲＡＢＯ製ＭＡＺＥＲＳＴＡＲ ＫＫ－４００Ｗを使用して、公転回転数１３６０ｒｐｍ、自転回転数１０４７ｒｐｍにて混合物を３０分間処理することにより均一な水溶液を得た。この水溶液を石英容器に充填し、小型ロータリーキルン（株式会社モトヤマ製）を用いて酸素雰囲気中で９２０℃に加熱した。その後、小型ロータリーキルン内を窒素で雰囲気を置換し、同温度でアンモニアガスを１００ｍＬ／ｍｉｎで小型ロータリーキルン内に５時間流すことにより窒化還元処理を実施した。終了後回収した粉末を乳鉢で粉砕し、Ｓｉ原子を含み、粉末状の比表面積８５ｍ２／ｇのチタンブラック（Ａ－１）〔チタンブラック粒子及びＳｉ原子を含む被分散体〕を得た。 <Preparation of dispersion liquid 1>
(Preparation of titanium black (A-1))
120 g of titanium oxide TTO-51N (trade name: manufactured by Ishihara Sangyo) with a BET specific surface area of 110 m 2 /g, 25 g of silica particles AEROSIL 300 (registered trademark) 300/30 (manufactured by Evonik) with a BET surface area of 300 m 2 /g, and Weighed 100g of the dispersant Disperbyk190 (trade name: manufactured by BYK Chemie), added 71g of ionized electric exchange water, and mixed the mixture for 30 minutes at a revolution speed of 1360 rpm and an autorotation speed of 1047 rpm using KURABO MAZERSTAR KK-400W. A homogeneous aqueous solution was obtained by treatment. This aqueous solution was filled into a quartz container and heated to 920° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the atmosphere in the small rotary kiln was replaced with nitrogen, and a nitriding reduction treatment was performed by flowing ammonia gas at 100 mL/min into the small rotary kiln for 5 hours at the same temperature. After the completion of the process, the collected powder was ground in a mortar to obtain a powdered titanium black (A-1) [dispersed element containing titanium black particles and Si atoms] containing Si atoms and having a specific surface area of 85 m 2 /g.
（分散液１の調製）
　下記組成１に示す成分を、攪拌機（ＩＫＡ社製ＥＵＲＯＳＴＡＲ）を使用して、１５分間混合し、分散物ａを得た。 (Preparation of dispersion liquid 1)
The components shown in Composition 1 below were mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion a.
《組成１》
・上述の手順により合成したチタンブラック（Ａ－１）　　・・・２５．０質量部
・下記分散樹脂Ａ－１のプロピレングリコールモノメチルエーテルアセテート２０質量％溶液　　　　　　　　　　　　　　　　・・・３７．５質量部
・プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）
　　　　　　　　　　　　　　　　　　　　　　　　・・・１０．５質量部
・酢酸ブチル（溶媒）　　　　　　　　　　　　　　・・・２７．０質量部 《Composition 1》
・Titanium black (A-1) synthesized by the above procedure: 25.0 parts by mass ・20% by mass solution of the following dispersion resin A-1 in propylene glycol monomethyl ether acetate: 37.5 parts by mass ・Propylene glycol Monomethyl ether acetate (PGMEA)
...10.5 parts by mass ・Butyl acetate (solvent) ...27.0 parts by mass
（分散樹脂Ａ－１：下記構造。表３に重量平均分子量を示す。酸価は５７．２ｍｇＫＯＨ／ｇであり、ガラス転移温度は３３℃である。）
　なお、下記構造式中、主鎖の括弧に添えられた数値の単位は質量％であり、側鎖の括弧に添えられた値は、平均付加数に相当する。 (Dispersion resin A-1: The following structure. Table 3 shows the weight average molecular weight. The acid value is 57.2 mgKOH/g, and the glass transition temperature is 33°C.)
In the structural formula below, the unit of the numerical value appended to the parentheses of the main chain is mass %, and the value appended to the parentheses of the side chain corresponds to the average number of additions.
