TW202022498A - Light-shielding film, method for manufacturing light-shielding film, optical element, solid-state imaging element, and headlight unit - Google Patents

Abstract

This light-shielding film comprises: a black layer containing a black coloring material; and an oxygen barrier layer formed on the black layer. The oxygen barrier layer is a single layer made from an inorganic material, and the thickness of the oxygen barrier layer is 10-500 nm. This method for manufacturing a light-shielding film comprises: a step in which a support is coated with a light-shielding composition containing a black coloring material, a resin, a polymerizable compound and a polymerization initiator, and the obtained coating film is cured to form a black layer; and a step in which an oxygen barrier layer is formed on the black layer.

Description

Light-shielding film, manufacturing method of light-shielding film, optical element, solid-state imaging element, headlight unit

The present invention relates to a light-shielding film, a manufacturing method of the light-shielding film, an optical element, a solid-state imaging element, and a headlight unit.

A color filter used in a liquid crystal display device is provided with a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. In addition, currently, mobile terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistant) are equipped with small and thin camera units. In solid-state imaging devices such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors, to prevent noise and improve image quality A light-shielding film is provided for the purpose.

There is known a technology in which an oxygen blocking layer is provided on a light-shielding film and colored pixels in this type of color filter. For example, Patent Document 1 discloses a color filter having a black matrix, a color filter layer, an oxygen group split layer covering the black matrix and the color filter layer and containing at least an oxygen-blocking compound on a substrate, and a color filter The layer and the oxygen blocking layer contain a mixed layer of dye and oxygen blocking compound. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2011-248197 A

The inventors of the present invention conducted studies on the black matrix provided with an oxygen blocking layer described in Patent Document 1, and found that there is a possibility that the light resistance and moisture resistance of the black matrix (light-shielding film) may not be sufficiently satisfied.

Therefore, the subject of the present invention is to provide a light-shielding film excellent in light resistance and moisture resistance. Furthermore, the subject of the present invention is to provide a method for manufacturing a light shielding film, an optical element, a solid-state imaging element, and a headlight unit.

As a result of intensive research, the inventor found that the above-mentioned problems can be solved by the following configuration, and completed the present invention.

[1] A light-shielding film comprising a black layer containing a black color material and an oxygen blocking layer formed on the black layer, wherein the oxygen blocking layer is a single layer composed of an inorganic material, and the oxygen blocking layer The thickness is 10~500nm. [2] The light-shielding film according to [1], wherein the black color material contains an oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium, and niobium. [3] The light-shielding film according to [1], wherein the black color material contains carbon black, a benzofuranone compound, or a perylene compound. [4] The light-shielding film according to any one of [1] to [3], wherein the content of the black color material is 20 to 80% by mass relative to the total mass of the black layer. [5] The light-shielding film according to any one of [1] to [4], wherein the oxygen blocking layer contains silicon oxide. [6] The light-shielding film according to any one of [1] to [5], wherein the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is 2-100. [7] The light-shielding film according to any one of [1] to [6], wherein the oxygen permeability of the oxygen blocking layer is 10 ml/(m ² •day•atm) or less. [8] The light-shielding film according to any one of [1] to [7], wherein the oxygen blocking layer does not substantially contain particles. [9] A method of manufacturing a light-shielding film, which comprises coating a light-shielding composition containing a black color material, a resin, a polymerizable compound, and a polymerization initiator on a support, and curing the obtained coating film The process of forming the black layer and the process of forming the oxygen blocking layer on the black layer. The oxygen blocking layer is a single layer composed of inorganic materials, and the thickness of the oxygen blocking layer is 10 to 500 nm. [10] The method of manufacturing a light-shielding film as described in [9], wherein the process of forming the oxygen blocking layer includes a process of vapor deposition of inorganic materials. [11] The method for producing a light-shielding film as described in [9] or [10], wherein the resin includes a copolymer selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and these copolymers. At least one alkali-soluble resin in the group. [12] The method for producing a light-shielding film according to any one of [9] to [11], wherein the light-shielding composition contains at least two polymerizable compounds. [13] The method for producing a light-shielding film according to any one of [9] to [12], wherein the polymerization initiator is a compound represented by the following formula (C-13). [14] The method for manufacturing a light-shielding film according to any one of [9] to [13], wherein the resin contains a resin having an ethylenically unsaturated group. [15] An optical element comprising the light-shielding film according to any one of [1] to [8]. [16] A solid-state imaging device comprising the light-shielding film according to any one of [1] to [8]. [17] A headlight unit, which is a headlight unit of a vehicle lamp, the headlight unit having: a light source; and a light shielding portion that shields at least a part of light emitted from the light source, the light shielding portion including [1]~[ 8] The light-shielding film of any one of. [Invention Effect]

According to the present invention, it is possible to provide a light-shielding film excellent in light resistance and moisture resistance. In addition, the present invention can provide a method for manufacturing a light shielding film, an optical element, a solid-state imaging element, and a headlight unit.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be completed based on the representative embodiments of the present invention, but the present invention is not limited to these embodiments. In addition, in this specification, the numerical range indicated by "~" means a range that contains the numerical values described before and after "~" as the lower limit and the upper limit.

In addition, in the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes groups that do not contain substituents and groups that contain substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups).

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

In addition, in this specification, "(meth)acrylate" means acrylate and methacrylate. In this specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. In this specification, "(meth)acryloyl group" means an allyl group and a methacryloyl group. In this specification, "(meth)acrylamide" means acrylamide and methacrylamide. In this specification, "monomer" and "monomer: monomer" have the same meaning.

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

In addition, in this specification, the weight average molecular weight (Mw) is a polystyrene conversion value based on GPC (Gel Permeation Chromatography) method. In this specification, the GPC method is based on the following method: HLC-8020GPC (manufactured by TOSOH CORPORATION), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID×15cm) as the column THF (tetrahydrofuran) was used for the extract.

[Shading film] The light-shielding film of the present invention includes a black layer containing a black color material and an oxygen blocking layer provided on the black layer. The oxygen blocking layer is a single layer made of an inorganic material. The thickness of the oxygen blocking layer is 10 to 500 nm.

In addition, the light-shielding film of the present invention can be manufactured by a manufacturing method comprising coating a light-shielding composition containing a black color material, a resin, a polymerizable compound, and a polymerization initiator on a support, and The obtained coating film is cured to form a black layer and an oxygen blocking layer is formed on the black layer.

[Black layer] The black layer contained in the light-shielding film of the present invention contains a black color material. The black layer is not limited by its manufacturing method, and is, for example, a black layer (including a patterned black layer) obtained by curing a coating film formed using the light-shielding composition.

[Light-shielding composition] The light-shielding composition (hereinafter, also simply referred to as "composition") for forming the black layer will be described. The light-shielding composition contains at least a black color material, a resin, a polymerizable compound, and a polymerization initiator.

＜Black color material＞ The light-shielding composition contains a black color material. As a black color material, 1 or more types selected from the group which consists of black pigments and black dyes are mentioned. The black color material may be used alone or in two or more types.

The content of the black color material in the black layer is not particularly limited. For example, it may be 20 to 80% by mass relative to the total mass of the black layer. From the viewpoint of better heat resistance of the light-shielding film, the content of the black color material relative to the total mass of the black layer is preferably greater than 20% by mass, more preferably 30% by mass or more, and more preferably 50% by mass or more. Also, from the viewpoint of better moisture resistance of the light-shielding film, the content of the black color material relative to the total mass of the black layer is preferably less than 80% by mass, 70% by mass or less is more preferably, and 65% by mass or less is further Better.

In addition, for example, the content of the black color material in the light-shielding composition may be 20 to 80% by mass relative to the total solid content of the light-shielding composition. From the viewpoint that the heat resistance of the light-shielding film is more excellent, compared to the light-shielding composition The total solid content of the substance is preferably more than 20% by mass, more preferably 30% by mass or more, and more preferably 50% by mass or more. In addition, from the viewpoint of better moisture resistance of the light-shielding film, the content of the black color material in the light-shielding composition relative to the total solid content of the light-shielding composition is preferably less than 80% by mass, and 70% by mass or less is More preferably, 65% by mass or less is even more preferable. In addition, in this specification, the "total solid content" of the composition means the components that form a layer or film by curing or the like, and when the composition contains a solvent (organic solvent, water, etc.), it means all components except the solvent. Moreover, as long as it is a film-forming component, a liquid component is also regarded as a solid component. That is, by adjusting the content of the black color material with respect to the total solid content of the light-shielding composition, the content of the black color material in the black layer can be adjusted to a desired value.

In addition, it is possible to combine plural kinds of coloring agents that cannot be used as a black color material alone, and adjust the whole to become black as a black color material. For example, it is also possible to combine a plurality of kinds of pigments having colors other than black when used alone as a black pigment. Similarly, a plurality of dyes having a color other than black when alone can be combined as a black dye, or a pigment having a color other than black when alone and a dye having a color other than black when alone can be combined as a black dye.

In this specification, black color material means a color material that absorbs in all wavelengths of 400 to 700 nm. More specifically, for example, a black color material suitable for the evaluation criteria Z described below is preferable. First, a composition containing a color material, a transparent resin matrix (acrylic resin, etc.) and a solvent is prepared, and the content of the color material relative to the total solid content is 60% by mass. The obtained composition was applied on a glass substrate until the film thickness of the dried coating film became 1 μm, thereby forming a coating film. The light-shielding property of the coating film after drying was evaluated by a spectrophotometer (UV-3600 manufactured by Hitachi, LTD., etc.). If the maximum value of the transmittance in the wavelength 400 to 700 nm of the dried coating film is less than 10%, it can be determined that the color material is a black color material that meets the evaluation criteria Z.

(Black pigment) As the black pigment, various known black pigments can be used. The black pigment can be an inorganic pigment or an organic pigment. From the viewpoint that the light resistance of the black layer is more excellent, the black color material-based black pigment is preferable.

As the black pigment, a pigment that expresses black alone is preferable, and a pigment that expresses black alone and absorbs infrared rays is more preferable. Among them, the black pigment that absorbs infrared rays has absorption in the wavelength region of the infrared region (preferably 650 to 1300 nm). Black pigments that have great absorption in the wavelength region of 675 to 900 nm are also preferred.

The particle size of the black pigment is not particularly limited. From the viewpoint of a more excellent balance between workability and the stability of the composition over time (black pigment does not settle), 5~100nm is preferred, and 5~50nm is more preferred , 5~30nm is more preferable.

In addition, in this specification, "particle size" means the average primary particle size of particles measured by the following method. The average primary particle size can be measured by a transmission electron microscope (Transmission Electron Microscope, TEM). As a transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used. Measure the maximum length (Dmax: the maximum length of 2 points on the outline of the particle image) and the maximum vertical length (DV-max: clamped by two straight lines parallel to the maximum length) of the particle image obtained by using a transmission electron microscope When capturing the image, vertically connect the shortest length between two straight lines), and multiply the average value (Dmax×DV-max) ^1/2 as the particle size. The particle size of 100 particles is measured by this method, and the arithmetic average value is taken as the average primary particle size of the particles.

•Inorganic pigments The inorganic pigment is not particularly limited as long as it has light-shielding properties and contains particles of an inorganic compound, and known inorganic pigments can be used. From the viewpoint that the low reflectivity and light-shielding properties of the black layer are more excellent, inorganic pigments are preferred as the black color material.

Examples of inorganic pigments include metal elements selected from the group consisting of titanium (Ti) and zirconium (Zr), group 5 metal elements such as vanadium (V) and niobium (Nb), cobalt (Co), One or more of chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn) and silver (Ag) Metal oxides, metal nitrides and metal oxynitrides of the metal elements. As the aforementioned metal oxide, metal nitride, and metal oxynitride, particles in which other atoms are further mixed can be used. For example, metal-containing nitride particles further containing atoms (preferably oxygen atoms and/or sulfur atoms) selected from elements of groups 13 to 17 of the periodic table can be used.

The method for producing the metal nitride, metal oxide, or metal oxynitride is not particularly limited as long as a black pigment having desired physical properties can be obtained, and a known production method such as a gas phase reaction method can be used. Examples of the gas phase reaction method include an electric furnace method and a thermoplasma method. However, the thermoplasma method is preferred from the viewpoints that the mixing of impurities is small, the particle size is easily uniform, and the productivity is high. The above-mentioned metal nitrides, metal oxides or metal oxynitrides may be subjected to surface modification treatment. For example, a surface treatment agent having both a silyl group and an alkyl group can be used for surface modification treatment. Examples of such inorganic particles include "KTP-09" series (manufactured by Shin-Etsu Chemical Co., LTD.) and the like.

Among them, from the viewpoint of being able to suppress the generation of undercuts when forming the black layer, nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium, and niobium is more preferable. In addition, from the viewpoint of better light resistance and moisture resistance of the light-shielding film, the black color material preferably contains an oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium, and niobium, and contains Titanium oxynitride (titanium black) is particularly preferred.

Titanium black contains black particles of titanium oxynitride. Titanium black can be surface modified as needed for the purposes of improving dispersibility and inhibiting cohesion. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can also be treated with water-repellent substances shown in Japanese Patent Application Laid-Open No. 2007-302836.

As a method of manufacturing titanium black, there are a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reduction atmosphere (Japanese Patent Laid-Open No. 49-005432), and a method of reducing titanium tetrachloride in a hydrogen-containing reduction atmosphere. A method of reducing ultrafine titanium dioxide obtained in high-temperature hydrolysis (Japanese Patent Laid-Open No. 57-205322), and a method of high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonium (Japanese Patent Laid-Open No. 60-065069, Japanese Patent Application Laid-Open No. 61-201610) and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and performing high-temperature reduction in the presence of ammonium (Japanese Patent Application Laid-Open No. 61-201610), but not limited to these.

The particle size of titanium black is not particularly limited, preferably 10~45nm, more preferably 12~20nm. The specific surface area of titanium black is not particularly limited. In order to make the water repellency after surface treatment with a water repellent agent become a prescribed performance, the value measured by the BET (Brunauer, Emmett, Teller: Brunauer, Emmett, Taylor) method is 5 ~ 150m ² / g is preferred, 20 ~ 100m ² / g is more preferred.

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

The light-shielding composition preferably contains titanium black as a dispersed body containing titanium black and Si atoms. In this aspect, titanium black is contained as a dispersion in the composition. The content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersion is calculated by mass conversion, preferably 0.05 to 0.5, and more preferably 0.07 to 0.4. Here, the above-mentioned dispersed body includes both those in the state of titanium black-based primary particles and those in the state of aggregates (secondary particles). In addition, if the Si/Ti of the dispersion is too small, when the coating film using the dispersion is patterned by photolithography, etc., residues are likely to remain in the removed part. If the Si/Ti of the dispersion is too large, Then the shading ability tends to decrease.

In order to change the Si/Ti of the dispersion (for example, 0.05 or more), the following method can be used. First, by using a disperser to disperse titanium oxide particles and silicon oxide particles to obtain a dispersion, the mixture is reduced at a high temperature (for example, 850 ~ 1000 ℃), thereby obtaining titanium black particles as the main Composition and containing Si and Ti to be dispersed. The Si/Ti adjusted titanium black can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of JP 2008-266045. In addition, the content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersion can be determined by the method (2-1) or the method (2-3) described in paragraphs 0054 to 0056 of WO2011/049090, for example. Determination.

Among the dispersions containing titanium black and Si atoms, the above-mentioned titanium black can be used. In addition, in the dispersion, for the purpose of adjusting dispersibility, coloring properties, etc., titanium black can be mixed with a composite oxide including a plurality of metals selected from Cu, Fe, Mn, V, and Ni, cobalt oxide, One or two or more of black pigments such as iron oxide, carbon black, and aniline black are combined and used as a dispersion. At this time, it is preferable that the dispersed body including titanium black accounts for 50% by mass or more of the total dispersed body. It is also preferable that the light-shielding composition contains zirconium nitride or zirconium oxynitride. Zirconium nitride or zirconium oxynitride is preferably coated with an inorganic compound. By coating the surface of zirconium nitride or zirconium oxynitride with an inorganic compound, the photocatalytic activity of the light-shielding pigment is suppressed without impairing the light-shielding properties of the pigment (light-shielding pigment), and it is easy to prevent the deterioration of the light-shielding composition. Preferred specific examples of the inorganic compound include titanium dioxide, zirconium oxide, silicon dioxide, aluminum oxide, etc., silicon dioxide and aluminum oxide. Combinations of titanium black and zirconium nitride, titanium black and zirconium oxynitride, titanium black and silicon dioxide coated zirconium nitride, titanium black and aluminum oxide coated zirconium nitride are also preferred.

As an inorganic pigment, carbon black can also be mentioned. The black color material preferably contains carbon black from the standpoint that it is excellent in light resistance and light resistance, and particularly excellent in suppression of changes in optical properties after a light resistance test.

Examples of carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black. As carbon black, carbon black manufactured by a well-known method, such as an oil furnace method, can be used, and a commercial item can also be used. Specific examples of commercially available products of carbon black include organic pigments such as C.I. Pigment Black 1, and inorganic pigments such as C.I. Pigment Black 7.

As carbon black, surface-treated carbon black is preferable. Surface treatment can modify the surface state of carbon black particles and improve the dispersion stability in the composition. The surface treatment includes resin-based coating treatment, acidic group-introduced surface treatment, and silane coupling agent-based surface treatment.

As carbon black, carbon black subjected to resin-based coating treatment is preferred. By covering the surface of the carbon black particles with an insulating resin, the light shielding and insulating properties of the black layer can be improved. In addition, the reliability of the image display device can be improved by the reduction of leakage current and the like. Therefore, it is preferable to use the black layer for applications requiring insulation. Examples of the coating resin include epoxy resin, polyamide, polyamide imide, novolac resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkyl Benzene resin, polystyrene, polycarbonate, polybutylene terephthalate and modified polyphenylene ether. From the viewpoint of better light shielding and insulating properties of the black layer, the content of the coating resin relative to the total of the carbon black and the coating resin is preferably 0.1-40% by mass, and more preferably 0.5-30% by mass.

•Organic Pigments The organic pigment is not particularly limited as long as it has light-shielding properties and contains particles of an organic compound, and known organic pigments can be used. Specific examples of organic pigments include, for example, benzofuranone compounds, methine azo compounds, perylene compounds, and azo compounds. From the viewpoint that the light-shielding film is more excellent in moisture resistance, the black color material preferably contains a benzofuranone compound or a perylene compound.

(Benzofuranone compound) The benzofuranone compound is a compound that has a benzofuran-2(3H)-one structure or a benzofuran-3(2H)-one structure in the molecule, which is colored black by absorbing light of a wavelength of visible light.

As the benzofuranone compound, compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, and Japanese Patent Application Publication No. 2012-515234 may be mentioned. Moreover, as a benzofuranone compound, the compound represented by any one of general formulas (63) to (68) is preferable.

[Chemical Formula 1]

In the general formulas (63) to (65), R ²⁰⁶ , R ²⁰⁷ , R ²¹² , R ²¹³ , R ²¹⁸ and R ²¹⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. An alkyl group with 20 fluorine atoms and carbon number 1-10. ^{R 208, R 209, R 214} , R 215, R 220 and R ²²¹ each independently represent a hydrogen atom, a halogen ^{atom, R 251, COOH, COOR 251} , COO -, CONH 2, CONHR 251, CONR 251 R 252, CN ^{, OH, OR 251, OCOR 251} , OCONH 2, OCONHR 251, OCONR 251 R 252, NO 2, NH 2, NHR 251, NR 251 R 252, NHCOR 251, NR 251 COR 252, N = CH 2, N = CHR ^{251, N = CR 251 R 252} , SH, SR 251, SOR 251, SO 2 R 251, SO 3 R 251, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 251 or SO ₂ NR ²⁵¹ R ²⁵² , R ²⁵¹ and R ²⁵² each independently represent an alkyl group with 1 to 10 carbons, a cycloalkyl group with 4 to 10 carbons, an alkenyl group with 2 to 10 carbons, a cycloalkenyl group with 4 to 10 carbons, or carbon Alkynyl of 2-10. A plurality of R ²⁰⁸ , R ²⁰⁹ , R ²¹⁴ , R ²¹⁵ , R ²²⁰ or R ²²¹ may be directly bonded or may form a ring through an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR ²⁵¹ bridge. R ²¹⁰ , R ²¹¹ , R ²¹⁶ , R ²¹⁷ , R ²²² and R ²²³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbons, or an aryl group having 6 to 15 carbons. a, b, c, d, e, and f each independently represent an integer of 0-4. In the general formulas (63) to (65), R ²⁰⁶ , R ²⁰⁷ , R ²¹² , R ²¹³ , R ²¹⁸ and R ²¹⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or having 1 to An alkyl group having 12 fluorine atoms and a carbon number of 1 to 6 is preferred. In addition, R ²⁵¹ and R ²⁵² are each independently an alkyl group with 1 to 6 carbons, a cycloalkyl group with 4 to 7 carbons, an alkenyl group with 2 to 6 carbons, a cycloalkenyl group with 4 to 7 carbons, or carbon The alkynyl group of 2 to 6 is preferable. In addition, R ²¹⁰ , R ²¹¹ , R ²¹⁶ , R ²¹⁷ , R ²²² and R ²²³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The aforementioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, and aryl group may have a hetero atom, and may be either unsubstituted or substituted.

[Chemical Formula 2]

In the general formulas (66) to (68), R ²⁵³ , R ²⁵⁴ , R ²⁵⁹ , R ²⁶⁰ , R ²⁶⁵ and R ²⁶⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. An alkyl group with 20 fluorine atoms and carbon number 1-10. ^{R 255, R 256, R 261} , R 262, R 267 and R ²⁶⁸ each independently represent a hydrogen atom, a halogen ^{atom, R 271, COOH, COOR 271} , COO -, CONH 2, CONHR 271, CONR 271 R 272, CN ^{, OH, OR 271, OCOR 271} , OCONH 2, OCONHR 271, OCONR 271 R 272, NO 2, NH 2, NHR 271, NR 271 R 272, NHCOR 271, NR 271 COR 272, N = CH 2, N = CHR ^{271, N = CR 271 R 272} , SH, SR 271, SOR 271, SO 2 R 271, SO 3 R 271, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 271 or SO ₂ NR ²⁷¹ R ²⁷² , R ²⁷¹ and R ²⁷² each independently represent an alkyl group with 1 to 10 carbons, a cycloalkyl group with 4 to 10 carbons, an alkenyl group with 2 to 10 carbons, a cycloalkenyl group with 4 to 10 carbons, or carbon Alkynyl of 2-10. A plurality of R ²⁵⁵ , R ²⁵⁶ , R ²⁶¹ , R ²⁶² , R ²⁶⁷ or R ²⁶⁸ may be directly bonded or may form a ring through an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR ²⁷¹ bridge. R ²⁵⁷ , R ²⁵⁸ , R ²⁶³ , R ²⁶⁴ , R ²⁶⁹ and R ²⁷⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbons, or an aryl group having 6 to 15 carbons. a, b, c, d, e, and f each independently represent an integer of 0-4. In the general formulas (66) to (68), R ²⁵³ , R ²⁵⁴ , R ²⁵⁹ , R ²⁶⁰ , R ²⁶⁵ and R ²⁶⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. An alkyl group having 12 fluorine atoms and a carbon number of 1 to 6 is preferred. In addition, R ²⁷¹ and R ²⁷² are each independently an alkyl group having 1 to 6 carbons, a cycloalkyl group having 4 to 7 carbons, an alkenyl group having 2 to 6 carbons, a cycloalkenyl group having 4 to 7 carbons, or a carbon The alkynyl group of 2 to 6 is preferable. Moreover, R ²⁵⁷ , R ²⁵⁸ , R ²⁶³ , R ²⁶⁴ , R ²⁶⁹ and R ²⁷⁰ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The aforementioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, and aryl group may have a hetero atom, and may be either unsubstituted or substituted.

The benzofuranone compound can be obtained as Irgaphor Black S0100CF (trade name, manufactured by BASF Corporation), for example.

(Perylene compound) The perylene compound is a compound that has a perylene structure in the molecule and is colored black by absorbing light of the wavelength of visible light.

Examples of the perylene compound include compounds described in Japanese Patent Application Publication No. 62-001753 and Japanese Patent Application Publication No. 63-026784. Furthermore, as the perylene compound, a perylene compound represented by any one of general formulas (69) to (71) is preferable.

[Chemical formula 3]

In the general formulae (69) to (71), X ⁹² , X ⁹³ , X ⁹⁴ and X ⁹⁵ each independently represent an alkylene group having 1 to 10 carbon atoms. R ²²⁴ and R ²²⁵ each independently represent hydrogen, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. R ²⁷³ and R ²⁷⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. a and b each independently represent an integer of 0-5. In general formulas (69) to (71), X ⁹² , X ⁹³ , X ⁹⁴ and X ⁹⁵ are each independently an alkylene group having 1 to 6 carbon atoms. Moreover, it is preferable that R ²²⁴ and R ²²⁵ are each independently a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or an acyl group having 2 to 4 carbon atoms. Preferably, R ²⁷³ and R ²⁷⁴ are independently hydrogen or an alkyl group having 1 to 6 carbon atoms. The above-mentioned alkylene group, alkoxy group, acyl group, and alkyl group may have a hetero atom, and may be either unsubstituted or substituted.

Perylene compounds can be used as CI Pigment Black 21, 30, 31, 32, 33 and 34, and Paliogen Black S0084, Paliogen Black K0084, Paliogen Black L0086, Paliogen Black K0086, Paliogen Black EH0788, and Paliogen Black FK4281 (the above trade names are all), for example. It is obtained by BASF Corporation.

(Black dye) As the black dye, a dye that can express black alone can be used. For example, a pyrazole azo compound, a pyrromethene compound, an aniline azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, and an oxacyanine ( oxonol) compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds and pyrrolopyrazole azomethine compounds. In addition, as black dyes, refer to Japanese Patent Application Publication No. 64-090403, Japanese Patent Application Publication No. 64-091102, Japanese Patent Application Publication No. 1-094301, Japanese Patent Application Publication No. 6-011614, Japanese Patent Application Publication No. 2592207 Bulletin, U.S. Patent No. 4808501, U.S. Patent No. 5,667,920, U.S. Patent No. 505,950, Japanese Patent Publication No. 5-333207, Japanese Patent Publication No. 6-035183, Japanese Patent Publication No. 6-051115, and Japanese Patent The compounds described in Kaihei 6-194828 and others are incorporated into this specification.

As specific examples of these black dyes, the dyes specified in the colorimetric index (C.I.) of Solvent Black 27 to 47 can be cited, and the dyes specified in C.I. of Solvent Black 27, 29 or 34 are preferred. In addition, as commercial products of these black dyes, Spilon Black MH, Black BH (above, manufactured by Hodogaya Chemical Co., Ltd.), VALIFAST Black 3804, 3810, 3820, and 3830 (above, ORIENT CHEMICAL INDUSTRIES CO ., LTD.), Savinyl Black RLSN (above, manufactured by Clariant Chemicals), KAYASET Black KR, K-BL (above, manufactured by Nippon Kayaku Co., Ltd.).

In addition, as the black dye, a dye polymer can be used. Examples of the dye multimer include the compounds described in Japanese Patent Application Publication No. 2011-213925 and Japanese Patent Application Publication No. 2013-041097. In addition, polymerizable dyes having polymerizability in the molecule can also be used. As a commercially available product, for example, the RDW series manufactured by Wako Pure Chemical Industries, LTD. Furthermore, as described above, it is also possible to use a combination of a plurality of dyes having colors other than black when they are singly used as a black dye. As such coloring dyes, for example, in addition to color dyes (color dyes) such as R (red), G (green), and B (blue), the dyes described in paragraphs 0027 to 0200 of JP 2014-042375 can also be used. .

From the viewpoint of being able to suppress the generation of undercuts when forming the black layer, the black color material preferably contains nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium and niobium. From the viewpoint that the light resistance and moisture resistance of the light-shielding film are more excellent, it is more preferable to contain an oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium and niobium, and more preferably to contain titanium oxynitride (titanium oxynitride). Black) is particularly good. Moreover, it is also preferable that the black color material contains carbon black, a benzofuranone compound, or a perylene compound.

(Colorant) The light-shielding composition may contain coloring agents other than the black color material. It is possible to adjust the light-shielding characteristics of the black layer (light-shielding film) using both a black color material and one or more colorants. Moreover, for example, when a black layer is used as a light attenuation film, it is easy to uniformly attenuate each wavelength with respect to light containing a wide-wavelength component. Examples of the coloring agent include pigments and dyes other than the above-mentioned black color materials. When the composition contains a coloring agent, the total content of the black color material and the coloring agent relative to the total mass of the solid content of the composition is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and 40 to 60% by mass It is further preferred. In addition, when a black layer formed of a light-shielding composition is used as a light attenuating film, it is also preferable that the total content of the black color material and the coloring agent is less than the above-mentioned preferable range. In addition, the mass ratio of the content of the colorant to the content of the black color material (the content of the colorant/the content of the black color material) is preferably 0.1 to 9.0.

(Infrared absorber) The composition may contain an infrared absorber. Infrared absorber means a compound that absorbs in the wavelength region of the infrared region (preferably 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption in the wavelength region of 675 to 900 nm is preferred. Examples of coloring agents having such spectroscopic properties include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, and transition metal oxide compounds. Compounds, squarylium compounds, naphthalocyanine compounds, quaterrylene compounds, dithiol metal complex compounds, croconium compounds, etc. As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, aromatic acid cyanine compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-111750 A can be used. The content is incorporated into this manual. For the cyanine compound, for example, refer to "Functional pigment, Ogawara Nobuyuki / Matsuoka Ken / Kitao Teijiro / Hirashima Hiroshi, Kodansha Scientific Ltd.", and this content is incorporated into this specification.

As a coloring agent having the above-mentioned spectroscopic properties, the compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Laid-Open No. 07-164729 and/or the compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Laid-Open No. 2002-146254 can also be used. The compound, disclosed in paragraphs 0034 to 0067 of JP 2011-164583 A, includes near-infrared absorbing particles containing Cu and/or P oxide crystallites and having a number average aggregate particle size of 5 to 200 nm.

As a compound having a maximum absorption in the wavelength region of 675 to 900 nm, at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, aromatic acid cyanine compounds, phthalocyanine compounds, and naphthalocyanine compounds is more preferred. good. In addition, it is preferable that the infrared absorber dissolves 1% by mass or more of the compound in water at 25°C, and more preferably the compound dissolves 10% by mass or more in water at 25°C. By using these compounds, solvent resistance is improved. For the pyrrolopyrrole compound, reference can be made to 0049 to 0062 of JP 2010-222557 A, and this content is incorporated in this specification. Cyanine compounds and aromatic acid cyanine compounds can refer to paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of Japanese Patent Application Publication No. 2014-059550, Paragraphs 0013 to 0091 of International Publication No. 2012/169447, Paragraphs 0019 to 0033 of JP 2015-176046, Paragraphs 0053 to 0099 of JP 2014-063144, and JP 2014-052431 Paragraphs 0085 to 0150, paragraphs 0076 to 0124 of JP 2014-044301, paragraphs 0045 to 0078 of JP 2012-008532, paragraphs 0027 to 0067 of JP 2015-172102, JP Paragraphs 0029~0067 of 2015-172004, Paragraphs 0029 to 0085 of JP 2015-040895, Paragraphs 0022 to 0036 of JP 2014-126642, Paragraph 0011 of JP 2014-148567 ~0017, paragraphs 0010~0025 of JP 2015-157893, paragraphs 0013~0026 of JP 2014-095007, paragraphs 0013~0047 of JP 2014-080487, and JP 2013- Paragraphs 0007~0028 of Bulletin No. 227403 are incorporated into this specification.

＜Resin＞ The light-shielding composition contains resin. Examples of resins include dispersion resins and alkali-soluble resins. The content of the resin in the composition is not particularly limited. With respect to the total solid content of the composition, 3-60% by mass is preferable, 10-40% by mass is more preferable, and 15-35% by mass is more preferable. . A resin may be used individually by 1 type, and may use 2 or more types together. For example, as the resin, a dispersion resin described later and an alkali-soluble resin described later may be used in combination. When two or more resins are used in combination, it is preferable that the total content is within the above range. In addition, resin means a component that is dissolved in the composition and has a molecular weight greater than 2,000. When the molecular weight of the resin is polydisperse, the weight average molecular weight of the resin is greater than 2,000.

(Dispersed resin) The light-shielding composition preferably contains a dispersed resin. In addition, in this specification, the dispersion resin means a compound different from the alkali-soluble resin mentioned later. The content of the dispersing resin in the composition is not particularly limited. With respect to the total solid content of the composition, 2-40% by mass is preferable, 5-30% by mass is more preferable, and 10-20% by mass is more preferable. good. Dispersing resin may be used individually by 1 type, and may use 2 or more types together. When two or more dispersing resins are used in combination, it is preferable that the total content is within the above range. In addition, the mass ratio of the content of the dispersed resin (preferably grafted polymer) to the content of the black color material in the composition (the content of the dispersed resin/the content of the black color material) is preferably 0.05 to 1.00, preferably 0.05 ~0.35 is more preferred, and 0.20~0.35 is even more preferred.

As the dispersion resin, for example, a known dispersant can be appropriately selected and used. Among them, polymer compounds are preferred. As the dispersing resin, a polymer dispersant (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)acrylic acid copolymer, naphthalenesulfonate formalin condensate), polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine and pigment derivatives. Polymer compounds can be further classified into linear polymers, terminal modified polymers, grafted polymers, and block polymers based on their structures.

•High molecular compound The polymer compound is adsorbed on the surface of the dispersed body such as black pigments and other pigments used in combination as required (hereinafter, black pigments and other pigments are also simply referred to as "pigments"), and play a role in preventing re-aggregation of the dispersed body. Therefore, a terminal-modified polymer, a graft-type (containing polymer chain) polymer, or a block-type polymer containing a fixing site to the surface of the pigment is preferable.

The above-mentioned polymer compound may contain a curable group. As the curable group, for example, a group having an ethylenically unsaturated bond (hereinafter, also described as "ethylenically unsaturated group") (for example, (meth)acryloyl group, vinyl group, styryl group, etc.) And cyclic ether groups (for example, epoxy groups, oxetanyl groups, etc.), but not limited to these. Among them, as the curable group, an ethylenically unsaturated group is preferred, and a (meth)acryloyl group is more preferred from the viewpoint of enabling polymerization control in a radical reaction.

From the viewpoint that the light-shielding film is more excellent in light resistance, moisture resistance, and heat resistance, the light-shielding composition preferably contains a dispersion resin having a curable group (more preferably an ethylenically unsaturated group). As the dispersion resin having a curable group, for example, a polymer compound containing a structural unit having a curable group (more preferably an ethylenically unsaturated group such as a (meth)acryloyl group) can be cited. In addition, in this specification, "structural unit" and "repeating unit" have the same meaning. For example, a hardening group may be introduced at the end of the graft chain containing the structural unit of the graft chain described below. More specifically, among the structural units constituting the polymer compound, a part or all of one or more of units derived from (meth)acrylic acid and/or other addition polymerizable vinyl monomers may be introduced There is a curable group (preferably an ethylenically unsaturated group such as a (meth)acryloyl group). In the polymer compound, in terms of mass conversion, the content of the structural unit having a curable group relative to the total mass of the polymer compound is preferably 2 to 90% by mass, and more preferably 5 to 30% by mass.

The resin having a curable group preferably contains at least one 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. As described later, when the resin contains a structural unit containing a graft chain, the polymer chain may contain a polyester structure and/or a polyether structure. As the resin, it is more preferable that the polymer chain contains a polyester structure.

The polymer compound preferably contains a structural unit containing a graft chain. In addition, in this specification, "structural unit" and "repeating unit" have the same meaning. The polymer compound containing the structural unit containing the graft chain has affinity with the solvent due to the graft chain, and therefore, the dispersibility of the pigment and the like and the dispersion stability over time (stability over time) are excellent. In addition, by the presence of the graft chain, the polymer compound including the structural unit containing the graft chain has affinity with the polymerizable compound or other resins that can be used in combination. As a result, residues are less likely to be generated during alkali development. If the graft chain becomes longer, the steric repulsion effect is improved and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorption force to the pigment or the like will decrease, and the dispersibility of the pigment or the like will tend to decrease. Therefore, in the graft chain, the number of atoms other than hydrogen atoms is preferably 40~10000, the number of atoms other than hydrogen atoms is more preferably 50~2000, and the number of atoms other than hydrogen atoms is 60~500. Better. Here, the graft chain means the root of the main chain of the copolymer (atoms bonded to the main chain from the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure. Examples of the polymer structure include poly(meth)acrylate structure (for example, poly(meth)acrylic acid structure), polyester structure, and polyurethane structure. Acid ester structure, polyurea structure, polyamide structure and polyether structure, etc. In order to improve the interaction between the graft chain and the solvent, and thereby improve the dispersibility of pigments, etc., the graft chain contains selected from the group consisting of polyester structure, polyether structure and poly(meth)acrylate structure At least one graft chain is preferable, and a graft chain containing at least one of a polyester structure and a polyether structure is more preferable.

As a macromonomer containing such a graft chain (a monomer having a polymer structure that is bonded to the main chain of the copolymer to form the graft chain), there is no particular limitation, and it can be preferably used. The giant monomer of the base. In addition, from the viewpoint that the light-shielding film is more excellent in light resistance, moisture resistance, and heat resistance, it is preferable that the polymer compound has a curable group, and it is more preferable to contain an ethylenically unsaturated group such as a (meth)acryloyl group. .

As the structural unit containing the graft chain contained in the polymer compound, commercially available macromonomers that can be preferably used in the synthesis of polymer compounds can be used AA-6, AA-10, AB-6, AS-6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30 and AK-32 (all trade names, manufactured by TOAGOSEI CO., LTD.), And BLEMMER PP-100, BLEMMER PP-500, BLEMMER PP-800, BLEMMER PP-1000, BLEMMER 55-PET-800, BLEMMER PME-4000, BLEMMER PSE-400, BLEMMER PSE-1300 and BLEMMER 43PAPE-600B (all Trade name, manufactured by NOF CORPORATION). Among them, AA-6, AA-10, AB-6, AS-6, AN-6 or BLEMMER PME-4000 are preferred.

The above-mentioned dispersing resin preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyesters. At least one structure in the group of methyl methacrylate and chain-like polyester is more preferred, and contains a structure selected from the group consisting of polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure, and polypentane At least one structure in the group of lactone structures is more preferable. The dispersing resin may contain the above-mentioned structures in one resin alone, or may contain a plurality of these structures in one resin. Here, the polycaprolactone structure means a structure containing a ring-opened ε-caprolactone structure as a repeating unit. The polyvalerolactone structure means a structure containing a ring-opened δ-valerolactone structure as a repeating unit. As a specific example of the dispersion resin containing a polycaprolactone structure, the dispersion resin in which j and k in following formula (1) and following formula (2) are 5 is mentioned. Moreover, as a specific example of the dispersing resin containing a polyvalerolactone structure, the dispersing agent whose j and k in following formula (1) and following formula (2) are 4 are mentioned. As a specific example of a dispersion resin containing a polymethyl acrylate structure, a dispersion resin in which X ⁵ in the following formula (4) is a hydrogen atom and R ⁴ is a methyl group can be mentioned. Moreover, as a specific example of the dispersion resin containing a polymethyl methacrylate structure, the dispersion resin in which X ⁵ in the following formula (4) is a methyl group, and R ⁴ is a methyl group can be mentioned.

•Containing structural units of grafted chains As the structural unit containing the graft chain, the polymer compound preferably contains a structural unit represented by any one of the following formulas (1) to (4), and contains the following formula (1A), the following formula (2A) ), the structural unit represented by any one of the following formula (3A), the following formula (3B), and the following (4) is more preferred.

[Chemical formula 4]

In formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ and W ⁴ are preferably oxygen atoms. 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. Regarding X ¹ , X ² , X ³ , X ⁴ and X ⁵ , from the viewpoint of synthesis constraints, it is preferable that each independently be a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (carbon atoms), respectively It is more preferable to independently be a hydrogen atom or a methyl group, and a methyl group is even more preferable.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and there is no particular restriction on the structure of the linking group. Specific examples of the bivalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following linking groups (Y-1) to (Y-21). In the structure shown below, A and B respectively represent the bonding site with the left end group and the right end group in formulas (1) to (4). Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.

[Chemical formula 5]

In formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited. Specifically, it includes an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an arylene sulfide group, and a heteroarylene sulfide group. And amino groups, etc. Among them, as the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ , especially from the viewpoint of improving dispersibility, a group having a stereo-repelling effect is preferred, and each independently has a carbon number of 5 to 24 The alkyl group or alkoxy group of is more preferable, and among them, each independently is a branched alkyl group having 5 to 24 carbons, a cyclic alkyl group having 5 to 24 carbons, or an alkoxy group having 5 to 24 carbons. It is further preferred. In addition, the alkyl group contained in the alkoxy group may be any of linear, branched and cyclic.

In formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500. In addition, in formulas (1) and (2), j and k each independently represent an integer of 2-8. From the viewpoint of the stability and developability of the composition over time, it is preferable that j and k in the formulas (1) and (2) are integers of 4 to 6, and 5 is more preferable. Moreover, in formulas (1) and (2), n and m are preferably integers of 10 or more, and more preferably integers of 20 or more. In addition, when the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, as the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of the polyvalerolactone, an integer of 10 or more is preferred, and an integer of 20 or more For better.

In the formula (3), R ³ represents a branched or linear alkylene group, and an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 2 or 3 carbon atoms is more preferred. When p is 2 to 500, there are a plurality of R ³ which may be the same or different from each other. In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent structure is not particularly limited. As R ⁴ , a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom or an alkyl group is more preferable. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbons, a branched alkyl group having 3 to 20 carbons, or a cyclic alkyl group having 5 to 20 carbons. The linear alkyl group having 1 to 20 is more preferable, and the linear alkyl group having 1 to 6 carbons is more preferable. In the formula (4), when q is 2 to 500, multiple X ⁵ and R ^{4 in the} graft copolymer may be the same or different from each other.

In addition, the polymer compound may contain two or more structural units with different structures and a graft chain. That is, the molecules of the polymer compound may contain structural units represented by formulas (1) to (4) with different structures, and in formulas (1) to (4), n, m, p, and q are respectively When it represents an integer greater than or equal to 2, in formulas (1) and (2), structures with different j and k can be included in the side chain. In formulas (3) and (4), there are multiple R ³ , R ⁴ and X ⁵ may be the same or different from each other.

As the structural unit represented by the formula (1), the structural unit represented by the following formula (1A) is more preferable from the viewpoint of the stability and developability of the composition over time. In addition, as the structural unit represented by the formula (2), the structural unit represented by the following formula (2A) is more preferable from the viewpoint of the stability and developability of the composition over time.

[Chemical formula 6]

In the formula ^{(1A), 1, Y 1} , Z ¹ and n have the same meaning as X ^1, Y ^1, Z ¹ and n of formula X (1) is, preferred ranges are also the same. In formula ^{(2A), X 2, Y} 2, Z 2 and X m in the formula (2) is ^2, the Y ^2, Z ² and m have the same meaning and preferred ranges are also the same.

In addition, as the structural unit represented by the formula (3), from the viewpoint of the temporal stability and developability of the composition, the structural unit represented by the following formula (3A) or formula (3B) is more preferable.

[Chemical formula 7]

In formula (3A) or ^{(3B), 3, Y 3} , Z ³ and p have the same meaning of X ^3, Y ^3, Z ³ and p of formula X (3) is, preferred ranges are also the same.

As the structural unit containing the graft chain, it is more preferable that the polymer compound contains the structural unit represented by formula (1A).

In the polymer compound, the content of the structural unit containing the graft chain (for example, the structural unit represented by the above formula (1) to (4)) is calculated by mass conversion, relative to the total mass of the polymer compound, 2~90 The mass% is more preferable, and 5-30 mass% is more preferable. If the structural unit containing the graft chain is included in this range, the dispersibility of the pigment is high, and the developability when forming a cured film is good.

•Hydrophobic structural unit In addition, the polymer compound preferably contains a hydrophobic structural unit different from the structural unit containing the graft chain (that is, it is not equivalent to the structural unit containing the graft chain). Among them, in the present invention, the hydrophobic structural unit system does not contain structural units of acid groups (for example, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, phenolic hydroxyl groups, etc.).

The hydrophobic structural unit is preferably derived from (corresponding to) the structural unit of a compound (monomer) having a ClogP value of 1.2 or more, and the structural unit derived from a compound having a ClogP value of 1.2 to 8 is more preferable. Thereby, the effect of the present invention can be more reliably expressed.

The ClogP value is the value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "calculated logP" calculated by Hansch, Leo's fragment approach (refer to the following documents). The fragment approach divides the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and totals the logP contribution allocated to the fragment, thereby inferring the logP value of the compound. The details are described in the following documents. In this manual, the ClogP value calculated by the program CLOGP v4.82 is used. AJ Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammnens, JB Taylor and CA Ramsden, Eds., p. 295, Pergamon Press, 1990 C. Hansch & AJ Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. AJ Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP represents the common logarithm of the partition coefficient P (Partition Coefficient), which is a quantitative value to indicate how to distribute the physical property value of an organic compound in the two-phase equilibrium of oil (usually 1-octanol) and water, by the following formula Said. logP=log(Coil/Cwater) In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase. If the value of logP is based on 0, the positive direction (plus) increases, the oil solubility increases, if the absolute value negative direction (minus) increases, the water solubility increases, which is negatively correlated with the water solubility of organic compounds. It is widely used to estimate the hydrophilic and hydrophobic parameters of organic compounds.

As the hydrophobic structural unit, the polymer compound preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii).

[Chemical formula 8]

In the above formulas (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a carbon number of 1 to 6 Alkyl (e.g., methyl, ethyl, propyl, etc.). R ¹ , R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R ² and R ³ are more preferably hydrogen atoms. X represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferred.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), two Valence aromatic group (for example, aryl group, substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-) , Substituted imino group (-NR ³¹ -, where R ³¹ is an aliphatic group, aromatic group or heterocyclic group), carbonyl group (-CO-), and combinations thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but a saturated aliphatic group is preferred. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups, heterocyclic groups, and the like.

The carbon number of the divalent aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. In addition, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. In addition, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR ³² , in which, R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L-based single bond, alkylene group or divalent linking group containing an oxyalkylene structure is preferable. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may contain a polyoxyalkylene structure including two or more alkylene oxide structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by -(OCH ₂ CH ₂ )n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2-10.

Examples of Z include aliphatic groups (for example, alkyl groups, substituted alkyl groups, unsaturated alkyl groups, and substituted unsaturated alkyl groups), aromatic groups (for example, aryl groups, substituted aryl groups, and arylene groups). , Substituted aryl group), heterocyclic group and combinations thereof. These groups may contain oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imino groups (-NR ³¹ -, where R ³¹ is aliphatic Group, aromatic group or heterocyclic group) or carbonyl group (-CO-).

The aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group also includes a polycyclic hydrocarbon group and a cross-linked cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include bicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. As the crosslinked cyclic hydrocarbon ring, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2 ]Octane ring, bicyclic [3.2.1] octane ring, etc.) and other 2-cyclic hydrocarbon rings; homobredane, adamantane, tricyclic [5.2.1.0 ^2,6 ]decane, tricyclic [4.3 .1.1 3 cyclic hydrocarbon rings such as ^2,5 ]undecane ring; tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ]dodecane and perhydro-1,4-methylene-5,8 -4-cyclic hydrocarbon rings such as methylene naphthalene ring, etc. In addition, the cross-linked cyclic hydrocarbon ring also includes a fused-ring hydrocarbon ring, for example, perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydronaphthalene. A fused ring in which a plurality of 5- to 8-membered cycloalkane rings are fused together, such as a bi-ring. Compared with unsaturated aliphatic groups, aliphatic groups are preferably saturated aliphatic groups. In addition, the aliphatic group may have a substituent. Examples of the substituent include halogen atoms, aromatic groups and heterocyclic groups. Among them, the aliphatic group does not have an acid group as a substituent.

The carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. In addition, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups. Among them, as a substituent, the aromatic group does not have an acid group.

The heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. In addition, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR ³² , in which, R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. However, as a substituent, the heterocyclic group does not have an acid group.

In the above formula (iii), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example , Methyl, ethyl, propyl, etc.), Z or LZ. Among them, L and Z have the same meanings as the above groups. As R ⁴ , R ⁵ and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

As the monomer represented by the above formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, L is a single bond or an alkylene group or a divalent linking group containing an oxyalkylene structure, and X is oxygen A compound having an atom or an imino group, and Z being an aliphatic group, a heterocyclic group or an aromatic group is preferred. Moreover, as the monomer represented by the above formula (ii), a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable. In addition, as the monomer represented by the above formula (iii), compounds in which R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or methyl groups, and Z is an aliphatic group, heterocyclic group or aromatic group are preferred.

Examples of representative compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, and styrenes. In addition, as examples of representative compounds represented by formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of JP 2013-249417 A, and these contents are incorporated in this specification.

In the polymer compound, in terms of mass conversion, the content of the hydrophobic structural unit relative to the total mass of the polymer compound is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. When the content is within the above range, a pattern can be sufficiently formed.

•Functional groups that can interact with pigments, etc. The polymer compound can introduce functional groups that can interact with pigments and the like (for example, black pigments). Among them, the polymer compound preferably 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 or the like include acid groups, base groups, coordinating groups, and reactive functional groups. When the polymer compound has an acid group, a base, a coordination group or a reactive functional group, it contains a structural unit with an acid group, a structural unit with a base, a structural unit with a coordination group, or a reactive The structural unit of sex is preferred. In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be provided with developability for pattern formation by alkali development. That is, when an alkali-soluble group is introduced into the polymer compound, the polymer compound as a dispersion resin that contributes to the dispersion of pigments and the like in the above-mentioned composition contains alkali-solubility. Regarding the composition containing such a polymer compound, the black layer formed by exposure has excellent light-shielding properties, and the alkali developability of the unexposed portion is improved. In addition, if the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be easily compatible with the solvent and the coating properties are also improved. It is presumed that this is because the acid group in the structural unit containing the acid group easily interacts with the pigment, etc., the polymer compound makes the pigment etc. stably dispersed, and the viscosity of the dispersed polymer compound of the pigment etc. becomes low, and the polymer compound itself It is also easy to disperse stably.

Among them, the structural unit containing the alkali-soluble group as an acid group may be the same structural unit as the above-mentioned graft chain-containing structural unit, or a different structural unit, but a structural unit system containing an alkali-soluble group as an acid group A structural unit different from the aforementioned hydrophobic structural unit (that is, it does not correspond to the aforementioned hydrophobic structural unit).

As an acid group capable of forming a functional group that interacts with pigments, for example, there are carboxylic acid group, sulfonic acid group, phosphoric acid group and phenolic hydroxyl group. At least one of carboxylic acid group, sulfonic acid group and phosphoric acid group is more Preferably, the carboxylic acid group is more preferable. The carboxylic acid group has good adsorption power for pigments and the like, and has high dispersibility. That is, the polymer compound preferably further includes a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or more structural units containing acid groups. The polymer compound may or may not contain the structural unit containing the acid group, but when it is contained, the content of the structural unit containing the acid group is preferably 5 to 80% by mass relative to the total mass of the polymer compound. From the viewpoint of image intensity damage, 10-60% by mass is more preferable.

As the bases that can form functional groups that interact with pigments, for example, there are primary amine groups, secondary amine groups, tertiary amine groups, heterocycles containing N atoms, and amide groups. From the viewpoint of good and high dispersibility, the preferred base is a tertiary amino group. The polymer compound can contain one or more of these bases. The polymer compound may or may not contain the structural unit containing the base, but when it contains, the content of the structural unit containing the base is calculated by mass conversion, and is preferably 0.01-50% by mass relative to the total mass of the polymer compound. From the viewpoint of suppressing the hindrance of developability, 0.01 to 30% by mass is more preferable.

Coordinating groups and reactive functional groups that can form functional groups that interact with pigments and the like include, for example, acetylacetoxy groups, trialkoxysilyl groups, isocyanate groups, acid anhydrides, and chlorinated groups. Wait. From the viewpoints of good adsorption to pigments and the like and high dispersibility of the pigments and the like, the preferred functional group is acetylacetoxy. The polymer compound may have one or more of these groups. The polymer compound may or may not include structural units containing coordination groups or structural units containing reactive functional groups, but when it contains, the content of these structural units is calculated by mass, relative to the total polymer compound The mass is preferably 10 to 80% by mass, and from the viewpoint of inhibiting the developmental property from being inhibited, 20 to 60% by mass is more preferable.

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

[Chemical formula 9]

In formulas (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom, etc.) or an alkane having 1 to 6 carbon atoms Group (for example, methyl, ethyl, propyl, etc.). In formulas (iv) to (vi), as R ¹¹ , R ¹² and R ¹³ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. In the general formula (iv), as R ¹² and R ¹³ , a hydrogen atom is more preferable.

X ₁ in the formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferred. In addition, Y in formula (v) represents a methine group or a nitrogen atom.

Moreover, L ₁ in formulas (iv) to (v) represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above formula (i).

L ₁ is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L ₁ may include a polyoxyalkylene structure repeatedly including two or more alkylene oxide structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by -(OCH ₂ CH ₂ )n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2-10.

In formulas (iv) to (vi), Z _{1 in} addition to the graft chain also represents a functional group capable of forming an interaction with pigments, etc. A carboxylic acid group or a tertiary amine group is preferred, and a carboxylic acid is more preferred.

In formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl and propyl, etc.), - Z ₁ or L ₁ -Z _1. Wherein, L ₁ and Z ₁ have the same meaning as the above-mentioned L ₁ and Z ₁ , and preferred examples are also the same. As R ¹⁴ , R ¹⁵ and R ¹⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

As a monomer represented by formula (iv), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, L ₁ is an alkylene group or a divalent linking group containing an oxyalkylene structure, and X ₁ is The oxygen atom or imino group is preferably a compound in which Z ₁ is a carboxylic acid group. In addition, as the monomer represented by the formula (v), a compound in which R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine group is preferred. Furthermore, as the monomer represented by formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z ₁ is a carboxylic acid group. Better.

The following shows representative examples of monomers (compounds) represented by formulas (iv) to (vi). Examples of monomers include the reaction of methacrylic acid, crotonic acid, isocrotonic acid, compounds containing addition polymerizable double bonds and hydroxyl groups in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride The reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and phthalic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride, A reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group and trimellitic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid Oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol and 4-hydroxybenzyl acrylate, etc.

From the viewpoint of interaction with pigments, etc., stability over time, and permeability to developing solutions, in terms of mass conversion, the content of structural units containing functional groups capable of interacting with pigments is relative to that of polymer compounds. The total mass is preferably from 0.05 to 90% by mass, more preferably from 1.0 to 80% by mass, and even more preferably from 10 to 70% by mass.

•Other structural units Furthermore, for the purpose of improving various properties such as image strength, the polymer compound can be further provided with a structural unit containing a graft chain, a hydrophobic structural unit, and a structure capable of forming interaction with pigments, etc., without compromising the effect of the present invention. Other structural units with various functions that have different structural units of functional functional groups (for example, structural units containing functional groups that have affinity for the solvent described below). Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles. The polymer compound can use one or more of these other structural units, and the content is calculated by mass conversion. It is preferably 0~80% by mass relative to the total mass of the polymer compound, and more preferably 10~60% by mass. good. The content can maintain sufficient pattern formability within the above range.

• Physical properties of polymer compounds The acid value of the polymer compound is preferably 0 to 250 mgKOH/g, more preferably 10 to 200 mgKOH/g, more preferably 30 to 180 mgKOH/g, and particularly preferably in the range of 70 to 120 mgKOH/g. If the acid value of the polymer compound is 160 mgKOH/g or less, it is possible to more effectively suppress pattern peeling during development when the cured film is formed. In addition, when the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability is more favorable. In addition, when the acid value of the polymer compound is 20 mgKOH/g or more, the sedimentation of pigments and the like can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability of the composition can be further improved.

In this specification, for example, the acid value can be calculated from the average content of acid groups in the compound. In addition, if the constituent components of the resin, that is, the content of structural units containing acid groups, are changed, a resin having a desired acid value can be obtained.

The weight average molecular weight of the polymer compound is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, more preferably 6,000 to 100,000, and particularly preferably 10,000 to 50,000. The polymer compound can be synthesized according to a known method.

Specific examples of polymer compounds include "DA-7301" manufactured by Kusumoto Chemicals, LTD., "Disperbyk-101 (polyamide phosphate), 107 (carboxylate), 110 (containing acid) manufactured by BYKChemie Base copolymer), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)", "BYK-P104, P105 (High molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050-4010-4165 (polyurethane series), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylic acid) manufactured by EFKA Ester), 5010 (polyamide ester), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", Ajinomoto Fine-Techno Co., Inc. "AJISPER PB821, PB822, PB880, PB881", KYOEISHA CHEMICAL Co., LTD. "FLOREN TG-710 (urethane oligomer)", "Polyflow No.50E, No. 300 (acrylic copolymer)", Kusumoto Chemicals, LTD. "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA -705, DA-725", Kao Corporation "DEMOL RN, N (formalin naphthalenesulfonate condensation polymer), MS, C, SN-B (aromatic sulfonate formalin condensation polymer)", "HOMOGENOL L-18 (Polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)", "ACETAMIN 86 (stearyl amine acetate)", "SOLSPERSE 5000 (manufactured by The Lubrinzol corporation) Phthalocyanine derivatives), 22000 (azo pigment derivatives), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymers with functional parts at the end), 24000, 28000, 32000, 38500 (Graft copolymer)", "Nikkor T106 (polyoxyethylene sorbitol monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikkol Chemicals CO., LTD., Kawaken Fine Chemical s HINOAKUTO T-8000E manufactured by CO., LTD., polyorganosiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., LTD., "W001: Cationic Surfactant" manufactured by Yusho Co Ltd, Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene Nonionic surfactants such as glycol distearate and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, and W017", "EFKA-46, EFKA-47 manufactured by MORISHITA & CO., LTD. , EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" and other polymers manufactured by SAN NOPCO LIMITED Dispersant, "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION and Sanyo Chemical "Ionet (trade name) S-20" manufactured by Industries, LTD., etc. In addition, Acrybase FFS-6752 and Acrybase FFS-187 can also be used.

Moreover, it is also preferable to use an amphoteric resin containing acid groups and bases. Amphoteric resin resins having an acid value of 5 mgKOH/g or more and an amine value of 5 mgKOH/g or more are preferred. As commercial products of amphoteric resins, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK manufactured by BYK-Chemie GmbH -2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822 and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. These polymer compounds may be used individually by 1 type, and may use 2 or more types together.

In addition, as an example of a specific example of a polymer compound, the polymer compound described in paragraphs 0127 to 0129 of JP 2013-249417 A can be referred to, and these contents are incorporated in this specification.

In addition, as the dispersion resin, in addition to the above-mentioned polymer compounds, the graft copolymers of paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 of US2011/0124824) of JP 2010-106268 A can also be used. And other content, and introduced into this manual. Moreover, in addition to the above, the side chain structure containing acidic groups in paragraphs 0028 to 084 (corresponding to paragraphs 0075 to 0133 of US2011/0279759) of JP 2011-153283 A can also be used. The polymer compounds of the constituent components can use these contents and be incorporated into this specification.

In addition, as the dispersion resin, the resins described in paragraphs 0033 to 0049 of JP 2016-109763 A can also be used, and this content is incorporated in this specification.

(Alkali-soluble resin) The composition preferably contains an alkali-soluble resin. In this specification, the alkali-soluble resin means a resin containing a group that promotes alkali solubility (alkali-soluble group, for example, an acid group such as a carboxylic acid group), and means a resin different from the dispersion resin described above. The content of the alkali-soluble resin in the composition is not particularly limited. It is preferably 1-30% by mass relative to the total solid content of the composition, more preferably 2-20% by mass, and more preferably 5-15% by mass. Better. Alkali-soluble resin may be used individually by 1 type, and may use 2 or more types together. When two or more alkali-soluble resins are used in combination, the total content is preferably within the above range.

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

As a specific example of the alkali-soluble resin, a copolymer resin of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be mentioned. The unsaturated carboxylic acid is not particularly limited. Examples 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. Acid, or its anhydride; and mono(2-(meth)acryloyloxyethyl) phthalate and other polycarboxylic acid monoesters; etc.

As the ethylenically unsaturated compound which can be copolymerized, methyl (meth)acrylate etc. are mentioned. In addition, the compounds described in paragraph 0027 of JP 2010-097210 A and paragraphs 0036 to 0037 of JP 2015-068893 A can also be used, and the above-mentioned contents are incorporated into this specification.

In addition, a copolymerizable ethylenically unsaturated compound and a compound containing an ethylenically unsaturated group in the side chain may be used in combination. As the ethylenically unsaturated group, a (meth)acrylic group is preferred. The acrylic resin containing an ethylenically unsaturated group in the side chain is obtained by, for example, the addition reaction of the carboxylic acid group of the acrylic resin containing a carboxylic acid group with a glycidyl group or an ethylenically unsaturated compound containing an alicyclic epoxy group.