　得られた分散物ａに対し、（株）シンマルエンタープライゼス製のＮＰＭ－Ｐｉｌｏｔを使用して下記条件にて分散処理を行い、分散液１を得た。
《分散条件》
・ビーズ径：φ０．０５ｍｍ、ジルコニア製  
・ビーズ充填率：６５体積％  
・ミル周速：１０ｍ／ｓｅｃ  
・セパレータ周速：１１ｍ／ｓ  
・分散処理する混合液量：１５ｋｇ  
・循環流量（ポンプ供給量）：６０ｋｇ／ｈｏｕｒ  
・処理液温度：１９～２１℃   
・冷却水：水  
・パス回数：９０パス The obtained dispersion a was subjected to a dispersion treatment using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. under the following conditions to obtain dispersion liquid 1.
《Dispersion conditions》
・Bead diameter: φ0.05mm, made of zirconia
・Bead filling rate: 65% by volume
・Mill peripheral speed: 10m/sec
・Separator peripheral speed: 11m/s
・Amount of mixed liquid to be dispersed: 15kg
・Circulation flow rate (pump supply amount): 60kg/hour
・Processing liquid temperature: 19-21℃
・Cooling water: water
・Number of passes: 90 passes
＜分散液２の調製＞
　分散樹脂Ａ－１にかえて下記構造の分散樹脂Ａ－２を使用した点以外は＜分散液１の調製＞と同様の手順により、分散液２を調製した。 <Preparation of dispersion liquid 2>
Dispersion 2 was prepared in the same manner as <Preparation of Dispersion 1> except that Dispersion Resin A-2 having the following structure was used instead of Dispersion Resin A-1.
（分散樹脂Ａ－２：下記構造。表３に重量平均分子量を示す。酸価は５５．７ｍｇＫＯＨ／ｇであり、ガラス転移温度は５５℃である。）
　なお、下記構造式中、主鎖の括弧に添えられた数値の単位は質量％であり、側鎖の括弧に添えられた値は、平均付加数に相当する。 (Dispersion resin A-2: The following structure. Table 3 shows the weight average molecular weight. The acid value is 55.7 mgKOH/g, and the glass transition temperature is 55°C.)
In the structural formula below, the unit of the numerical value appended to the parentheses of the main chain is mass %, and the value appended to the parentheses of the side chain corresponds to the average number of additions.
〔重合性化合物〕
　表３に示す重合性化合物（Ｄ－１～Ｄ－３）を以下に示す。
・Ｄ－１：ＫＡＹＡＲＡＤ　ＤＰＨＡ（日本化薬社製、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートとの混合物）
・Ｄ－２：ＮＫエステル　Ａ－ＤＰＨ－１２Ｅ（新中村化学社製、エトキシ化ジペンタエリスリトールポリアクリレート）
・Ｄ－３：ＮＫエステル　Ａ－ＴＭＭＴ（新中村化学社製、ペンタエリスリトールテトラアクリレート） [Polymerizable compound]
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 dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
・D-2: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated dipentaerythritol polyacrylate)
・D-3: NK ester A-TMMT (manufactured by Shin Nakamura Chemical Co., Ltd., pentaerythritol tetraacrylate)
〔開始剤〕
　表３に示す開始剤（Ｅ－１～Ｅ－４）を以下に示す。
・Ｅ－１：アデカアークルズＮＣＩ－８３１Ｅ（ＡＤＥＫＡ社製、オキシムエステル系重合開始剤）
・Ｅ－２：下記構造の化合物（オキシムエステル系重合開始剤） [Initiator]
The initiators (E-1 to E-4) shown in Table 3 are shown below.
・E-1: ADEKA Arkles NCI-831E (manufactured by ADEKA, oxime ester polymerization initiator)
・E-2: Compound with the following structure (oxime ester polymerization initiator)
・Ｅ－３：ＩＲＧＡＣＵＲＥ　ＯＸＥ０２（ＢＡＳＦ社製、オキシムエステル系重合開始剤）
・Ｅ－４：ＩＲＧＡＣＵＲＥ　ＯＸＥ０１（ＢＡＳＦ社製、オキシムエステル系重合開始剤） ・E-3: IRGACURE OXE02 (manufactured by BASF, oxime ester polymerization initiator)
・E-4: IRGACURE OXE01 (manufactured by BASF, oxime ester polymerization initiator)
〔溶媒〕
　表３に示す溶媒を以下に示す。
・シクロペンタノン（富士フイルム和光純薬社製）
・プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）（昭和電工社製）
・酢酸ブチル（三協化学社製） 〔solvent〕
The solvents shown in Table 3 are shown below.