As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferable. As the above-mentioned curable group, a curable group that may contain the above-mentioned polymer compound is similarly exemplified, and the preferable range is also the same. As the alkali-soluble resin containing a curable group, an alkali-soluble resin having a curable group in the side chain or the like is preferable. Examples of alkali-soluble resins containing curable groups include DIANAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), VISCOAT R -264, KS RESIST 106 (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (e.g. ACA230AA), PLACCEL CF200 series (all manufactured by Daicel Corporation), Ebecryl3800 (manufactured by DAICEL-ALLNEX LTD.) and ACRYCURE RD -F8 (manufactured by NIPPON SHOKUBAI CO., LTD.) etc.

As the alkali-soluble resin, for example, Japanese Patent Publication No. 59-044615, Japanese Patent Publication No. 54-034327, Japanese Patent Publication No. 58-012577, Japanese Patent Publication No. 54-025957, and Japanese Patent Application Publication No. 54-092723 can be used, for example. Radical polymers containing carboxylic acid groups in the side chain described in Japanese Patent Publication No. 59-053836 and Japanese Patent Application Publication No. 59-071048; European Patent No. 993966 and European Patent No. 1204000 Alkali-soluble group-containing acetal-modified polyvinyl alcohol binder resin described in the manual and Japanese Patent Application Publication No. 2001-318463; polypyrrolidone; polyvinyloxy; alcohol-soluble nylon and 2,2-bis-( The reaction product of 4-hydroxyphenyl)-propane and epichlorohydrin, namely polyether, etc.; and the polyimide resin described in the pamphlet of International Publication No. 2008/123097; etc.

As the alkali-soluble resin, for example, the compounds described in paragraphs 0225 to 0245 of JP 2016-075845 A can also be used, and the above contents are incorporated in this specification.

As the alkali-soluble resin, a polyimide precursor can also be used. The polyimide precursor refers to a resin obtained by an addition polymerization reaction between a compound containing an acid anhydride group and a diamine compound at 40-100°C. As the polyimide precursor, for example, a resin containing a repeating unit represented by formula (1) can be cited. As the structure of the polyimide precursor, for example, the amide structure represented by the following formula (2), and the following formula (3) which contains a part of the amide ring closed by the amide structure ) And all imines are ring-closed to form the polyimines precursors of the imines structure represented by the following formula (4). In addition, in this specification, the polyimide precursor having an amino acid structure is sometimes referred to as polyimide acid.

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

In the above formulas (1) to (4), R ₁ represents a tetravalent organic group having ₂ to 22 carbon atoms, R ₂ represents a divalent organic group having 1 to 22 carbon atoms, and n represents 1 or 2.

As specific examples of the aforementioned polyimide precursors, for example, the compounds described in paragraphs 0011 to 0031 of JP 2008-106250 A, and the compounds described in paragraphs 0022 to 0039 of JP 2016-122101 A can be cited. For the compounds and the compounds described in paragraphs 0061 to 0092 of JP 2016-068401 A, the above contents are incorporated into this specification.

From the viewpoint that the pattern shape of the patterned black layer obtained by using the composition is more excellent, it is also preferable that the alkali-soluble resin contains at least one selected from the group consisting of polyimide resin and polyimide precursor.

The polyimide resin containing an alkali-soluble group is not particularly limited, and polyimide resins containing known alkali-soluble groups can be used. Examples of the polyimide resin include the resin described in paragraph 0050 of JP 2014-137523 A, the resin described in paragraph 0058 of JP 2015-187676 A, and JP 2014-106326 For the resins described in paragraphs 0012 to 0013 of the Bulletin, the above contents are incorporated into this specification.

As the alkali-soluble resin, a polybenzoxazole precursor can also be used. The polybenzoxazole precursor is a resin synthesized from a hydroxyl-containing diamine and a dicarboxylic acid derivative. As a diamine containing a hydroxyl group, the aromatic diamine which has a phenolic hydroxyl group, such as a diamino phenol compound, is mentioned, for example. Specific examples of diamines containing hydroxyl groups include 3,3-dihydroxybenzidine and 3,3'-dihydroxy-4,4'-diaminodiphenyl ether. Examples of dicarboxylic acid derivatives include dicarboxylic acid derivatives such as dicarboxylic acid chloride and dicarboxylic acid esters, and aromatic dicarboxylic acid derivatives are preferred. Specific examples of the dicarboxylic acid derivative include isophthalic acid chloride and terephthalic acid chloride. Specific examples of polybenzoxazole precursors include polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide.

Specific examples of polybenzoxazole precursors include, for example, the compounds described in paragraphs 0049 to 0062 of JP 2003-121997 A, and the compounds described in paragraphs 0050 to 0057 of the specification of International Publication No. 2017/057281. The compounds described in paragraphs 0015~0043 of International Publication No. 2016/043203 specification, etc., the above contents are incorporated into this specification.

The copolymer of the polyimide precursor and the polybenzoxazole precursor is a copolymer having a polyamide structural unit and a hydroxypolyamide structural unit, for example, a polyamide structural unit may be mentioned And a copolymer of an interactive copolymer structure of hydroxyl polyamide structural units.

As an alkali-soluble resin, at least 1 selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and copolymers from the viewpoint of better light resistance and heat resistance of the light-shielding film Kind is preferable, and polyimide resin is more preferable.

In addition, as alkali-soluble resins, [benzyl (meth)acrylate/(meth)acrylic acid/other addition polymerizable vinyl monomers as required] copolymer, and [allyl (meth)acrylate/ The (meth)acrylic acid/addition polymerizable vinyl monomer as required] copolymer has excellent film strength, sensitivity, and developability in balance, and this is preferable. The above-mentioned other addition polymerizable vinyl monomers may be one type alone or two or more types. From the viewpoint that the black layer is more excellent in moisture resistance, it is preferable that the copolymer has a curable group, and it is more preferable to contain an ethylenically unsaturated group such as a (meth)acryloyl group. For example, as the above-mentioned other addition polymerizable vinyl monomer, a monomer having a curable group can be used to introduce the curable group into the copolymer. In addition, a part or all of one or more of the units derived from the (meth)acrylic acid in the copolymer and/or the units derived from the other addition polymerizable vinyl monomers may be introduced with curable groups (more Preferred is an ethylenically unsaturated group such as (meth)acryloyl group). As said other addition polymerizable vinyl monomer, for example, methyl (meth)acrylate, styrene monomer (hydroxystyrene etc.) and ether dimer are mentioned. Examples of the ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).

[Chemical formula 14]

In the general formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.

[Chemical formula 15]

In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), reference can be made to the description in JP 2010-168539 A.

As a specific example of the ether dimer, for example, paragraph 0317 of JP 2013-029760 A can be referred to, and this content is incorporated in this specification. There may be only one type of ether dimer, or two or more types.

The acid value of the alkali-soluble resin is not particularly limited. Generally, 30 to 500 mgKOH/g is preferable, and 50 to 200 mgKOH/g or more is more preferable.

＜Polymerizable compound＞ The light-shielding composition contains a polymerizable compound. In this specification, a polymerizable compound means a compound that is polymerized by the action of a polymerization initiator described later, and means a component different from the above-mentioned dispersing resin and alkali-soluble resin.

The content of the polymerizable compound in the composition is not particularly limited. It is preferably 5 to 35% by mass relative to the total solid content of the composition, more preferably 10 to 30% by mass, and more preferably 15 to 25% by mass. Better. A polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When two or more polymerizable compounds are used in combination, the total content is preferably within the above range. The molecular weight (or weight average molecular weight) of the polymerizable compound is not particularly limited, but 2,000 or less is preferable.

As the polymerizable compound, a compound containing an ethylenically unsaturated group is preferred. That is, the light-shielding composition preferably contains a low-molecular compound containing an ethylenically unsaturated group as the polymerizable compound. As the polymerizable compound, compounds containing one or more ethylenic unsaturated bonds are preferred, compounds containing two or more are more preferred, compounds containing three or more are more preferred, and compounds containing five or more are particularly preferred. good. The upper limit is, for example, 15 or less. As an ethylenically unsaturated group, a vinyl group, (meth)aryl group, (meth)acryloyl group, etc. are mentioned, for example.

As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP 2008-260927 A and paragraph 0040 of JP 2015-068893 A can be used, and the above contents are incorporated in this specification.

The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, mixtures of these, and polymers of these. The polymerizable compound is preferably a 3 to 15 functional (meth)acrylate compound, and a 3 to 6 functional (meth)acrylate compound is more preferable.

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 2013-029760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, and this content is incorporated in this specification.

The polymerizable compound is dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku CO., LTD.), and dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku CO. , LTD.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku CO., LTD.), dipentaerythritol hexa(meth)acrylate (as a commercial product) , KAYARAD DPHA; manufactured by Nippon Kayaku CO., LTD., A-DPH-12E; manufactured by Shin-Nakamura Chemical CO., LTD) and these (meth)acrylic groups mediate ethylene glycol residues or propylene glycol residues The structure (for example, SR454 and SR499 commercially available from Sartomer company Inc.) is preferable. These oligomer types can also be used. In addition, NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Co., LTD.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 ( All are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. The aspect of the preferable polymerizable compound is shown below.

The light-shielding composition preferably contains at least two types of polymerizable compounds. Among them, from the viewpoint of better heat resistance and moisture resistance of the light-shielding film, it has a similar structure, contains two or more polymerizable compounds with different numbers of ethylenically unsaturated groups, and the number of ethylenically unsaturated groups Fewer compounds are preferably compounds containing at least one hydroxyl group. The reason for improving the heat resistance and moisture resistance of the light-shielding film by using these two or more polymerizable compounds is not clear, but the reason is presumed to be as follows: By using a polymerizable compound having a hydroxyl group, it is compatible with alkali-soluble resin. The solubility is improved, the polymerizable compound is uniformly distributed in the black layer, and the entire black layer is uniformly hardened. As such a mixture of two or more compounds having a similar structure and different numbers of ethylenically unsaturated groups, for example, the following formula (Z-1), formula (Z-4) or formula (Z- 5) Represents a mixture of compounds having different numbers of ethylenically unsaturated groups (preferably (meth)acryloyl groups) at the ends, and compounds with fewer ethylenically unsaturated groups contain at least 1 A mixture of compounds with more than one hydroxyl group.

The polymerizable compound may have acid groups such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred. The non-aromatic carboxylic acid anhydride is reacted with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to give it an acid group The polymerizable compound is more preferable, and among the esters, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Examples of commercially available products include ARONIX TO-2349, M-305, M-510, and M-520 manufactured by TOAGOSEICO., LTD.

As the acid value of the polymerizable compound containing an acid group, 0.1-40 mgKOH/g is preferable, and 5-30 mgKOH/g is more preferable. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development 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.

Regarding the polymerizable compound, a compound containing a caprolactone structure is also a preferable aspect. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylol Propane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol or trimethylolmelamine and other polyols are esterified with (meth)acrylic acid and ε-caprolactone to obtain, ε -Caprolactone upgrades multifunctional (meth)acrylates. Among them, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

[Chemical formula 16]

In formula (Z-1), all 6 Rs are groups represented by the following formula (Z-2), or 1 to 5 of the 6 Rs are groups represented by the following formula (Z-2) , And the remainder are groups represented by the following formula (Z-3).

[Chemical formula 17]

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

[Chemical formula 18]

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

Polymeric compounds containing a caprolactone structure, for example, are commercially available as KAYARAD DPCA series by Nippon Kayaku CO., LTD., DPCA-20 (in the above formulas (Z-1)~(Z-3), m=1, with The number of groups represented by formula (Z-2)=2, and R ¹ is a compound with all hydrogen atoms), DPCA-30 (in the above formulas (Z-1)~(Z-3), m=1, according to the formula The number of groups represented by (Z-2)=3, and R ¹ is a compound with all hydrogen atoms), DPCA-60 (in the above formulas (Z-1)~(Z-3), m=1, according to the formula ( The number of groups represented by Z-2)=6, R ¹ is a compound with all hydrogen atoms), DPCA-120 (in the above formulas (Z-1)~(Z-3), m=2, according to the formula (Z -2) The number of the represented group=6, the compound in which all R ¹ is a hydrogen atom) etc. Moreover, as a commercially available product of a polymerizable compound containing a caprolactone structure, M-350 (trade name) (trimethylolpropane triacrylate) manufactured by TOAGOSEI CO., LTD. can also be cited.

The polymerizable compound can also be a compound represented by the following formula (Z-4) or (Z-5).

[Chemical formula 19]

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

In the formula (Z-4), m is preferably an integer of 0-6, and more preferably an integer of 0-4. Moreover, it is preferable that the total of each m is an integer of 2-40, the integer of 2-16 is more preferable, and the integer of 4-8 is more preferable. In formula (Z-5), n is preferably an integer of 0-6, and more preferably an integer of 0-4. Moreover, it is preferable that the total of each n is an integer of 3-60, the integer of 3-24 is more preferable, and the integer of 6-12 is more preferable. In addition, in formula (Z-4) or formula (Z-5), -((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)- is on the oxygen atom side The form where the terminal is bonded to X is preferred.

The compound represented by formula (Z-4) or formula (Z-5) may be used singly or in combination of two or more kinds. In particular, in the formula (Z-5), all six X's are in the form of acryloyl groups, in the formula (Z-5), compounds in which all six X's are all acryloyl groups, and compounds in which at least one of the six Xs is a hydrogen atom The aspect of the mixture of the compounds is preferred. With such a structure, the heat resistance and moisture resistance of the light-shielding film can be improved, and the developability can be improved

In addition, as the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound, 20% by mass or more is preferable, and 50% by mass or more is more preferable. Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferable.

In addition, the polymerizable compound may contain a Cardo skeleton. As the polymerizable compound containing a cardo skeleton, a polymerizable compound having a 9,9-diarylfluorene skeleton is preferred. The polymerizable compound containing a cardo skeleton is not limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD) and Ogsol (manufactured by Osaka Gas Chemicals Co., LTD.). The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. As an example of such a polymerizable compound, NKEster A-9300 (manufactured by Shin Nakamura Chemical Co., LTD.) can be mentioned, for example. The content of the ethylenically unsaturated group of the polymerizable compound (representing the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g/mol) of the polymerizable compound) is preferably 5.0 mmol/g or more. The upper limit is not particularly limited, but is usually 20.0 mmol/g or less.

＜Polymerization initiator＞ The light-shielding composition preferably contains a polymerization initiator. The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. As the polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, etc. may be mentioned, and a photopolymerization initiator is preferred. In addition, as the polymerization initiator, a so-called radical polymerization initiator is preferred. The content of the polymerization initiator in the composition is not particularly limited, and it is preferably 0.5-20% by mass relative to the total solid content of the composition, more preferably 1.0-10% by mass, and 1.5-8% by mass Further better. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

(Thermal polymerization initiator) Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalononitrile, and dimethyl-(2,2')- Azo compounds such as azobis(2-propionic acid methyl ester) [V-601], and organic peroxides such as benzyl peroxide, lauryl peroxide, and potassium persulfate. Specific examples of the polymerization initiator include, for example, the polymerization initiator described on pages 65 to 148 of "Ultraviolet Curing System" by Kiyoshi Kato (published by Comprehensive Technology Center Co., Ltd.: 1989).

(Photopolymerization initiator) The above composition preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can initiate the polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from an ultraviolet region to a visible light region is preferable. In addition, the polymerization initiator may be an active agent that has some effect with the photosensitizer excited by light and generates active free radicals, or it may be an initiator that initiates cationic polymerization according to the type of polymerizable compound. In addition, it is preferable that the photopolymerization initiator contains at least one compound having an absorption coefficient of at least 50 mol in the range of 300 to 800 nm (more preferably, 330 to 500 nm).

The content of the photopolymerization initiator in the composition is not particularly limited, but it is preferably 0.5-20% by mass relative to the total solid content of the composition, more preferably 1.0-10% by mass, and 1.5-8% by mass. It is further preferred. A photoinitiator may be used individually by 1 type, and may use 2 or more types together. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

As the photopolymerization initiator, for example, halogenated hydrocarbon derivatives (for example, triazine skeleton-containing compounds, oxadiazole skeleton-containing compounds, etc.), phosphine compounds such as phosphine oxides, hexaaryl bis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, hydroxyacetophenone, etc. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP 2013-029760 A can be referred to, and this content is incorporated into this specification.

As the photopolymerization initiator, more specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the phosphine oxide described in Japanese Patent No. 4225898 can also be used. Material system initiator. As the hydroxyacetophenone compound, for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (brand names, all manufactured by BASF) can be used. As the aminoacetophenone compound, for example, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (brand names, all manufactured by BASF Corporation) can be used. As the aminoacetophenone compound, the compound described in JP 2009-191179 gazette whose absorption wavelength is matched with a long-wave light source such as a wavelength of 365 nm or a wavelength of 405 nm can also be used. As the phosphine compound, commercially available products IRGACURE-819 and IRGACURE-TPO (brand names, both manufactured by BASF Corporation) can be used.

(Oxime compound) As the photopolymerization initiator, an oxime ester-based polymerization initiator (oxime compound) is more preferable. In particular, the oxime compound has high sensitivity and high polymerization efficiency, and it is easy to set the content of the color material in the composition high, so it is preferable. As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-080068 A, or the compound described in JP 2006-342166 A can be used. As the oxime compound, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-acetoxyimino Butan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyloxy Imino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy) iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-benzene Propane-1-one and so on. In addition, JCS Perkin II (1979) pp.1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (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 Wait. Among the commercially available products, IRGACURE-OXE01 (made by BASF), IRGACURE-OXE02 (made by BASF), IRGACURE-OXE03 (made by BASF), or IRGACURE-OXE04 (made by BASF) are also preferred. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arkls NCI-831, Adeka Arkls NCI-930 (manufactured by ADEKA CORPORATION) or N-1919 (containing carbazole•oxime ester skeleton light Starter (manufactured by ADEKA CORPORATION).

In addition, as oxime compounds other than those described above, the compounds described in Japanese Patent Application Publication No. 2009-519904 in which an oxime is attached to the N-position of the carbazole can be used; those with a hetero substituent introduced at the benzophenone site The compound described in U.S. Patent No. 7626957; the compound described in Japanese Patent Laid-Open No. 2010-015025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into the pigment site; in the pamphlet of International Publication No. 2009-131189 The ketoxime compound described; and the compound described in the specification of U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule; Japanese Patent Laid-Open 2009- Compounds described in Bulletin No. 221114; etc. For example, paragraphs 0274 to 0275 of JP 2013-029760 A can be referred to, and this content is incorporated into this specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. In addition, the N-O bond of the oxime compound may be an oxime compound of the (E) body, or an oxime compound of the (Z) body, or a mixture of the (E) body and the (Z) body.

[Chemical formula 20]

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 the formula (OX-1), as the monovalent substituent represented by R, a monovalent non-metal atomic group is preferred. Examples of the monovalent non-metal atomic group include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. In addition, these groups may have one or more substituents. In addition, the aforementioned substituent may be further substituted with another substituent. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group. In formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferable, and an aryl group or a heterocyclic group is more preferable. These groups may have more than one substituent. As the substituent, the aforementioned substituents can be exemplified. In formula (OX-1), as the divalent organic group represented by A, an alkylene group, cycloalkylene group or alkynylene group having 1 to 12 carbon atoms is preferred. These groups may have more than one substituent. As the substituent, the aforementioned substituents can be exemplified.

As the photopolymerization initiator, an oxime compound containing a fluorine atom can also be used. Specific examples of the oxime compound containing a fluorine atom include the compounds described in JP 2010-262028 A; the compounds 24 and 36 to 40 described in JP 2014-500852 A; and JP 2013 -Compound (C-3) described in Bulletin No. 164471; etc. This content is incorporated into this manual.

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

[Chemical formula 21]

[Chemical formula 22]

In formula (1), R ¹ and R ² each independently represent an alkyl group with 1 to 20 carbons, an alicyclic hydrocarbon group with 4 to 20 carbons, an aryl group with 6 to 30 carbons, or 7 to 30 carbons. When R ¹ and R ² are phenyl groups, the phenyl groups can be bonded to each other to form a stilbene group. R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbons, and 6 carbons. ~30 aryl group, C7-30 aralkyl group, or C4-20 heterocyclic group, X represents a direct bond or a carbonyl group.

In the formula ^{(2), R 1, 1, R 2} , the same as R ^2, R ³ and R ⁴ meaning as in formula R (1) in R ³ and R ^4, R ⁵ represents -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, R ⁶ represents an alkyl group with 1 to 20 carbons, an aryl group with 6 to 30 carbons, an aralkyl group with 7 to 30 carbons, or a heterocyclic group with 4 to 20 carbons. X represents a direct bond or a carbonyl group , A represents an integer from 0 to 4.