・Cyclopentanone (manufactured by Fujifilm Wako Pure Chemical Industries)
・Propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko)
・Butyl acetate (manufactured by Sankyo Chemical Co., Ltd.)
〔界面活性剤〕
　表３に示す界面活性剤（Ｗ－１）を以下に示す。
・Ｗ－１：ＫＦ６００１（信越化学工業社製） [Surfactant]
The surfactant (W-1) shown in Table 3 is shown below.
・W-1: KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd.)
〔添加剤〕
　表３に示す添加剤（Ｘ－１）を以下に示す。
・Ｘ－１：ＥＨＰＥ　３１５０（ダイセル製）（ＣＡＳ　Ｎｏ．　２４４７７２－００－７） 〔Additive〕
The additive (X-1) shown in Table 3 is shown below.
・X-1: EHPE 3150 (manufactured by Daicel) (CAS No. 244772-00-7)
［組成物の調製］
　下記表３に示す成分及び配合量で混合して各組成物（組成物－１～２１、Ｒ１～Ｒ２）を調製した。また、組成物－Ｒ３として、国際公開第２０１７／０５７１９２号公報の実施例１と同様の組成物を調製した。
　なお、下記表中、溶媒Ａ～Ｃは、以下のとおりである。
　「溶媒Ａ」：シクロペンタノン
　「溶媒Ｂ」：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）
　「溶媒Ｃ」：酢酸ブチル 
　また、表３中、酸価の単位はｍｇＫＯＨ／ｇである。 [Preparation of composition]
Each composition (Compositions-1 to 21, R1 to R2) was prepared by mixing the components and amounts shown in Table 3 below. In addition, a composition similar to Example 1 of International Publication No. 2017/057192 was prepared as Composition-R3.
In addition, in the table below, solvents A to C are as follows.
"Solvent A": Cyclopentanone "Solvent B": Propylene glycol monomethyl ether acetate (PGMEA)
"Solvent C": Butyl acetate
Furthermore, in Table 3, the unit of acid value is mgKOH/g.
［遮光膜の作製］
　得られた組成物をガラス基板上にスピンコート法により塗布し、露光後の膜厚が５．０μｍになるような塗膜を作製した。９０℃で１２０秒間のプリベークを行った後、基板全面に対してＵＸ－１０００ＳＭ－ＥＨ０４（ウシオ電機社製）を用いて高圧水銀ランプ（ランプパワー５０ｍＷ／ｃｍ２）にて１０００ｍＪ／ｃｍ２の露光量で露光した。露光後の基板に対して２２０℃で３００秒間のポストベークを行い、遮光膜（硬化膜）付き基板を得た。 [Preparation of light shielding film]
The obtained composition was applied onto a glass substrate by a spin coating method to produce a coating film having a film thickness of 5.0 μm after exposure. After pre-baking at 90°C for 120 seconds, the entire surface of the substrate was exposed to 1000 mJ/cm 2 using a high-pressure mercury lamp (lamp power 50 mW/cm 2 ) using UX-1000SM-EH04 (manufactured by Ushio Inc.). exposed to light. The exposed substrate was post-baked at 220° C. for 300 seconds to obtain a substrate with a light-shielding film (cured film).
［評価］
〔遮光性の評価（ＯＤの測定）〕
　作製した遮光膜付き基板について、分光光度計Ｕ－４１００（日立ハイテクノロジーズ製）、積分球型受光ユニットにより、４００～１１００ｎｍの透過率スペクトルを測定した。
　最大透過率を示す波長における透過率（％）の値から次の式よりＯＤ値を算出し、下記基準に照らして評価した。Ａ～Ｂの評価であれば、実用上問題ないと判断した。結果を表４に示す。
　　　ＯＤ＝－ｌｏｇ１０（透過率／１００）
（評価基準）
　「Ａ」ＯＤが、３．０以上
　「Ｂ」ＯＤが、２．５以上、３．０未満
　「Ｃ」ＯＤが、２．５未満 [evaluation]
[Evaluation of light shielding property (OD measurement)]
The transmittance spectrum of the fabricated substrate with a light-shielding film from 400 to 1100 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies) and an integrating sphere type light receiving unit.
The OD value was calculated from the following formula from the value of transmittance (%) at the wavelength showing the maximum transmittance, and evaluated against the following criteria. If the evaluation was between A and B, it was determined that there was no problem in practical use. The results are shown in Table 4.
OD=-log10 (transmittance/100)
(Evaluation criteria)
"A" OD is 3.0 or more "B" OD is 2.5 or more, less than 3.0 "C" OD is less than 2.5
〔反射率の評価〕
　作製した遮光膜付き基板に対し、日本分光株式会社製分光器Ｖ７２００（商品名）ＶＡＲユニットを用いて角度５°の入射角で波長３５０～１２００ｎｍの光を入射し、得られた反射率スペクトルより評価した。具体的には、波長９４０ｎｍの光の反射率を評価の基準として下記区分に照らして評価した。Ａ～Ｃの評価であれば、実用上問題ないと判断した。結果を表４に示す。
（評価基準）
　「Ａ」：反射率が１％未満
　「Ｂ」：反射率が１％以上３％未満
　「Ｃ」：反射率が３％以上５％未満
　「Ｄ」：反射率が５％以上 [Evaluation of reflectance]
Light with a wavelength of 350 to 1200 nm was incident on the fabricated substrate with a light-shielding film at an incident angle of 5° using a spectrometer V7200 (trade name) VAR unit manufactured by JASCO Corporation, and from the reflectance spectrum obtained. evaluated. Specifically, the evaluation was made based on the reflectance of light at a wavelength of 940 nm in accordance with the following classification. If the evaluation is A to C, it is judged that there is no problem in practical use. The results are shown in Table 4.
(Evaluation criteria)
“A”: Reflectance is less than 1% “B”: Reflectance is 1% or more and less than 3% “C”: Reflectance is 3% or more and less than 5% “D”: Reflectance is 5% or more
〔表面粗さの評価〕
　ガラス基板（Ｃｏｒｎｉｎｇ １７３７［商品名］、Ｃｏｒｎｉｎｇ社製）上に、各組成物をそれぞれスピン塗布した後、１００℃のホットプレートを用いて２分間加熱処理（プリベーク）を行った。
　その後基板全面に対してＵＸ－１０００ＳＭ－ＥＨ０４（ウシオ電機社製）を用いて高圧水銀ランプ（ランプパワー５０ｍＷ／ｃｍ２）にて１０００ｍＪ／ｃｍ２の露光量で露光した。
　この後、ＴＭＡＨ（テトラメチルアンモニウムヒドロキシド）０．２９質量％の現像液を用いて、基板を１０～６０秒パドル現像し、水洗して乾燥後、基板を２２０℃のホットプレートを用いて３００秒間加熱処理（ポストベーク）し、樹脂膜付き基板を作製した。
　ＢＲＵＫＥＲ社製ＤｅｋｔａｋＸＴを用い、得られた基板上の樹脂膜１ｍｍの距離における表面粗さを測定し（解像度：１μｍ/点）、表面粗さＲａ（Å）を求めた。結果を表４に示す。 [Evaluation of surface roughness]
Each composition was spin-coated onto a glass substrate (Corning 1737 [trade name], manufactured by Corning Inc.), and then heat-treated (prebaked) for 2 minutes using a 100° C. hot plate.
Thereafter, the entire surface of the substrate was exposed to light at an exposure dose of 1000 mJ/cm 2 using a high-pressure mercury lamp (lamp power 50 mW/cm 2 ) using UX-1000SM-EH04 (manufactured by Ushio Inc.).
After this, the substrate was paddle-developed for 10 to 60 seconds using a developer containing 0.29% by mass of TMAH (tetramethylammonium hydroxide), washed with water, and dried. A heat treatment (post-bake) was performed for a second to produce a substrate with a resin film.
Using DektakXT manufactured by BRUKER, the surface roughness of the resin film on the obtained substrate was measured at a distance of 1 mm (resolution: 1 μm/point), and the surface roughness Ra (Å) was determined. The results are shown in Table 4.