In formula (3), R ¹ represents an alkyl group with 1 to 20 carbons, an alicyclic hydrocarbon group with 4 to 20 carbons, an aryl group with 6 to 30 carbons, or an aralkyl group with 7 to 30 carbons, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbons, an aryl group with 6 to 30 carbons, an aralkyl group with 7 to 30 carbons, or a heterocyclic group with 4 to 20 carbons, X Represents a direct bond or a carbonyl group.

In the formula (4), R ^{1, 1,} the same meaning as R ³ and R ⁴ R ³ and R ⁴ of the formula R (3) in, R ⁵ represents ^{-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, R ⁶ represents Alkyl group with 1-20 carbons, aryl group with 6-30 carbons, aralkyl group with 7-30 carbons or heterocyclic group with 4-20 carbons, X represents a direct bond or a carbonyl group, and a represents 0-4 Integer.

In the above formula (1) and formula (2), it is preferred that R ¹ and R ² are methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. R ⁴ is preferably an alkyl group or phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. In addition, in the above formulas (3) and (4), R ¹ is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, cyclohexyl group or phenyl group. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. R ⁴ is preferably an alkyl group or phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. As a specific example of the compound represented by Formula (1) and Formula (2), for example, the compound described in paragraphs 0076 to 0079 of JP 2014-137466 A can be cited. This content is incorporated into this manual.

Specific examples of oxime compounds that can be preferably used in the above composition are shown below. Among the oxime compounds shown below, the oxime compound represented by formula (C-13) is more preferable. In addition, as the oxime compound, for example, the compounds described in Table 1 of International Publication No. 2015-036910 pamphlet can also be used, and the above-mentioned contents are incorporated in this specification.

[化學式24]

[Chemical formula 23]

[Chemical formula 24]

It is preferable that the oxime compound has a maximum absorption in the wavelength region of 350 to 500 nm, and it is more preferable to have a maximum absorption in the wavelength region of 360 to 480 nm, and it is even more preferable that the absorbance at the wavelengths of 365 nm and 405 nm is higher. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and more preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured by a known method, for example, by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Corporation), using ethyl acetate at a concentration of 0.01 g/L. Better. The photopolymerization initiator can be used in combination of two or more types as necessary.

In addition, as the photopolymerization initiator, for example, paragraph 0052 of Japanese Patent Application Publication No. 2008-260927, paragraphs 0033 to 0037 of Japanese Patent Application Publication No. 2010-097210, and Japanese Patent Application Publication No. 2015-068893 may also be used. For the compound described in paragraph 0044 of, the above content is incorporated into this specification.

＜Polymerization inhibitor＞ The composition may contain a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used. As polymerization inhibitors, for example, phenolic polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tertiarybutyl-4-methylphenol, 2,6-di-tertiarybutyl- 4-methylphenol, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary butyl) Phenol), 4-methoxynaphthol, etc.); hydroquinone-based polymerization inhibitors (for example, hydroquinone, 2,6-di-tertiary butylhydroquinone, etc.); quinone-based polymerization inhibitors (for example, benzoquinone Etc.); radical polymerization inhibitors (for example, 2,2,6,6-tetramethylpiperidine 1-oxy radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Oxygen radicals, etc.); nitrobenzene-based polymerization inhibitors (for example, nitrobenzene, 4-nitrotoluene, etc.); and phenanthrene-based polymerization inhibitors (for example, phenanthrene, 2-methoxyphenanthrene 𠯤 etc.); etc. Among them, from the viewpoint that the composition has a more excellent effect, a phenol-based polymerization inhibitor or a radical-based polymerization inhibitor is preferable.

The effect of polymerization inhibitors is remarkable when used together with resins containing curable groups. The content of the polymerization inhibitor in the composition is not particularly limited. With respect to the total solid content of the composition, 0.0001 to 0.5% by mass is preferred, 0.001 to 0.2% by mass is more preferred, and 0.008 to 0.05% by mass is further preferred. Better. A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range. Furthermore, the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition (polymerization inhibitor content/polymerizable compound content (mass ratio)) is preferably greater than 0.0005, more preferably 0.0006 to 0.02, 0.0006 to 0.005 is more preferable.

＜Ultraviolet absorber＞ The composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of the black layer can be made a more excellent (fine) shape. As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used. As these specific examples, the compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012/0068292) of JP 2012-068418 A can be used, and these contents can be incorporated into this specification. In addition, diethylamino-phenylsulfonyl-based ultraviolet absorbers (manufactured by DAITO CHEMICAL CO., LTD., trade name, UV-503) and the like can also be preferably used. As the ultraviolet absorber, the compounds exemplified in paragraphs 0134 to 0148 of JP 2012-032556 A can be cited. The content of the ultraviolet absorber is preferably 0.001 to 15% by mass relative to the total solid content of the composition, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass.

＜Silane coupling agent (adhesive agent)＞ The composition may contain a silane coupling agent. When the black layer is formed on the substrate, the silane coupling agent functions as an adhesive that improves the adhesion between the substrate and the black layer. Silane coupling agent refers to a compound containing a hydrolyzable group and other functional groups in the molecule. In addition, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by a hydrolysis reaction and/or a condensation reaction. As the hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned. When the hydrolyzable group contains carbon atoms, the carbon number is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group with 4 or less carbon atoms or an alkenyloxy group with 4 or less carbon atoms are preferred.

In addition, when the black layer is formed on the substrate, in order to improve the adhesion between the substrate and the black layer, the silane coupling agent does not contain fluorine atoms and silicon atoms (except for the silicon atoms bonded by hydrolyzable groups). Preferably, it does not contain fluorine atoms, silicon atoms (excluding silicon atoms bonded by hydrolyzable groups), alkylene substituted by silicon atoms, linear alkyl groups with 8 or more carbons, and those with 3 or more carbons A branched alkyl group is preferred. The silane coupling agent may contain ethylenically unsaturated groups such as (meth)acrylic groups. When it contains an ethylenically unsaturated group, the number is preferably 1-10, more preferably 4-8. In addition, silane coupling agents containing ethylenically unsaturated groups (for example, compounds with a molecular weight of 2000 or less containing hydrolyzable groups and ethylenically unsaturated groups) do not meet the above-mentioned polymerizable compounds.

The content of the silane coupling agent in the composition is preferably 0.1-10% by mass relative to the total solid content in the composition, more preferably 0.5-8% by mass, and still more preferably 1.0-6% by mass. The above composition may include one type of silane coupling agent alone, or two or more types. When the composition contains two or more types of silane coupling agents, the total of them should be within the above range.

As the silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropylmethyl diethoxysilane, vinyl trimethoxysilane and vinyl triethoxysilane, etc.

＜Surface active agent＞ The composition may contain a surfactant. The surfactant helps to improve the coating properties of the composition. When the above composition contains a surfactant, the content of the surfactant relative to the total solid content of the composition is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 0.5 mass%, and more preferably 0.01 to 0.1 mass% Better. A surfactant may be used individually by 1 type, and may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.

Examples of surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

For example, if the composition contains a fluorine-based surfactant, the liquid properties (especially fluidity) of the composition are further improved. That is, when a film is formed using a composition containing a fluorine-based surfactant, the interfacial tension between the coated surface and the coating liquid is reduced to improve the wettability of the coated surface and increase the coated surface Coatability of the surface. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film with a uniform thickness with small thickness unevenness can be formed more preferably.

The fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and even more preferably 7-25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the coating film thickness and/or liquid-saving properties, and its solubility in the composition is also good.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F482, MEGAFACE F554 and MEGAFACE F780 (above, manufactured by DIC CORPORATION); Fluorad FC430, Fluorad FC431 and Fluorad FC171 (above, manufactured by Sumitomo 3M Limited); Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC -104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393 and Surflon KH-40 (above, manufactured by Asahi Glass Co., LTD.); and PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, a block polymer can also be used. As a specific example, for example, a compound described in JP 2011-089090 A can be cited.

＜Solvent＞ The composition preferably contains a solvent. The solvent is not particularly limited, and a known solvent can be used. The content of the solvent in the composition is not particularly limited. The solid content of the composition is preferably 10 to 90% by mass, more preferably 10 to 40% by mass, and 15 to 35% by mass. The amount is more preferable. A solvent may be used individually by 1 type, and may use 2 or more types together. When two or more solvents are used in combination, it is preferable to adjust the total solid content of the composition to fall within the above range.

Examples of the solvent include water and organic solvents.

(Organic solvents) Examples of organic solvents include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and propylene glycol. Monomethyl ether, propylene glycol monoethyl ether, acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, Ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, two Ethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxy propyl acetate, N,N-dimethylformamide, dimethyl sulfide, γ -Butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, ethyl lactate, etc., but not limited thereto.

(water) When the composition contains water, the content is preferably 0.001 to 5.0% by mass relative to the total mass of the composition, more preferably 0.01 to 3.0% by mass, and still more preferably 0.1 to 1.0% by mass. Among them, if the content of water is 3.0% by mass or less (more preferably 1.0% by mass or less) relative to the total mass of the composition, it is easy to suppress the deterioration of the viscosity stability over time of the components in the composition caused by hydrolysis or the like. If it is 0.01% by mass or more (preferably 0.1% by mass or more), it is easy to improve sedimentation stability over time.

＜Other optional ingredients＞ The composition may further contain optional components other than the above-mentioned components. For example, sensitizers, co-sensitizers, crosslinking agents, hardening accelerators, thermal hardening accelerators, fillers, plasticizers, diluents, and fat-sensitizing agents can be mentioned. Furthermore, the Adhesion promoters and other auxiliary agents on the substrate surface (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, antioxidants, fragrances, interfacial tension regulators, and chain transfer agents Etc.) and other well-known additives. For these components, for example, paragraphs 0183 to 0228 of JP 2012-003225 A (corresponding to paragraphs 0237 to 0309 of U.S. Patent Application Publication No. 2013/0034812) and paragraph 0101 of JP 2008-250074 A can be referred to. ~ 0102, paragraphs 0103 to 0104, paragraphs 0107 to 0109, and paragraphs 0159 to 0184 of JP 2013-195480 A, etc., and these contents are incorporated into the specification of this application.

<Method of manufacturing light-shielding composition> Regarding the composition, first, a color material composition containing a black color material is produced, and the obtained color material composition is further mixed with other components to form the composition. It is preferable to prepare a color material composition by mixing a black color material, a resin (preferably a dispersion resin), and a solvent. Furthermore, it is also preferable to make the color material composition contain a polymerization inhibitor.

The above-mentioned color material composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a mixer, a homogenizer, a high-pressure emulsifying device, a wet mill or a wet disperser, etc.).

When preparing the light-shielding composition, each component may be blended at once, or each component may be dissolved or dispersed in a solvent and then blended sequentially. In addition, there are no particular restrictions on the order of input and working conditions during blending.

For the purpose of removing foreign matter and reducing defects, it is preferable to filter the light-shielding composition with a filter. As the filter, as long as it is a filter conventionally used for filtering purposes, etc., it can be used without particular limitation. Examples include filters based on fluorine resins such as PTFE (polytetrafluoroethylene), polyamine resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). . Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, more preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. If it is set in this range, the filter clogging of the pigment (including black pigment) can be suppressed, and fine foreign matter such as impurities and aggregates contained in the pigment can be reliably removed. When using filters, different filters can be combined. At this time, the filtration by the first filter may be performed only once, or may be performed two or more times. When combining different filters to perform filtration more than two times, the pore size after the second filtration is preferably the same or larger than the pore size of the first filtration. In addition, it is possible to combine first filters with different pore diameters within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., Toyo Roshi Kaisha, LTD., Nihon Entegris K.K. (formerly Mykrolis Corpration), and KITZ MICROFILTER CORPORATION. As the second filter, a filter formed of the same material as the above-mentioned first filter can be used. The pore diameter of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and even more preferably 0.3 to 6.0 μm. It is preferable that the composition does not contain impurities such as metals, halogen-containing metal salts, acids, and alkalis. As for the content of impurities contained in these materials, 1 mass ppm or less is preferable, 1 mass ppb or less is more preferable, 100 mass ppt or less is more preferable, and 10 mass ppt or less is particularly preferable, and it does not substantially contain (measure Below the detection limit of the device) is the best. In addition, the aforementioned impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Electric Corporation, Agilent 7500cs type).

[Formation of the black layer] The method for forming the black layer is not particularly limited, and the light-shielding composition of the present invention is coated on a support, and the obtained coating film is cured to form a black layer (including a patterned black layer).

Preferably, the method for forming the black layer includes the following processes. • Coating film formation process • Hardening process •Development process Hereinafter, each process will be described.

＜Coating film forming process＞ In the coating film formation process, before curing (exposure), the light-shielding composition is coated on the support to form a coating film (composition layer). As the support, for example, an imaging element (light-receiving element) such as CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) provided on a substrate (for example, a silicon substrate) can be used. The solid-state imaging device substrate. In addition, if necessary, an undercoat layer for improving adhesion with the upper layer, preventing diffusion of substances, and flattening the surface of the substrate may be provided on the support.

As a method of coating the composition on the support, various coating methods such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, and a screen printing method can be applied. The thickness of the coating film is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.2 to 3 μm. The drying (pre-baking) of the coating film applied on the support can be performed at a temperature of 50 to 140° C. for 10 to 300 seconds using a hot plate, an oven, etc., for example.

<Curing process> In the curing process, the coating film formed in the coating film formation process is irradiated with actinic rays or radiation for exposure, and the coating film irradiated with light is cured. The method of light irradiation is not particularly limited, but it is preferable to perform light irradiation through a photomask having patterned openings. Exposure by radiation is preferable. As the radiation that can be used for exposure, ultraviolet rays such as g-rays, h-rays, and i-rays are particularly preferred. As the light source, a high-pressure mercury lamp is preferred. The irradiation intensity is 5 ~ 1500mJ / cm ² is preferred, 10 ~ 1000mJ / cm ² is more preferred. In addition, when the composition contains a thermal polymerization initiator, the coating film may be heated in the above-mentioned curing process. The heating temperature is not particularly limited, but 80 to 250°C is preferred. In addition, the heating time is not particularly limited, but 30 to 300 seconds is preferable. In addition, in the curing process, when heating the coating film, it can also be used as a post-baking as described later. In other words, during the curing process, when the coating film is heated, the manufacturing method of the black layer may not include the post-baking process.

＜Development process＞ The development process is a process of developing the above-mentioned coating film after exposure. Through this process, the non-light-irradiated part of the coating film in the curing process is eluted, leaving only the light-cured part, thereby obtaining a patterned black layer. The type of developer used in the development process is not particularly limited, and an alkaline developer that does not cause damage to the imaging elements and circuits of the substrate is preferred. The development temperature is, for example, 20 to 30°C. The development time is, for example, 20 to 90 seconds. In order to better remove the residue, in recent years, it has been implemented for 120 to 180 seconds. Furthermore, in order to further improve the residue removal performance, sometimes the process of spinning off the developer solution every 60 seconds is repeated several times, and further supplying the developer solution again.

As the alkaline developer, 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) is preferred. Examples of basic compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, hydroxide Tetraethylammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo[5.4.0]- 7-Undecene, etc. (Among them, organic bases are preferred.). In addition, when it is used as an alkali developer, it is usually washed with water after development.

＜Post-baking＞ After the hardening process, post-heating treatment (post-baking) is preferred. Post-baking is used for heat treatment after development for complete curing. The heating temperature is preferably 240°C or less, and more preferably 220°C or less. The lower limit is not particularly limited, and if efficient and effective treatment is considered, 50°C or higher is preferable, and 100°C or higher is more preferable. Post-baking can be carried out continuously or in batches using heating mechanisms such as a heating plate, a flow oven (hot air circulating dryer) or a high-frequency heating machine.

The above-mentioned post-baking 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, more preferably 10 vol% or less, particularly preferably 7 vol% or less, and most preferably 3 vol% or less. The lower limit is not particularly limited, but is actually 10 volume ppm or more.

In addition, it can be changed to be based on the above-mentioned heating and then baking, and curing is completed by UV (ultraviolet) irradiation. In this case, it is preferable that the aforementioned composition further contains a UV curing agent. The UV curing agent is preferably a UV curing agent that can be cured at the exposure wavelength of the polymerization initiator added for the lithography process based on the usual i-ray exposure, that is, shorter than the wavelength of 365 nm. As a UV curing agent, Ciba IRGACURE 2959 (trade name) is mentioned, for example. When UV irradiation is performed, it is preferable that the coating is cured at a wavelength of 340nm or less. The lower limit of the wavelength is not particularly limited, but it is usually 220 nm or more. In addition, the exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and more preferably 800 to 3500 mJ. In order to perform low-temperature hardening more effectively, the UV hardening process is preferably performed after the hardening process. The exposure light source is preferably a non-ozone mercury lamp.

[Physical properties of black layer] From the standpoint of having excellent light-shielding properties, the optical density (OD: Optical Density) per 1.0μm thickness of the black layer in the 400-1200nm wavelength region is preferably 1.7 or more, more preferably 2.0 or more, and 2.1 or more Further better. In addition, the upper limit is not particularly limited, but 10 or less is generally preferred. In addition, in this specification, the optical density per 1.0 μm thickness in the 400 to 1200 nm wavelength region of 2.0 or more means that the optical density per 1.0 μm thickness in the entire wavelength region of 400 to 1200 nm is 2.0 or more. In addition, the optical density of the black layer (light-shielding film) can be measured as follows. First, the black layer (light-shielding film) is formed on a glass substrate, using a spectrophotometer U-4100 (trade name, manufactured by Hitachi High-Technologies Corporation) integrating sphere type The light-receiving unit measures, and also measures the thickness of the measuring part, and calculates the optical density for each predetermined thickness.

The thickness of the black layer is preferably 0.1 to 4.0 μm, and more preferably 1.0 to 2.5 μm. Moreover, depending on the application, the black layer may be a thin film or a thick film compared to this range. In addition, when the black layer is used as a light attenuating film, the light-shielding property can be adjusted as a film thinner than the above range (for example, 0.1 to 0.5 μm). At this time, the optical density per 1.0 μm thickness in the wavelength region of 400 to 1200 nm is preferably 0.1 to 1.5, and more preferably 0.2 to 1.0.

[Oxygen blocking layer] The oxygen blocking layer is a layer formed on the black layer and has a function of blocking oxygen passing through the black layer from the surface opposite to the contact surface with the black layer. Examples of the oxygen blocking layer include a layer having an oxygen permeability in the thickness direction (hereinafter, also simply referred to as "oxygen permeability") of 50 ml/(m ² •day•atm) or less, and an oxygen permeability of 10 ml/( The layer below m ² •day•atm) is preferred, the layer below 1.5ml/(m ² •day•atm) is more preferred, and the layer below 1.0ml/(m ² •day•atm) is further preferred . The lower limit of the oxygen transmission rate is preferably 0.001 ml/(m ² •day•atm). The oxygen permeability can be measured with an oxygen permeability measuring device (Model 8001, manufactured by ILLINOIS), for example.

The oxygen blocking layer is a single layer made of inorganic materials. In this specification, "single layer" means a layer in which the composition of the material constituting the layer is uniform in the thickness direction and the in-plane direction. Therefore, for example, a laminate of a layer A composed of an inorganic material a and a layer B composed of an inorganic material b having a composition different from the inorganic material a has a function of blocking oxygen even in either of the layer A and the layer B, It also does not include the oxygen blocking layer specified in this specification. In addition, "comprised of an inorganic material" means that the content of carbon atoms in the material constituting the oxygen blocking layer is 5% by mass or less with respect to the total mass of the oxygen blocking layer. The content of the carbon atoms is preferably 2.5% by mass or less relative to the total mass of the oxygen blocking layer. In addition, the lower limit of the content of the above-mentioned carbon atoms is not particularly limited, and may be the detection limit or less. After a smooth surface is formed in the oxygen blocking layer by grinding or cutting, an electron probe microanalyzer (EPMA: Electron Probe Micro Analyzer) (for example, "JXA-8530F" (trade name) manufactured by JEOL Ltd. )) Analyze the formed smooth surface to determine the content of carbon atoms in the material constituting the oxygen blocking layer.

The thickness of the oxygen blocking layer is 10 to 500 nm. When the thickness of the oxygen blocking layer is in the above-mentioned range, a light-shielding film having a more excellent balance between light resistance and moisture resistance can be produced. In more detail, if the thickness of the oxygen blocking layer is 10 nm or more, the effect of suppressing changes in the thickness of the light-shielding film and changes in optical properties (transmittance and reflectance) after the light resistance test is improved. If the thickness is 500 nm or less, the effect of suppressing the peeling of the black layer from the substrate after the moisture resistance test is improved. If the thickness of the oxygen blocking layer is 500 nm or less, the reason for improving the moisture resistance is not clear, but it is presumed that the reason is as follows: if the thickness of the oxygen blocking layer is greater than 500 nm, after the humidity resistance test, the The stress generated by the difference in shrinkage between the black layer and the substrate becomes stronger, causing the black layer to peel off from the substrate. In addition, when the thickness of the oxygen blocking layer is 500 nm or less, it is possible to reduce the reflected light on the surface of the black layer and the surface of the oxygen blocking layer when the light blocking film including the black layer and the oxygen blocking layer is installed on the device. The interference of reflected light can prevent the degradation of device performance.