〔パターン形状の確認〕
　上述した方法により、得られた遮光膜の断面の１μｍ×１μｍあたりの第１相と第２相との境界線の合計長さ（境界距離Ｌ）を求めた。結果を表４に示す。
　なお、各実施例及び比較例の遮光膜は、いずれも、第１相と第２相とからなる相分離構造を有していた。 [Check pattern shape]
By the method described above, the total length of the boundary line between the first phase and the second phase (boundary distance L) per 1 μm×1 μm of the cross section of the obtained light shielding film was determined. The results are shown in Table 4.
Note that the light-shielding films of each Example and Comparative Example each had a phase-separated structure consisting of a first phase and a second phase.
　表の結果から、実施例の遮光膜は、遮光性に優れ、且つ、優れた低反射特性を示すことが明らかである。
　また、実施例１（組成物－１使用）と実施例１７（組成物－１７使用）及び実施例１８（組成物－１７使用）との対比から、遮光膜形成用組成物の溶媒としてシクロペンタノンを使用した場合、遮光膜の低反射特性がより優れることが確認された。
　また、実施例１（組成物－１使用）と実施例２（組成物－２使用との対比から、遮光膜形成用組成物のアルカリ可溶性樹脂のガラス転移温度が７０℃以下である場合、遮光膜の低反射特性がより優れることが確認された。
　また、実施例１（組成物－１使用）と実施例３（組成物－３使用）及び実施例４（組成物－４使用）との対比、及び、実施例５（組成物－５使用）～実施例８（組成物－８使用）の対比から、アルカリ可溶性樹脂の重量平均分子量が１８，０００～２５，０００である場合、遮光膜の低反射特性がより優れることが確認された。 From the results in the table, it is clear that the light shielding films of Examples have excellent light shielding properties and exhibit excellent low reflection characteristics.
Furthermore, from the comparison between Example 1 (using Composition-1), Example 17 (using Composition-17), and Example 18 (using Composition-17), cyclopentane was used as a solvent for the composition for forming a light-shielding film. It was confirmed that the light-shielding film had better low-reflection properties when non-containing material was used.
In addition, from a comparison between Example 1 (using composition-1) and Example 2 (using composition-2), when the glass transition temperature of the alkali-soluble resin in the composition for forming a light-shielding film is 70°C or lower, light-shielding It was confirmed that the film had better low reflection properties.
Also, a comparison between Example 1 (using composition-1), Example 3 (using composition-3) and Example 4 (using composition-4), and Example 5 (using composition-5) ~ From comparison with Example 8 (using composition-8), it was confirmed that when the weight average molecular weight of the alkali-soluble resin was 18,000 to 25,000, the light-shielding film had better low reflection characteristics.
　また、実施例１（組成物－１使用）と実施例１１（組成物－１１使用）との対比から、遮光膜形成用組成物の分散樹脂が分散樹脂Ａ－１である場合、遮光膜の低反射特性がより優れることが確認された。 Furthermore, from a comparison between Example 1 (using composition-1) and Example 11 (using composition-11), when the dispersion resin of the composition for forming a light-shielding film is dispersion resin A-1, the light-shielding film is It was confirmed that the low reflection characteristics were better.
　遮光膜形成用組成物の組成を変更して作製した比較例の遮光膜は、所期の効果が発現しなかった。 The light-shielding film of the comparative example prepared by changing the composition of the light-shielding film-forming composition did not exhibit the expected effect.