From the viewpoint of better moisture resistance and heat resistance of the light-shielding film, the thickness of the oxygen blocking layer is preferably greater than 50 nm and less than 250 nm, and more preferably 70 to 200 nm. In addition, the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer (thickness of the black layer/thickness of the oxygen blocking layer) can be 2 to 100, from the viewpoint of the moisture resistance and heat resistance of the light shielding film being more excellent , 7~30 is preferred, 10~25 is more preferred.

The inorganic material constituting the oxygen blocking layer is not particularly limited, and metal oxides, metal nitrides, and metal oxynitrides can be mentioned. As the metal contained in the inorganic material, silicon, titanium, aluminum, indium, tin, niobium, zirconium, cerium, tantalum, and zinc can be mentioned. Silicon, titanium or aluminum is preferred, and silicon is more preferred.

Specific examples of inorganic materials constituting the oxygen blocking layer include silicon oxide, silicon nitride, indium oxide, tin oxide, niobium oxide, titanium oxide, zirconium oxide, cerium oxide, tantalum oxide, aluminum oxide, and zinc oxide. Silicon oxide and silicon nitride are preferable, and silicon oxide is more preferable from the viewpoint of better light resistance and moisture resistance of the light-shielding film.

In addition, the oxygen blocking layer of the present invention is a single layer composed of an inorganic material and does not substantially contain an organic component. When the oxygen blocking layer contains organic components, the organic components contained in the oxygen blocking layer are decomposed due to light irradiation to the oxygen blocking layer, and the oxygen blocking ability is reduced. In contrast, a single layer made of an inorganic material, that is, the oxygen blocking layer of the present invention can prevent such a decrease in oxygen blocking ability. In addition, in this specification, the oxygen blocking layer "substantially does not contain organic components" means that the content of carbon atoms in the material constituting the oxygen blocking layer is 5% by mass or less with respect to the total mass of the oxygen blocking layer. By the above method, the content of carbon atoms in the material constituting the oxygen blocking layer is measured using an electron probe microanalyzer.

From the viewpoint of being more excellent in heat resistance, the oxygen blocking layer is preferably substantially free of particles. This is because when the oxygen barrier layer contains particles, the composition of the material constituting the layer becomes non-uniform, and regions with different shrinkage properties to heat are generated. Therefore, the oxygen barrier layer is greatly distorted in a high-temperature environment and the heat resistance is reduced. In addition, from the viewpoint that the surface becomes smoother and the in-plane uniformity of reflectance is more excellent, it is preferable that the oxygen blocking layer contains substantially no particles. In addition, the above-mentioned "particle" means a particle of a substance having a composition different from that of the inorganic material constituting the oxygen blocking layer, and the particle diameter is 10 nm or more.

The content of particles in the oxygen blocking layer can be measured by the following method using an electron probe microanalyzer (EPMA) (for example, "JXA-8530F" (trade name) manufactured by JEOL Ltd.). First, the oxygen blocking layer is polished or cut to form a smooth surface. After that, an electron probe microanalyzer is used to measure the distribution of the element composition on the formed smooth surface to obtain a mapping image of the element composition. In the obtained mapping image, according to the difference of element composition and continuous phase, the particle existence area is determined. Next, the total area of the particle area is divided by the observation area to obtain the area ratio of the particles in the observation surface. Then, the area ratio is converted into a volume ratio (3/2 of the area ratio), and then converted into a mass ratio based on the element composition, thereby obtaining the content of particles relative to the total amount of the oxygen blocking layer. For example, when silicon oxide particles are present in the oxygen blocking layer made of silicon oxide (SiO ₂ ), the outline of the silicon oxide particles will be displayed on the mapping image due to the silanol groups (SiOH) present on the surface of the silicon oxide particles Therefore, the presence of particles can be confirmed. In this way, according to the above method, the content of particles can be measured based on the difference in the composition of the continuous phase and the particles in the oxygen blocking layer. In addition, in this specification, the oxygen blocking layer "substantially does not contain particles" also means that the content of particles in the oxygen blocking layer measured by the above method is 5% by mass or less relative to the total mass of the oxygen blocking layer. Below the detection limit.

[Formation of oxygen blocking layer] The method of forming the oxygen blocking layer is not particularly limited, and a known method of forming a film of an inorganic material can be used. Examples of film formation methods include sputtering, vacuum deposition, ion beam assisted vapor deposition, ion plating, plasma CVD (chemical vapor deposition), and other vapor deposition methods, and spin coating Wet method such as dip coating method, casting method, slit coating method and spraying method.

Among them, from the standpoint of making it easier to form a thin film, it is preferable to form the oxygen blocking layer by vapor deposition. From the standpoint of making it easier to control the thickness and having better adhesion to the object, that is, the black layer, by sputtering It is more preferable to form the oxygen blocking layer by radiation. The sputtering method is not particularly limited, and may be known methods such as pulse sputtering, AC sputtering, and digital sputtering.

For example, when the oxygen blocking layer is formed by sputtering, it is necessary to arrange a substrate with a black layer formed on the surface in a chamber with a mixed gas atmosphere of inert gas and reactive gas (such as oxygen or nitrogen). The composition method selects the target to form the oxygen blocking layer. In addition, the type of inert gas is not particularly limited, and inert gas such as argon or helium can be used. In addition, the reactive gas may be selected according to the composition of the oxygen blocking layer to be formed.

The pressure in the chamber based on the mixed gas of the inert gas and the reactive gas is not particularly limited, and it may be 1.0 Pa or less, preferably 0.5 Pa or less. The lower limit of the pressure in the chamber based on the mixed gas of the inert gas and the reactive gas is not particularly limited. For example, 0.1 Pa or more is preferable. In addition, when the oxygen blocking layer is formed by a sputtering method, the thickness of the oxygen blocking layer can be adjusted by adjusting the discharge power or the film formation time.

[Manufacture of shading film] The manufacturing method of the light-shielding film of this invention is not specifically limited. The light-shielding film of the present invention can be manufactured by a manufacturing method comprising coating a light-shielding composition containing a black color material, a resin, a polymerizable compound, and a polymerization initiator on a support, and then The process of curing the coating film to form a black layer and the process of forming an oxygen blocking layer on the black layer. As the "process for forming the black layer", the method described in the "formation of the black layer" can be applied, and as the "process for forming the oxygen blocking layer", it is applicable to the "formation of the oxygen blocking layer". The method described is fine.

[Physical properties and uses of shading film] The thickness of the light-shielding film is preferably 0.1 to 6.0 μm, and more preferably 1.0 to 3.5 μm. In addition, depending on the application, the light-shielding film may be a thin film or a thick film compared to this range. The reflectance of the light-shielding film is preferably less than 5%, more preferably less than 3%, and more preferably less than 2%.

In addition, the above-mentioned light-shielding film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multifunction printers and scanners; surveillance cameras, barcode reading Industrial machines such as automated teller machines (ATM: automated teller machines), high-speed cameras, and machines with personal identification functions using facial recognition or biometrics; automotive camera machines; endoscopes, capsule endoscopes, catheters, etc. Medical camera equipment; and living body sensors, biosensors, military reconnaissance cameras, stereo map cameras, meteorological and ocean observation cameras, terrestrial resources reconnaissance cameras, and exploration for astronomical and deep-space targets in the universe Cameras and other aerospace machines; light-shielding members and light-shielding films of optical filters and modules used in such applications, and are further suitable for anti-reflection members and anti-reflection films.

The aforementioned light-shielding film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode: Organic Light Emitting Diode). In addition to optical filters and optical films used in micro LEDs and micro OLEDs, the above-mentioned light-shielding film is also suitable for components that provide light-shielding function or anti-reflection function. As examples of micro LEDs and micro OLEDs, examples described in Japanese Special Publication No. 2015-500562 and Japanese Special Publication No. 2014-533890 can be cited.

The above-mentioned light-shielding film is also preferable as an optical filter and an optical film for quantum dot sensors and quantum dot solid-state imaging devices. Moreover, it is suitable as a member which provides a light-shielding function and an anti-reflection function. As examples of quantum dot sensors and quantum dot solid-state imaging devices, there can be cited the examples described in US Patent Application Publication No. 2012/037789 and International Publication No. 2008/131313 pamphlets.

[Optical element, and solid-state imaging element and solid-state imaging device] The light-shielding film of the present invention is also preferably used in solid-state imaging devices. As described above, the light-shielding film of the present invention is excellent in light resistance and moisture resistance. In addition, the light-shielding film of the present invention has excellent heat resistance.

The present invention also includes the invention of optical elements. The optical element of the present invention is an optical element having the above-mentioned light-shielding film. Examples of optical elements include optical elements used in optical devices such as cameras, binoculars, microscopes, and semiconductor exposure devices. Among them, as the above-mentioned optical element, for example, a solid-state imaging element mounted in a camera or the like is preferable.

Furthermore, the solid-state imaging device of the present invention is a solid-state imaging device having the above-mentioned light-shielding film. The solid-state imaging element includes a light-shielding film, and there is no particular limitation. For example, a substrate having a plurality of photodiodes including a light-receiving area constituting the solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) Light-receiving elements such as bulk and polysilicon have a form in which a light-shielding film is provided on the side of the light-receiving element forming surface of the support (for example, parts other than the light-receiving part and/or pixels for color adjustment, etc.) or the opposite side of the forming surface. Furthermore, when the light-shielding film is used as the light attenuating film, for example, if the light attenuating film is arranged so that a part of the light enters the light receiving element after passing through the light attenuating film, the dynamic range of the solid-state imaging element can be improved. The solid-state imaging device includes the above-mentioned solid-state imaging element.

1 to 2, a configuration example of a solid-state imaging device and a solid-state imaging element will be described. In addition, in FIG. 1 to FIG. 2, in order to make each part clear, the mutual ratio of thickness and/or width is ignored, and a part is exaggerated and shown. FIG. 1 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device including the solid-state imaging element of the present invention. As shown in FIG. 1, the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Furthermore, the lens layer 111 is superposed on this cover glass 103 via the spacer 104. As shown in FIG. The lens layer 111 is composed of a support 113 and a lens material 112. The lens layer 111 may be integrally formed by the support 113 and the lens material 112. If stray light enters the peripheral region of the lens layer 111, the light condensing effect on the lens material 112 due to the diffusion of the light is weakened, and the light reaching the imaging unit 102 is reduced. In addition, noise caused by stray light also occurs. Therefore, a light shielding film 114 is provided in the peripheral region of the lens layer 111 to shield light. The light-shielding film of the present invention can be used as the light-shielding film 114 described above.

The solid-state imaging element 101 photoelectrically converts the optical image formed on the imaging section 102 as its light-receiving surface and outputs it as an image signal. The solid-state imaging element 101 includes a multilayer substrate 105 in which two substrates are laminated. The multilayer substrate 105 includes a rectangular wafer substrate 106 and a circuit substrate 107 of the same size, and the circuit substrate 107 is layered on the back area of the wafer substrate 106.

The material used as the substrate of the wafer substrate 106 is not particularly limited, and known materials can be used.

An imaging unit 102 is provided in the center of the surface of the wafer substrate 106. In addition, a light-shielding film 115 is provided in the peripheral region of the imaging unit 102. By shielding the scattered light incident on the peripheral region by the light shielding film 115, it is possible to prevent the generation of dark current (noise) from the circuits in the peripheral region. It is preferable to use the light-shielding film of the present invention as the light-shielding film 115.

A plurality of electrode pads 108 are provided on the edge of the surface of the wafer substrate 106. The electrode pad 108 is electrically connected to the imaging unit 102 via a signal wire (not shown in the figure) provided on the surface of the chip substrate 106.

On the back surface of the circuit board 107, external connection terminals 109 are provided substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to the electrode pad 108 via a through electrode 110 that penetrates the build-up substrate 105 vertically. In addition, each external connection terminal 109 is connected to a control circuit that controls the drive of the solid-state imaging element 101, an image processing circuit that performs image processing on the imaging signal output from the solid-state imaging element 101, and the like via wiring not shown.

FIG. 2 shows a schematic cross-sectional view of the imaging unit 102. As shown in FIG. 2, the imaging unit 102 is composed of light-receiving elements 201, color filters 202, microlenses 203, and other parts provided on a substrate 204. The color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The light-shielding film of the present invention can be used as the black matrix 205bm.

As the material of the substrate 204, the same material as the aforementioned wafer substrate 106 can be used. A p-well layer 206 is formed on the surface layer of the substrate 204. In the p-well layer 206, light-receiving elements 201 including n-type layers are formed in a square grid pattern and generate and accumulate signal charges by photoelectric conversion.

On one side of the light-receiving element 201, a vertical transfer path 208 including an n-type layer is formed through the readout gate portion 207 of the surface layer of the p-well layer 206. In addition, on the other side of the light receiving element 201, a vertical transmission path 208 belonging to adjacent pixels is formed through an element isolation region 209 including a p-type layer. The readout gate portion 207 is used to read out the signal charge accumulated in the light receiving element 201 to the channel area of the vertical transmission path 208.

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

On the vertical transfer electrode 211, a light-shielding film 212 is formed so as to cover the surface thereof. The light-shielding film 212 has an opening at a position directly above the light-receiving element 201 and shields areas other than it from light. The light-shielding film of the present invention can be used as the light-shielding film 212. A transparent intermediate layer is provided on the light-shielding film 212. The intermediate layer includes an insulating film 213 including BPSG (borophospho silicate glass), an insulating film (passivation film) 214 including P-SiN, a transparent resin, etc. The planarization film 215. The color filter 202 is formed on the intermediate layer.

[Image display device] The image display device of the present invention includes the light-shielding film of the present invention. As a form in which an image display device has a light-shielding film, for example, a form in which a color filter including a light-shielding film as a black matrix is used in an image display device can be cited. Next, the black matrix and the color filter including the black matrix will be described, and further, as a specific example of the image display device, a liquid crystal display device including such a color filter will be described.

[Black Matrix] The light-shielding film of the present invention is also preferably used as a black matrix. The black matrix is sometimes included in image display devices such as color filters, solid-state imaging elements, and liquid crystal display devices. Examples of the black matrix include those described above; a black edge provided on the periphery of an image display device such as a liquid crystal display device; a grid-like and/or linear black pattern between red, blue, and green pixels Part; dot-like and/or linear black patterns for TFT (thin film transistor) shading; etc. The definition of this black matrix is described in, for example, Yasuhira Kanno, "Dictionary of Terms for Liquid Crystal Display Manufacturing Device", 2nd Edition, NIKKAN KOGYO SHIMBUN, LTD., 1996, p. 64. In order to improve the display contrast, and to prevent the deterioration of image quality caused by light leakage current when using thin-film transistors (TFT) active matrix drive type liquid crystal display devices, the black matrix has high light-shielding properties (measured by optical density OD) 3 or more) is preferred.

The black matrix manufacturing method is not particularly limited, and it can be manufactured by the same method as the manufacturing method of the light shielding film described above. Specifically, the composition is applied to a substrate to form a coating film, and after exposure and development are performed to form a patterned black layer, an oxygen blocking layer is formed on the black layer, whereby a black matrix can be manufactured. In addition, the thickness of the light-shielding film used as the black matrix is preferably 0.1 to 4.0 μm.

The material of the above-mentioned substrate is not particularly limited, but it is preferable to have a transmittance of 80% or more for visible light (wavelength 400 to 800 nm). As such materials, specifically, for example, glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resin and polyolefin resin; etc., from chemical resistance and heat resistance From the viewpoint of performance, alkali-free glass or quartz glass is preferable.

＜Color filter＞ It is also preferable that the light-shielding film of the present invention is included in a color filter. There are no particular restrictions on the form in which the color filter includes a light-shielding film, and a color filter provided with a substrate and the above-mentioned black matrix can be mentioned. That is, it is possible to exemplify a color filter having red, green, and blue colored pixels formed in the opening of the black matrix formed on the substrate.

The color filter containing the black matrix can be manufactured by the following method, for example. First, a coating film of a composition containing a pigment corresponding to each colored pixel of the color filter is formed in the opening of the patterned black matrix formed on the substrate. In addition, there are no particular restrictions on the composition for each color, and known compositions can be used. Among the compositions described in this specification, a composition in which a black color material is used instead of a coloring agent corresponding to each pixel is Better. Next, the coating film is exposed through a photomask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed portion by a development process, baking can be performed to form colored pixels in the openings of the black matrix. For example, by performing a series of operations on the composition for each color containing red, green, and blue pigments, it is possible to manufacture color filters with red, green, and blue pixels.

＜Liquid crystal display device＞ The light-shielding film of the present invention is preferably included in a liquid crystal display device. The liquid crystal display device includes a light-shielding film, and there is no particular limitation, and examples include a color filter including the black matrix described above.

As the liquid crystal display device of the present embodiment, for example, a mode provided with a pair of substrates arranged facing each other and a liquid crystal compound enclosed between the substrates can be cited. As the above-mentioned substrate, the substrate for the black matrix has been described.

As a specific form of the above-mentioned liquid crystal display device, for example, a polarizer/substrate/color filter/transparent electrode layer/alignment film/liquid crystal layer/alignment film/transparent electrode layer/TFT (Thin Film Transistor : Thin film transistor) a laminate of components/substrate/polarizer/backlight unit.

In addition, the liquid crystal display device is not limited to the above, and examples include "electronic display devices (by Akio Sasaki, published by Kogyo Chosakai Publishing Co., LTD., 1990)" and "display devices (by Ibuki Junsho, Sangyo Tosho). Publishing Co., LTD. issued in 1989)" and other liquid crystal display devices. Also, for example, the liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (written by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. 1994)".

[Infrared Sensor] It is also preferable that the light shielding film of the present invention is included in an infrared sensor. The infrared sensor of the above embodiment will be described with reference to FIG. 3. Fig. 3 is a schematic cross-sectional view showing a configuration example of an infrared sensor provided with the light-shielding film of the present invention. The infrared sensor 300 shown in FIG. 3 includes a solid-state imaging element 310. The imaging area provided on the solid-state imaging element 310 is configured by combining the infrared absorption filter 311 and the color filter 312 of the embodiment of the present invention. The infrared absorption filter 311 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm), and shields light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm, more preferably a wavelength For the film of 900-1000nm light), as a coloring agent, a cured film containing an infrared absorber (the form of the infrared absorber is as described above) can be used. The color filter 312 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible light region, such as a color filter formed with pixels of red (R), green (G), and blue (B) The form of the device is as described above. Between the infrared transmission filter 313 and the solid-state imaging element 310, a resin film 314 (for example, a transparent resin film, etc.) capable of transmitting light of the wavelength of the infrared transmission filter 313 is arranged. The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light of a specific wavelength, and can use coloring agents that absorb light in the visible light region (such as perylene compounds and/or benzofuranone compounds) and infrared rays. Light-shielding film of absorber (for example, pyrrolopyrrole compound, phthalocyanine compound, naphthalocyanine compound, polymethine compound, etc.). The infrared transmission filter 313 shields light with a wavelength of 400 to 830 nm, and preferably transmits light with a wavelength of 900 to 1300 nm. The color filter 312 and the infrared transmission filter 313 are provided with a microlens 315 on the hν side of the incident light. A planarization film 316 is formed to cover the microlens 315. In the form shown in FIG. 3, a resin film 314 is arranged, but an infrared transmission filter 313 may be formed instead of the resin film 314. In other words, the infrared transmission filter 313 may be formed on the solid-state imaging element 310. In addition, in the form shown in FIG. 3, the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thicknesses of the two may be different. In addition, in the form shown in FIG. 3, the color filter 312 is provided at a position closer to the incident light hν side than the infrared absorption filter 311. However, the order of the infrared absorption filter 311 and the color filter 312 may also be changed. The infrared absorption filter 311 is provided at a position closer to the hν side of the incident light than the color filter 312. Furthermore, in the form shown in FIG. 3, the infrared absorption filter 311 and the color filter 312 are laminated adjacently, but the two filters do not have to be adjacent to each other, and another layer may be provided between the two filters. The light-shielding film of the present invention can be used as a light-shielding film for the end and/or side of the surface of the infrared absorption filter 311, if used on the inner wall of the infrared sensor device, it can also prevent internal reflection and/or interference. Unexpected light incident on the light receiving part increases sensitivity. According to this infrared sensor, since image information can be acquired at the same time, it is possible to perform motion sensing for identifying and detecting the object of motion. In addition, according to the infrared sensor, distance information can be obtained, and therefore, it is possible to perform photography of images including 3D information. Furthermore, the infrared sensor can also be used as a biometric sensor.