［遮光膜の作製］
〔遮光性組成物Ａの調製〕
　上記分散液２（７８．０質量部）、上記樹脂Ｂ－１２（０．３質量部）、重合性化合物として、アロニックスＭ－３０５（東亞合成社製、４．２質量部）、重合性開始剤として上記Ｅ－１（０．６質量部）及びＴＲ－ＰＢＧ－３０４（Ｔｒｏｎｌｙ社製、０．６質量部）溶剤としてシクロペンタノン（１５．８質量部）、重合禁止剤として４－メトキシフェノール（０．００２部）、添加剤として下記化合物（０．３部）及びＥＨＰＥ　３１５０（ダイセル製、０．３部）、並びに、界面活性剤として上記Ｗ－１（０．０２質量部）を混合して、遮光性組成物Ａを調製した。
　なお、下記化合物において、ｎは２～４であり、ｍは１又は２を表す。下記化合物は、ｎ及びｍが上記数値範囲のいずれかを示す化合物の混合物である。 [Preparation of light shielding film]
[Preparation of light-shielding composition A]
The above dispersion liquid 2 (78.0 parts by mass), the above 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, polymerization initiation The above E-1 (0.6 parts by mass) and TR-PBG-304 (manufactured by Tronly, 0.6 parts by mass) were used as agents, cyclopentanone (15.8 parts by mass) was used as a solvent, and 4-methoxy was used as a polymerization inhibitor. Phenol (0.002 part), the following compound (0.3 part) and EHPE 3150 (manufactured by Daicel, 0.3 part) as additives, and the above W-1 (0.02 part by mass) as a surfactant. A light-shielding composition A was prepared by mixing.
In addition, 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 have any of the above numerical ranges.
〔遮光パターン／ブラックマトリックス付きガラスの作製〕
　上段部にて調製した組成物－１９（表３参照）を１０ｃｍ角のガラス基板上にスピンコート法により塗布し、露光後の膜厚が６．０μｍになるような塗膜を作製した。得られた塗膜に対して９０℃で１２０秒間のプリベークを実施した後、ＥＶＧ６１０（ＥＶＧ社製）を用いて、外寸１０ｍｍ、内寸９．５ｍｍ、幅０．５ｍｍの額縁状のパターンを形成できるマスクを通して高圧水銀ランプ（ランプパワー２０ｍＷ／ｃｍ２）にて２００ｍＪ／ｃｍ２の露光量で露光処理を実施した。水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、純水を用いてスピンシャワーにてリンスを行った。次いで、ホットプレートを用い、２００℃で５分間加熱（ポストベーク）することで、額縁状のパターンを形成した。 [Production of light-shielding pattern/glass with black matrix]
Composition-19 (see Table 3) prepared in the upper section was applied onto a 10 cm square glass substrate by spin coating to produce a coating film with a film thickness of 6.0 μm after exposure. After pre-baking the obtained coating film at 90°C for 120 seconds, a frame-like pattern with an outer dimension of 10 mm, an inner dimension of 9.5 mm, and a width of 0.5 mm was formed using EVG610 (manufactured by EVG). Exposure treatment was performed with a high-pressure mercury lamp (lamp power 20 mW/cm 2 ) at an exposure dose of 200 mJ/cm 2 through a mask that could be formed. Paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, rinsing was performed using pure water in a spin shower. Next, a frame-shaped pattern was formed by heating (post-baking) at 200° C. for 5 minutes using a hot plate.
　上記額縁状遮光パターン付ガラスに、遮光性組成物Ａをスピンコート法により塗布し、露光後の膜厚が１．０μｍになるような塗膜を作製した。得られた塗膜に対して９０℃で１２０秒間のプリベークを実施した後、ＥＶＧ６１０（ＥＶＧ社製）を用いて、額縁パターン内に線幅１００μｍ、線間６００μｍの格子状のパターンを作製できるマスクを通して高圧水銀ランプ（ランプパワー２０ｍＷ／ｃｍ２）にて２００ｍＪ／ｃｍ２の露光量で露光処理を実施した。水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、純水を用いてスピンシャワーにてリンスを行った。次いで、ホットプレートを用い、２００℃で５分間加熱（ポストベーク）することで、ブラックマトリックスパターンを形成した。遮光パターン／ブラックマトリックス付きガラスは遮光性及び反射率に優れているものであった。 Light-shielding composition A was applied to the frame-shaped light-shielding patterned glass by spin coating to produce a coating film having a film thickness of 1.0 μm after exposure. A mask that can create a lattice-like pattern with a line width of 100 μm and a line spacing of 600 μm in a frame pattern using EVG610 (manufactured by EVG) after pre-baking the obtained coating film at 90° C. for 120 seconds. Exposure treatment was carried out using a high-pressure mercury lamp (lamp power 20 mW/cm 2 ) with an exposure amount of 200 mJ/cm 2 through a high-pressure mercury lamp (lamp power 20 mW/cm 2 ). Paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, rinsing was performed using pure water in a spin shower. Next, a black matrix pattern was formed by heating (post-baking) at 200° C. for 5 minutes using a hot plate. The glass with the light-shielding pattern/black matrix had excellent light-shielding properties and reflectance.