Next, a solid-state imaging device to which the above-mentioned infrared sensor is applied will be described. The solid-state imaging device described above includes a lens optical system, a solid-state imaging element, an infrared light-emitting diode, and the like. In addition, regarding each configuration of the solid-state imaging device, reference can be made to paragraphs 0032 to 0036 of JP 2011-233983 A, which are incorporated into this specification.

[Headlight Unit] The light-shielding film of the present invention is preferably included in a headlight unit of a vehicle lamp such as an automobile. In order to shield at least a part of the light emitted from the light source, the cured film of the present invention included in the headlight unit is preferably formed in a pattern. The headlight unit of the above-mentioned embodiment will be described using FIGS. 4 and 5. 4 is a schematic diagram showing a configuration example of the headlight unit, and FIG. 5 is a schematic perspective view showing a configuration example of the light shielding portion of the headlight unit. As shown in FIG. 4, the headlight unit 10 has a light source 12, a light shielding part 14, and a lens 16, and the light source 12, the light shielding part 14, and the lens 16 are arrange|positioned in this order. As shown in FIG. 5, the light shielding portion 14 has a base 20 and a light shielding film 22. The light shielding film 22 has a patterned opening 23 for irradiating light emitted from the light source 12 in a specific shape. The light distribution pattern irradiated from the lens 16 is determined by the shape of the opening 23 of the light shielding film 22. The lens 16 projects the light L from the light source 12 passing through the light shielding portion 14. As long as the light source 12 can irradiate a specific light distribution pattern, the lens 16 is not necessarily required. The lens 16 is appropriately determined according to the irradiation distance and irradiation range of the light L. In addition, as long as the base 20 can hold the light-shielding film 22, its structure is not particularly limited. However, it is preferable that it is not deformed by the heat of the light source 12 or the like. For example, it is made of glass. FIG. 5 shows an example of a light distribution pattern, but it is not limited to this. In addition, the light source 12 is not limited to one. For example, it may be arranged in a row or in a matrix. When a plurality of light sources are installed, for example, one light shielding part 14 may be provided for one light source 12. At this time, all the light-shielding films 22 of the plurality of light-shielding parts 14 may have the same pattern or may have different patterns.

The light distribution pattern based on the pattern of the light shielding film 22 will be described. 6 is a schematic diagram showing an example of a light distribution pattern based on the headlight unit, and FIG. 7 is a schematic diagram showing another example of a light distribution pattern based on the headlight unit. In addition, the light distribution pattern 30 shown in FIG. 6 and the light distribution pattern 32 shown in FIG. 7 both indicate areas where light is irradiated. In addition, the area 31 shown in FIG. 6 and the area 31 shown in FIG. 7 both represent the irradiation area irradiated by the light source 12 (refer to FIG. 4) when the light shielding film 22 is not provided. For example, in the light distribution pattern 30 shown in FIG. 6, due to the pattern of the light shielding film 22, the intensity of light drops sharply at the edge 30a. For example, the light distribution pattern 30 shown in FIG. 6 is a pattern that does not irradiate light to an oncoming car when driving to the left. In addition, the light distribution pattern 32 shown in FIG. 7 can also be a pattern in which a part of the light distribution pattern 30 shown in FIG. 6 is cut off. At this time, similarly to the light distribution pattern 30 shown in FIG. 6, the intensity of the light drops sharply at the edge 32a, for example, it becomes a pattern that does not irradiate light to the oncoming car when driving to the left. Furthermore, the intensity of light also drops sharply in the notch 33. Therefore, in the area corresponding to the notch 33, for example, a sign indicating that the road is turning, uphill, or downhill can be displayed. This can improve safety during night driving.

In addition, the light-shielding portion 14 is not limited to be fixed and arranged between the light source 12 and the lens 16, and can also be set as a drive mechanism not shown in the figure to be arranged between the light source 12 and the lens 16 to obtain a specific configuration. The structure of the light pattern. In addition, the light-shielding portion 14 may be used to constitute a light-shielding member capable of shielding the light from the light source 12. At this time, it can also be set as a structure in which a drive mechanism not shown is provided between the light source 12 and the lens 16 as necessary to obtain a specific light distribution pattern. [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, processing contents, and processing procedures shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the embodiments shown below.

[Preparation of color material composition] Prepare the color material composition containing the following black color materials for the preparation of the light-shielding composition.

<Preparation of titanium black dispersion (color material composition A-1)> Weigh 100g of titanium oxide MT-150A (trade name, manufactured by TAYCA CORPORATION) with an average particle diameter of 15nm, 25g of BET surface area 300m ² /g oxidation Silicon particles AEROGIL (registered trademark) 300/30 (manufactured by EVONIK) and 100 g of dispersing agent Disperbyk 190 (trade name, manufactured by BYK-Chemie GmbH) were mixed. 71 g of ion exchange water was added to the obtained mixture. Using MAZERSTAR KK-400W manufactured by KURABO, the obtained mixture was processed for 20 minutes at a shaft speed of 1360 rpm and a self speed of 1047 rpm, thereby obtaining a more uniform dispersion. This dispersion liquid was filled in a quartz container, and heated to 920°C in an oxygen atmosphere in a small rotary kiln (manufactured by Motoyama Co., Ltd.). After that, the atmosphere was replaced with nitrogen, and ammonium gas was circulated at 100 mL/min for 5 hours at the same temperature, thereby performing nitridation reduction treatment. After the nitridation reduction treatment was completed, the recovered powder was pulverized with a mortar, thereby obtaining powdery titanium black (color material a-1) with a specific surface area of 73 m ² /g.

After adding dispersing resin X-1 (5.5 parts by mass) having a structure represented by the following formula (X-1) to the color material a-1 (20 parts by mass) obtained above, further adding propylene glycol monomethyl ether ethyl The acid ester (hereinafter referred to as "PGMEA") until the solid content concentration becomes 35% by mass.

[Chemical formula 25]

In the above formula (X-1), the numbers attached to each repeating unit indicate the molar ratio of each repeating unit. In addition, the weight average molecular weight of the dispersion resin X-1 was 32,000. The obtained dispersion was thoroughly stirred with a mixer and premixed. Using a dispersing machine NPM Pilot (trade name, manufactured by SHINMARU ENTERPRISES CORPORATION), the obtained dispersion was subjected to dispersion treatment under the following conditions, thereby obtaining a dispersion containing color material a-1, that is, color material composition A- 1.

(Dispersion condition) •Bead diameter: φ0.05mm •Bead filling rate: 65% by volume • Grinding peripheral speed: 10m/sec • Peripheral speed of separator: 11m/s •Amount of mixed liquid for dispersion treatment: 15.0g •Circulation flow (pump supply): 60kg/hour • Treatment liquid temperature: 20~25℃ •Cooling water: tap water (5℃) • Internal volume of the ring channel of the bead mill: 2.2L • Number of passes: 84 passes

＜Preparation of organic pigment dispersion (color material composition A-2)＞ As the color material a-2, an organic pigment containing a benzofuranone compound (trade name "Irgaphor Black S0100CF", manufactured by BASF Corporation) (150 parts by mass), dispersion resin X-1 (75 parts by mass), SOLSPERSE 20000 ( Pigment derivative, Lubrizol Japan Ltd. make) (25 parts by mass), and 3-methoxybutyl acetate (MBA) (750 parts by mass). The dispersing resin X-1 is the same as that used in the preparation of the dispersion liquid of the above-mentioned color material composition A-2. Using a homogenizer (manufactured by PRIMIX Corporation), the obtained mixture was stirred for 20 minutes to obtain a pre-dispersion liquid. Furthermore, using ULTRA APEX MILL (manufactured by KOTOBUKI KOGYOU CO., LTD.) equipped with a centrifugal separator, the obtained pre-dispersed liquid was subjected to a dispersion treatment for 3 hours under the following dispersion conditions, thereby obtaining a dispersion composition. After the dispersion was completed, the beads and the dispersion were separated by a filter, thereby obtaining a dispersion containing the color material a-2, that is, the color material composition A-2. The solid content concentration of the obtained dispersion liquid was 25% by mass, and the ratio of the color material a-2/resin component (the total of the dispersion resin X-1 and the pigment derivative) was 60/40 (mass ratio). In addition, SOLSPERSE 20000 is a compound with an amine value of 29 mgKOH/g, no acid value, and a tertiary amine as a pigment adsorption group.

(Dispersion condition) •Using microbeads: φ0.30mm zirconia beads (YTZ balls, manufactured by Neturen Co., Ltd.) •Bead filling rate: 75% by volume • Grinding peripheral speed: 8m/sec •The amount of mixed liquid for dispersion treatment: 1000g •Circulation flow (pump supply): 13kg/hour • Treatment liquid temperature: 25~30℃ •Cooling water: tap water (5℃) •Inner volume of ring channel of bead mill: 0.15L • Number of passes: 90 passes

＜Preparation of organic pigment dispersion (color material composition A-3)＞ An organic pigment containing a perylene compound (trade name "PALIOGEN Black S0084", manufactured by BASF) is used as the color material a-3 instead of the color material a-2. Otherwise, according to the production of the color material composition A-2 above By the method, the dispersion liquid containing the color material a-3, that is, the color material composition A-3 is obtained.

<Preparation of carbon black dispersion (color material composition A-4)> Carbon black was produced by the usual oil furnace method. However, as the raw material oil, an ethylene base oil with a small amount of Na, Ca, and S was used for combustion with gas fuel. Furthermore, as the reaction stop water, pure water treated with an ion exchange resin was used. Using a homogenizer, the obtained carbon black (540 g) and pure water (14500 g) were stirred at 5,000 to 6,000 rpm for 30 minutes to obtain slurry. The slurry was transferred to a container with a screw-type mixer, and while mixing at about 1,000 rpm, toluene (600 g) which dissolved epoxy resin "Epikote 828" (manufactured by JER) (60 g) was added to the container little by little. . After about 15 minutes, all the carbon black dispersed in the water was transferred to the toluene side and became particles with a particle size of about 1 mm. Next, after controlling the water with a 60-mesh metal net, the separated particles were put into a vacuum dryer and dried at 70°C for 7 hours to remove toluene and water, thereby obtaining resin-coated carbon black (color material a-4 ). The resin coating amount of the obtained resin-coated carbon black was 10% by mass relative to the total amount of carbon black and resin.

The color material a-4 (20 parts by mass), dispersing resin X-1 (4.5 parts by mass) and SOLSPERSE 12000 (manufactured by Lubrizol Japan Ltd.) (1 part by mass) obtained in the above were mixed, and PGMEA was added to the obtained mixture Until the solid content concentration becomes 35% by mass. The dispersing resin X-1 is the same as that used in the preparation of the above-mentioned color material composition A-1. The obtained dispersion was thoroughly stirred with a mixer and premixed. Using ULTRA APEX MILL UAM015 manufactured by KOTOBUKI KOGYOU CO., LTD., the obtained dispersion was subjected to a dispersion treatment under the following conditions to obtain a dispersion composition. After the dispersion was completed, the beads and the dispersion were separated by a filter, thereby obtaining a dispersion containing the color material a-4, that is, the color material composition A-4.

(Dispersion condition) •Bead diameter: φ0.05mm •Bead filling rate: 75% by volume • Grinding peripheral speed: 8m/sec •Amount of mixed liquid for dispersion treatment: 500g •Circulation flow (pump supply): 13kg/hour • Treatment liquid temperature: 25~30℃ •Cooling water: tap water (5℃) •Inner volume of ring channel of bead mill: 0.15L • Number of passes: 90 passes

<Preparation of titanium black dispersion (color material composition A-5)> The dispersion resin X-2 having the structure represented by the following formula (X-2) was used instead of the dispersion resin X-1. In addition, the color material containing color material was obtained according to the manufacturing method of the color material composition A-1 above The dispersion of a-1 is the color material composition A-5.

[Chemical formula 26]

In the above formula (X-2), the numbers attached to each repeating unit indicate the molar ratio of each repeating unit. In addition, the weight average molecular weight of the dispersion resin X-2 was 33,000.

[Alkali-soluble resin] ＜Synthesis of alkali-soluble resin B-1＞ Under a stream of dry nitrogen, 30.03g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.082mol), 1.24g of 1,3-bis(3-aminopropyl) ) Tetramethyl disiloxane (0.005 mol) and 2.73 g of 3-aminophenol (0.025 mol) as a blocking agent are dissolved in 100 g of N-methyl-2-pyrrolidone (below, also Described as "NMP"). 31.02 g of bis(3,4-dicarboxyphenyl) ether dianhydride (0.10 mol) and 30 g of NMP were added to the obtained solution. The obtained solution was stirred at 20°C for 1 hour, and further stirred at 180°C for 4 hours while removing water. After the completion of the reaction, the reaction liquid was poured into 2 L of water, and the generated precipitate was collected by filtration. The obtained precipitate was washed with water three times and dried in a vacuum dryer at 80°C for 20 hours, thereby synthesizing alkali-soluble resin B-1 (polyimide resin).

＜Alkali-soluble resin B-2＞ In addition, as the alkali-soluble resin B-2, a resin having a structure represented by the following formula (B-2) was used.

[Chemical formula 27]

＜Synthesis of alkali-soluble resin B-3＞ Under nitrogen flow, 41.3 g of diphenyl ether-4,4'-dicarboxylic acid and 43.2 g of 1-hydroxy-1,2,3-benzotriazole were reacted to obtain a mixture of dicarboxylic acid derivatives 0.16 mol And 73.3 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane were dissolved in 560 g of NMP, and then reacted at 75°C for 12 hours. Next, 13.1 g of 5-norcamphene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added, and the mixture was further stirred for 12 hours. After filtering the reaction mixture, it was added dropwise to a solution of water/methanol=3/1 (volume ratio), thereby obtaining a white precipitate. After washing the precipitate 3 times with water, it was dried with a vacuum dryer at 80°C for 24 hours, thereby obtaining alkali-soluble resin B-3 (resin including polybenzoxazole precursor).

[Polymerization initiator] The following polymerization initiators were used in the preparation of the light-shielding composition. •Polymerization initiator C-1: a compound represented by the following formula (C-1) •Polymerization initiator C-2: IRGACURE OXE-02 (trade name, manufactured by BASF Corporation) •Polymerization initiator C-3: IRGACURE 369 (trade name, manufactured by BASF) The above-mentioned polymerization initiators are all photopolymerization initiators. Among the above-mentioned polymerization initiators, the polymerization initiator C-1 and the polymerization initiator C-2 are oxime ester-based polymerization initiators.

[Chemical formula 28]

[Polymerizable compound] The polymerizable compound D-1 represented by the following formula (D-1) and the polymerizable compound D-2 represented by the following formula (D-2) were used for the preparation of the composition. The polymerizable compound D-1 is a mixture of a pentafunctional polymerizable compound and a hexafunctional polymerizable compound, and the mixing ratio thereof is pentafunctional polymerizable compound/6 functional polymerizable compound=30/70 (mass ratio). In addition, the value of the aforementioned "functional" indicates the number of ethylenically unsaturated groups possessed by one molecule of the polymerizable compound.

[Chemical formula 29]

[Chemical formula 30]

[Surfactant] The surfactant represented by the following formula (S-1) was used for the preparation of the composition. In addition, the symbol of each repeating unit in formula (S-1) represents the molar ratio of each repeating unit, and l+n=14, m=17. In addition, the weight average molecular weight of the surfactant represented by formula (S-1) is 15,000.

[Chemical formula 31]

[Polymerization inhibitor] As a polymerization inhibitor, p-methoxyphenol is used for the preparation of the light-shielding composition.

[Solvent] As a solvent, cyclohexanone was used for the preparation of the light-shielding composition.

[Example 1] <Preparation of light-shielding composition 1> The following components were mixed with a mixer, thereby preparing the light-shielding composition 1 of Example 1. • Color material composition A-1 prepared in the above 63 parts by mass •Alkali-soluble resin B-1 3.5 parts by mass •Polymerization initiator C-1 1.8 parts by mass •Polymer compound D-1 6.1 parts by mass •Surface active agent 0.02 parts by mass •Polymerization inhibitors 0.003 parts by mass • Solvent 25.5 parts by mass

<Preparation of a black layer> The light-shielding composition 1 obtained in the above was applied on a glass substrate by a spin coating method, thereby forming a coating film with a thickness of 1.7 μm. The coated substrate was prebaked at 100°C for 120 seconds. Then, through the mask of the L/S (line and space) pattern with the opening line width of 50μm, using UX-1000SM-EH04 (trade name, manufactured by USHIO INC.), using a high-pressure mercury lamp (lamp power 50mW/cm ² ), The coated substrate was exposed in proximity. Next, AD-1200 (manufactured by MIKASA Corporation) was used, and a developing solution "CD-2060" (trade name, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used to perform spin immersion development for 15 seconds. Next, a shower nozzle was used to wash with pure water for 30 seconds to remove the uncured part, thereby forming a black layer on the substrate.

<Formation of oxygen blocking layer E-1> A mixed gas of argon and oxygen (oxygen: 40% by volume) was introduced into the vacuum chamber of a sputtering device (manufactured by SHINKO SEIKI CO., LTD., trade name "SRV-4300") ), using a silicon target for sputtering, thereby forming an oxygen blocking layer E-1 (thickness: 100 nm) composed of silicon oxide (SiO ₂ ) on the surface of the black layer produced above. Thereby, the light-shielding film of Example 1 in which the black layer and the oxygen blocking layer E-1 were sequentially formed on the substrate was obtained.

[Examples 2~6, 8, 9, 14~17] Instead of each component used or adjust the addition amount of the color material composition A-1 so that the composition of the light-shielding composition becomes the composition described in Table 1 and Table 2, other than that, the method described in Example 1 was followed, The light-shielding composition of each example was prepared separately. Using each of the light-shielding compositions obtained in the above, other than that, according to the method described in Example 1, Examples 2 to 6 and 8 were prepared in which a black layer and an oxygen blocking layer were sequentially formed on a substrate. , 9 and 14~17 shading film.

[Embodiment 7] In the sputtering process, sputtering was performed by introducing a mixed gas of argon and nitrogen (nitrogen: 50% by volume) in a vacuum chamber, and a silicon nitride (Si ₃ N ₄ ) The oxygen-blocking layer E-2 (thickness: 100nm) of the composition, except that, according to the method described in Example 1, a black layer and oxygen-blocking layer E-2 were sequentially formed on the substrate. The light-shielding film of Example 7.

[Examples 10 to 13] In the sputtering process, the discharge power and the film forming time were adjusted to form oxygen blocking layers E-3 to E- composed of silicon oxide (SiO ₂ ) having the thicknesses described in Table 2 respectively 6. In addition to this, according to the method described in Example 1, the light-shielding films of Examples 10 to 13 in which a black layer and an oxygen blocking layer were sequentially formed on a substrate were respectively produced.

[Comparative Example 1] <Preparation of composition for forming oxygen barrier layer> The following components were mixed to prepare composition 1 for comparison. •Polyvinyl alcohol (PVA): 32.2 parts by mass (trade name: PVA205, manufactured by KURARAY CO., LTD, degree of imitation = 88%, degree of polymerization 550) •Polyvinylpyrrolidone (PVP): 14.9 parts by mass (trade name: K-30, manufactured by Ashland group) • Distilled water: 524 parts by mass • Methanol: 429 parts by mass

＜Formation of CE-1 for comparative oxygen blocking layer＞ According to the manufacturing method of the black layer described in Example 1, a black layer was formed on the substrate. Using a spin coater, the composition 1 was applied to the surface of the produced black layer. The coating amount of the composition 1 was adjusted so that the thickness of the layer after drying became 1000 nm. After that, the coating film of the resin composition 1 was dried at 100° C. for 120 seconds using a hot plate, thereby forming a comparative oxygen blocking layer CE-1 (thickness: 1000 nm). Thereby, the light-shielding film of Comparative Example 1 in which the black layer and the oxygen blocking layer CE-1 were sequentially formed on the substrate was obtained.

[Comparative Example 2] In the process of forming the oxygen blocking layer, the coating amount of the composition 1 was adjusted so that the thickness of the layer after drying became 500 nm. Other than that, the method described in Comparative Example 1 was followed to form a black substrate. The light-shielding film of Comparative Example 2 formed by the layer and the oxygen blocking layer CE-2.

[Comparative Example 3] In the preparation process of the light-shielding composition, the alkali-soluble resin B-2 was used instead of the alkali-soluble resin B-1. Otherwise, according to the method described in Comparative Example 1, a black layer and oxygen barrier were sequentially formed on the substrate. The light-shielding film of Comparative Example 3 formed by cutting CE-1.