　Ａ：第１相
　Ｂ：第２相 A: 1st phase B: 2nd phase

Claims (12)

  1. 　黒色顔料を含む遮光膜であって、
    　前記遮光膜が、前記黒色顔料を含む第１相と、前記黒色顔料を実質的に含まない第２相とからなる相分離構造を有し、
    　前記遮光膜の表面に直交する断面の１×１μｍ２の範囲を観察した際に、前記第１相と前記第２相との境界線の合計長さが２．５０～１５．００μｍである、遮光膜。     A light-shielding film containing a black pigment,
    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 a 1×1 μm 2 area of a cross section perpendicular to the surface of the light shielding film, the total length of the boundary line between the first phase and the second phase is 2.50 to 15.00 μm. Light-shielding film.
  2. 　表面粗さＲａが、４００～２０００Åである、請求項１に記載の遮光膜。 The light shielding film according to claim 1, having a surface roughness Ra of 400 to 2000 Å.
  3. 　黒色顔料、樹脂、及び重合性化合物を含む組成物を用いて形成された、請求項１に記載の遮光膜。 The light-shielding film according to claim 1, which is formed using a composition containing a black pigment, a resin, and a polymerizable compound.
  4. 　前記合計長さが、２．５０～７．００μｍである、請求項１～３のいずれか１項に記載の遮光膜。 The light shielding film according to any one of claims 1 to 3, wherein the total length is 2.50 to 7.00 μm.
  5. 　前記第１相が、酸価が４０～１００ｍｇＫＯＨ／ｇである第１樹脂を含み、
    　前記第２相が、酸価が４０～９０ｍｇＫＯＨ／ｇである第２樹脂を含む、請求項１～３のいずれか１項に記載の遮光膜。     The first phase includes a first resin having an acid value of 40 to 100 mgKOH/g,
    The light shielding film according to any one of claims 1 to 3, wherein the second phase contains a second resin having an acid value of 40 to 90 mgKOH/g.
  6. 　前記第１樹脂の重量平均分子量が、２０，０００～４０，０００であり、
    　前記第２樹脂の重量平均分子量が、１５，０００～４０，０００である、請求項５に記載の遮光膜。     The weight average molecular weight of the first resin is 20,000 to 40,000,
    The light shielding film according to claim 5, wherein the second resin has a weight average molecular weight of 15,000 to 40,000.
  7. 　前記第１樹脂のガラス転移温度が、－１０～６０℃であり、
    　前記第２樹脂のガラス転移温度が、０～７０℃である、請求項５に記載の遮光膜。     The first resin has a glass transition temperature of -10 to 60°C,
    The light shielding film according to claim 5, wherein the second resin has a glass transition temperature of 0 to 70°C.
  8. 　前記黒色顔料が、金属窒化物粒子及び金属酸窒化物粒子からなる群より選ばれる粒子を含む、請求項１～３のいずれか１項に記載の遮光膜。 The light-shielding film according to any one of claims 1 to 3, wherein the black pigment contains particles selected from the group consisting of metal nitride particles and metal oxynitride particles.
  9. 　パターン状である、請求項１～３のいずれか１項に記載の遮光膜。 The light shielding film according to any one of claims 1 to 3, which is patterned.
  10. 　請求項１～３のいずれか１項に記載の遮光膜を含む、固体撮像素子。 A solid-state imaging device comprising the light-shielding film according to any one of claims 1 to 3.
  11. 　請求項１～３のいずれか１項に記載の遮光膜を含む、画像表示装置。 An image display device comprising the light shielding film according to any one of claims 1 to 3.
  12. 　請求項１～３のいずれか１項に記載の遮光膜を含む、赤外センサ。 An infrared sensor comprising the light shielding film according to any one of claims 1 to 3.
PCT/JP2023/012618 2022-03-31 2023-03-28 Light-shielding film, solid-state imaging element, image display device, and infrared sensor WO2023190567A1 (en)

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