[Comparative Examples 4~6] During the sputtering process, the discharge power and the film forming time were adjusted to form layers with the thicknesses listed in Table 3. In addition, according to the method described in Example 1, the black layers and layers were formed sequentially on the substrate. The light-shielding film of Comparative Examples 4 to 6 composed of the oxygen blocking layer CE-3 to CE-5.

[Comparative Example 7] <Preparation of composition for forming oxygen barrier layer> According to the method described in paragraphs 0032~0034 and 0042 (Example 1-1) of JP 2013-253145, the mixture of tetramethoxysilane (TMOS) and trifluoropropyltrimethoxysilane (TFPTMS) The hydrolyzate and the silica gel in which beads-shaped colloidal silica particles were dispersed were used to prepare comparative composition 2.

＜Formation of CE-6 oxygen blocking layer for comparison＞ In the process of forming the oxygen blocking layer, the comparison composition 2 prepared above was used instead of the composition 1, and the coating amount of the comparison composition 2 was adjusted so that the thickness of the layer after drying became 190 nm. In accordance with the method described in Comparative Example 1, a light-shielding film of Comparative Example 7 in which a black layer and an oxygen blocking layer CE-6 were sequentially formed on a substrate was produced. In addition, the surface of the oxygen blocking layer CE-6 was polished to form a smooth surface, and then, the formed smooth surface was analyzed with an electron probe microanalyzer ("JXA-8530F" (trade name) manufactured by JEOL Ltd.) . As a result, the content of carbon atoms in the material constituting the oxygen blocking layer CE-6 was 27% by mass relative to the total mass of the oxygen blocking layer.

[Comparative Examples 8~10] Except that the oxygen blocking layer E-1 was not formed, according to the methods described in Examples 1, 6, and 5, the light-shielding films of Comparative Examples 8 to 10 in which only the black layer was formed on the substrate were respectively produced.

[Evaluation] Each oxygen blocking layer or each light-shielding film obtained in the above was used for the following test and evaluation.

[Measurement of Oxygen Permeability] A substrate with a release layer was used instead of a substrate with a black layer, and each oxygen blocking layer was formed on the release layer. Other than that, according to Examples 1, 7, and 10 to 13, and Comparative Examples The methods described in 1, 2 and 4 to 7 respectively produced a laminate in which a release layer and an oxygen blocking layer were sequentially formed on a substrate. Next, the oxygen barrier layer was peeled off from the obtained laminate, and an oxygen barrier layer for oxygen permeability evaluation was produced. The oxygen transmission rate (ml/(m ² •day•atm)) of the oxygen blocking layer for evaluation prepared in the above was measured using an oxygen transmission rate measuring device (Model 8001, manufactured by ILLINOIS).

[Evaluation of light resistance] <irradiation test> A light resistance tester (manufactured by Suga Test Instruments Co., Ltd., Super Xenon Weather Meter (trade name)) was used at a lamp illuminance of 75W/m ² (300-400nm) and a humidity of 50 Under the condition of %RH, the light-shielding film obtained above was subjected to an irradiation test for 500 hours.

<Change in film thickness before and after irradiation test> The film thickness of the light-shielding film before and after the irradiation test was measured with a contact film thickness meter. The rate of change of the film thickness of the light-shielding film before and after the irradiation test was calculated by the following formula, and evaluated from the following viewpoints. In addition, "the film thickness of the light-shielding film" means the total of the thickness of the black layer and the thickness of the oxygen blocking layer, and does not include the thickness of the substrate. Change rate of film thickness (%)=((film thickness of shading film before irradiation test-film thickness of shading film after irradiation test)/(film thickness of shading film before irradiation test)×100) A: The rate of change of film thickness is less than 2% B: The rate of change of film thickness is 2% or more and less than 5% C: The rate of change of film thickness is 5% or more and less than 10% D: The rate of change of film thickness is more than 10%

＜Changes in transmittance and reflectance before and after irradiation test＞ Using a spectroscope V7200 (trade name, manufactured by JASCO Corporation), light was incident on the light-shielding film before and after the irradiation test at an angle of incidence of 5°. In the obtained transmission spectrum and reflection spectrum, the maximum wavelength of 350~1200nm was measured. Transmittance (hereinafter referred to as transmittance.) and reflectance at a wavelength of 550 nm. The change rate of the transmittance and reflectance of the light-shielding film before and after the irradiation test calculated by the following formula was evaluated from the following viewpoints. Transmittance change rate (%)=((Transmittance before irradiation test-Transmittance after irradiation test)/Transmittance before irradiation test×100) Change rate of reflectance (%)=((reflectance before irradiation test-reflectance after irradiation test)/reflectance before irradiation test×100) A: The change rate of transmittance and reflectance are both less than 2% B: One of the change rate of transmittance and reflectance is 2% or more, and the other is less than 2% C: The change rate of transmittance and reflectance are both 2% or more

[Evaluation of heat resistance] The light-shielding film obtained above was put into an oven, and a heat resistance test was conducted for 500 hours at 150°C. The film thickness of the light-shielding film before and after the heat resistance test was measured with a contact film thickness meter. The rate of change in the film thickness of the light-shielding film before and after the heat resistance test was calculated by the following formula, and evaluated from the following viewpoints. Change rate of film thickness (%)=((film thickness before heat resistance test-film thickness after heat resistance test)/(film thickness of light-shielding film before heat resistance test-thickness of substrate)×100) A: The rate of change of film thickness is less than 2% B: The rate of change of film thickness is 2% or more and less than 4% C: The rate of change of film thickness is 4% or more and less than 6% D: The rate of change of film thickness is 6% or more

[Evaluation of moisture resistance] The light-shielding film obtained above was placed in a constant temperature and humidity chamber, and a humidity resistance test was conducted for 500 hours under the conditions of 85°C and 85% RH. Using a scanning electron microscope (SEM) S-4800 (trade name, manufactured by JEOL Ltd.), a cross section of a line pattern with an opening line width of 50 μm was observed on the substrate after the moisture resistance test. Based on the obtained SEM image of the cross section, the presence or absence of pattern peeling was evaluated from the following viewpoints. A: No peeling was found in all patterns. B: Peeling is found in the range of less than 20% of the entire pattern. C: Peeling is found in the range of 20% or more and less than 50% of the entire pattern. D: Peeling is found in the range of 50% or more of the entire pattern.

[result] Tables 1 to 3 show the composition of the light-shielding composition prepared in Examples 1 to 17 and Comparative Examples 1-10, and the results of each test on the light-shielding film produced using the light-shielding composition. In Tables 1 to 3, the "color material content" column shows the ratio (mass %) of the black color material content to the total solid content of each light-shielding composition.

In Tables 1 to 3, the "composition" column of the "oxygen blocking layer" indicates that the oxygen blocking layer is a layer composed of the following materials. A: Sputtering layer of silicon oxide (SiO ₂ ) B: Sputtering layer of silicon nitride (Si ₃ N ₄ ) C: Organic layer composed of PVA and PVP D: Polyorganosiloxane containing silicon oxide particles Organic layer

In Tables 1 to 3, the "thickness" column of the "oxygen blocking layer" indicates the thickness (nm) of each oxygen blocking layer measured with a contact-type film thickness meter. In addition, in Tables 1 to 3, the column "thickness of the black layer/thickness of the oxygen blocking layer" indicates the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer measured by a contact-type film thickness meter.

[Table 1]

[Table 2]

[table 3]

From the results shown in Table 1 to Table 3, it was confirmed that the light-shielding composition of the present invention can solve the problem of the present invention.

It was confirmed that, from the viewpoint that the moisture resistance of the light-shielding film is more excellent, the content of the black color material is preferably 70% by mass or less, and more preferably 65% by mass or less (Comparison of Example 1, Examples 15 and 17). It was confirmed that from the viewpoint that the heat resistance of the light-shielding film is more excellent, the content of the black color material is preferably 30% by mass or more, and more preferably 50% by mass or more (comparison of Examples 1, 14 and 16).

It was confirmed that the black color material preferably contains a titanium oxynitride, a benzofuranone compound, or a perylene compound from the viewpoint of better moisture resistance of the light-shielding film (comparison of Examples 1, 3, 4, and 5). In addition, it was confirmed that the black color material preferably contains titanium oxynitride or carbon black from the viewpoint of better light resistance of the light-shielding film (comparison of Examples 1, 3, 4, and 5). Furthermore, it was confirmed from Examples 18 to 20 described later that, from the viewpoint of better moisture resistance and light resistance of the light-shielding film, black color materials containing vanadium nitride, niobium nitride or zirconium nitride and titanium oxynitride The black color material is also better.

It was confirmed that from the viewpoint of the light resistance, heat resistance, and moisture resistance of the light-shielding film being more excellent, the dispersion resin preferably contains an ethylenically unsaturated group (comparison of Example 1 and Example 9). It was confirmed that the alkali-soluble resin-based polyimide resin is preferable from the viewpoint of more excellent light resistance and heat resistance of the light-shielding film (comparison of Example 1 and Example 6). In addition, it was confirmed from Example 21 described later that from the viewpoint of the light resistance and moisture resistance of the light-shielding film being more excellent, as the alkali-soluble resin, a resin composed of a polybenzoxazole precursor is the same as the polyimide resin Better. It was confirmed that the polymerization initiator-based polymerization initiator C-1 is preferable from the viewpoint of better light resistance and heat resistance of the light-shielding film (comparison of Example 1 and Example 8). It was confirmed that the polymerizable compound-based polymerizable compound D-1 is preferable from the viewpoint of better heat resistance and moisture resistance of the light-shielding film (comparison of Example 1 and Example 2).

It was confirmed that the oxygen blocking layer preferably contains silicon oxide from the viewpoint of better light resistance and moisture resistance of the light shielding film (comparison of Example 1 and Example 7). It was confirmed that the thickness of the oxygen blocking layer is preferably greater than 50 nm and less than 250 nm from the viewpoint of better moisture resistance and heat resistance of the light-shielding film (comparison of Examples 1, 24, and 25 with Examples 10 and 11). It was confirmed that from the viewpoint of better moisture resistance and heat resistance of the light-shielding film, it is preferable that the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is 7-30 (Example 1 and Examples 10 and 11 Compare).

[Examples 18-20] The following color materials a-5 to a-7 were used instead of titanium black (color material a-1). In addition, the color material composition A was prepared in accordance with the preparation method of the above color material composition A-1. -6~A-8. • Color material a-5: Vanadium nitride (trade name "VN-O, manufactured by Japan New Metals Co., Ltd.) • Color material a-6: Niobium nitride (trade name "NbN-O", manufactured by Japan New Metals Co., Ltd.) • Color material a-7: Zirconium nitride (prepared by the method of Example 1 of JP 2017-222559 A) The color material compositions A-6 to A-8 prepared in the above were used instead of the color material composition A-1. Other than that, the examples were prepared according to the method of preparing the light-shielding composition 1 of Example 1. A light-shielding composition of 18-20. The obtained light-shielding composition was used in place of the light-shielding composition 1, and other than that, according to the method described in Example 1, an example in which a black layer and an oxygen blocking layer were sequentially formed on a substrate were produced. 18-20 shading film. The evaluation results of the light-shielding films of Examples 18 to 20 are all equal to Example 1. The color material a-8 was used instead of titanium black (color material a-1), except that the color material composition was prepared according to the preparation method of the color material composition A-1 above, and the same evaluation as in Example 1 was performed . • Color material a-8: silicon dioxide coated zirconium nitride (Japanese Patent Laid-Open No. 2015-117302) The evaluation results are the same as in Example 1. Use a mixture of color material a-1 and color material a-7 with a weight ratio of a-1:a-7=1:9, 3:7, 5:5, 7:3, and 9:1 to replace titanium black (Color material a-1) Except for this, a color material composition was prepared in accordance with the above-mentioned preparation method of color material composition A-1, and the same evaluation as in Example 1 was performed. The evaluation results are the same as in Example 1. Also, use a mixture of color material a-1 and color material a-8 with a weight ratio of a-1:a-8=1:9, 3:7, 5:5, 7:3, and 9:1, respectively Titanium black (color material a-1), except for that, a color material composition was prepared in accordance with the above-mentioned preparation method of color material composition A-1, and the same evaluation as in Example 1 was performed. The evaluation results are the same as in Example 1.

[Example 21] Except for using alkali-soluble resin B-3 instead of alkali-soluble resin B-1, the light-shielding composition of Example 21 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1. The obtained light-shielding composition was used in place of the light-shielding composition 1. Except for this, the method described in Example 1 was followed to produce Example 21 in which a black layer and an oxygen blocking layer were sequentially formed on a substrate Shading film. The evaluation results of the light-shielding film of Example 21 are all equal to those of Example 1.

[Example 22] The polymerization initiator C-3 was used instead of the polymerization initiator C-2, and the light-shielding composition of Example 22 was prepared in accordance with the method of preparing the light-shielding composition 1 of Example 1, except that the polymerization initiator C-3 was used. The obtained light-shielding composition was used in place of the light-shielding composition 1. Except for this, the method described in Example 1 was followed to produce Example 22 in which a black layer and an oxygen blocking layer were sequentially formed on a substrate Shading film. In the evaluation result of the light-shielding film of Example 22, the heat resistance was C, and other than that, it was equal to Example 8.

[Example 23] In the preparation of light-shielding composition 1, 6.1 parts by mass of a mixture of polymerizable compound D-1 and polymerizable compound D-2 at a mass ratio of 1:1 were used instead of 6.1 parts by mass of polymerizable compound D-1, except Otherwise, according to the method of Example 1, the light-shielding composition of Example 23 was prepared. The obtained light-shielding composition was used in place of the light-shielding composition 1. Except for this, the method described in Example 1 was followed to produce Example 23 in which a black layer and an oxygen blocking layer were sequentially formed on a substrate Shading film. In the evaluation result of the light-shielding film of Example 23, the moisture resistance was B, and other than that, it was equal to Example 1.

[Examples 24 to 25] In the sputtering process, the discharge power and the film forming time were adjusted to form oxygen blocking layers E-7 and E-8 composed of silicon oxide (SiO ₂ ) with thicknesses of 70 nm and 200 nm, respectively In addition to this, according to the method described in Example 1, the light-shielding films of Examples 24 and 25 were respectively produced in which a black layer and an oxygen blocking layer were sequentially formed on a substrate. The evaluation results of the light-shielding films of Examples 24 and 25 are all equal to those of Example 1.

[Examples 26~27] The light-shielding composition of Example 26 was prepared according to the method of preparing the light-shielding composition 1 of Example 1 except that no polymerization inhibitor was used. In addition, the light-shielding composition of Example 27 was prepared in accordance with the method of preparing the light-shielding composition 1 of Example 1, except that no surfactant was used. The obtained light-shielding composition was used in place of the light-shielding composition 1, and other than that, according to the method described in Example 1, an example in which a black layer and an oxygen blocking layer were sequentially formed on a substrate were produced. 26 and 27 shading film. The evaluation results of the light-shielding films of Examples 26 and 27 are both equal to Example 1.

[Example 28] <Production of color filter with black matrix> The light-shielding composition 1 of Example 1 was applied to a glass wafer by a spin coating method to form a composition layer. Next, the glass wafer was placed on a hot plate, and prebaked at 120°C for 2 minutes. Next, using an i-ray stepper, the composition layer was exposed with an exposure amount of 500 mJ/cm ² through a mask having an island pattern of 0.1 mm. Next, with a 0.3% aqueous solution of tetramethylammonium hydroxide, the exposed composition layer was subjected to spin immersion development at 23° C. for 60 seconds, thereby obtaining a cured film. The hardened film obtained was rinsed by rotating spray, and then rinsed with pure water, thereby forming a patterned black layer. Next, in accordance with the method for forming the oxygen blocking layer E-1 of Example 1, an oxygen blocking layer made of silicon oxide was formed on the surface of the black layer prepared above, thereby fabricating an oxygen blocking layer formed sequentially on a glass wafer A light-shielding film (black matrix) composed of a black layer and an oxygen blocking layer. As a result of using the above black matrix to make a color filter, it has good performance.

[Example 29] <Preparation of a solid-state imaging element with a light-shielding film> A curable composition for lenses (p-alicyclic epoxy resin (manufactured by Daicel Corporation, trade name "EHPE-3150")) was added with aryl sulfonium Salt derivative (manufactured by ADEKA CORPORATION, trade name "SP-172") 1% by mass composition) (2 mL) was coated on a 5 x 5 cm glass substrate (thickness 1 mm, manufactured by Schott AG, trade name "BK7") The coating film was heated at 200°C for 1 minute to harden, thereby forming a lens film capable of evaluating residue on the lens. The light-shielding composition 1 of Example 1 was coated on a glass wafer on which the lens film was formed, thereby forming a composition layer. Next, the glass wafer was placed on a hot plate, and pre-baked at 120°C for 120 seconds. The thickness of the composition layer after heating was 2.0 μm. Next, using a high-pressure mercury lamp, the composition layer was exposed at an exposure amount of 500 mJ/cm ² through a mask having a hole pattern of 10 mm. Next, the exposed composition layer was spin-dipped and developed at a temperature of 23° C. for 60 seconds with a 0.3% aqueous solution of tetramethylammonium hydroxide, thereby obtaining a cured film. The hardened film obtained was rinsed by rotating spray, and then rinsed with pure water, thereby forming a patterned black layer. Next, in accordance with the method for forming the oxygen blocking layer E-1 of Example 1, an oxygen blocking layer made of silicon oxide was formed on the surface of the black layer prepared above, thereby fabricating an oxygen blocking layer formed sequentially on a glass wafer A light-shielding film made of black layer and oxygen blocking layer.

On the glass wafer on which the light-shielding film produced in the above is formed, a curable composition for lenses (p-alicyclic epoxy resin (made by Daicel Corporation, trade name "EHPE-3150") is added with arylsulfonium salt Derivatives (manufactured by ADEKA CORPORATION, trade name "SP-172") 1% by mass composition) formed a curable resin layer. Next, transfer the shape using a quartz mold with a lens shape, and use a high-pressure mercury lamp to expose at an exposure of 400mJ/cm ² to harden the curable resin layer, thereby fabricating a wafer-level wafer with multiple wafer-level lenses Lens array. After cutting the manufactured wafer-level lens array and using the obtained wafer-level lens to manufacture a lens module, the imaging element and the sensor substrate are mounted, thereby manufacturing the solid-state imaging element with the light-shielding film of the present invention. In the obtained solid-state imaging device, the lens opening of the wafer-level lens had no residues and had good transmittance, and the light-shielding film also had high uniformity of the coated surface and high light-shielding properties.

[Example 30] <Production of a headlight unit with a light-shielding film> The light-shielding composition 1 of Example 1 obtained in the above was coated on a glass substrate of 10 cm square by a spin coating method to form Composition layer. The above-mentioned glass substrate was placed on a hot plate and prebaked at 120°C for 2 minutes. Using an i-ray stepper, the obtained composition layer was exposed through a mask (exposure amount 1000 mJ/cm ² ) to obtain a cured film with the light distribution pattern shown in FIG. 6. Next, a developing device (Act-8 manufactured by Tokyo Electron Limited) was used for developing processing. As the developing solution, a 0.3% aqueous solution of tetramethylammonium hydroxide was used, and spin-dip development was performed at 23°C for 60 seconds. Afterwards, the cured film obtained was rinsed with a rotating spray of pure water, thereby obtaining a black layer with a prescribed light distribution pattern. Next, according to the method of forming the oxygen blocking layer E-1 of Example 1, an oxygen blocking layer made of silicon oxide was formed on the surface of the black layer produced above, thereby fabricating a black layer formed on the glass substrate. A light-shielding film composed of layers and oxygen blocking layers. The result of using the obtained shading film, light source and lens to make the headlight unit has good performance.

10: Headlight unit 12: light source 14: Shading part 16: lens 20: Matrix 22: Shading film 23: Opening 30: Light distribution pattern 30a: Edge 31: area 32: light distribution pattern 32a: Edge 33: Notch 100: Solid state camera 101: solid-state image sensor 102: Camera Department 103: cover glass 104: Spacer 105: Multilayer substrate 106: Wafer substrate 107: Circuit board 108: Electrode pad 109: External connection terminal 110: Through electrode 111: lens layer 112: lens material 113: Support 114, 115: shading film 201: Light receiving element 202: color filter 203: Micro lens 204: Substrate 205b: blue pixel 205r: red pixel 205g: green pixels 205bm: black matrix 206: p-well layer 207: Readout gate 208: Vertical transmission path 209: component separation area 210: Gate insulating film 211: Vertical transfer electrode 212: Shading film 213, 214: insulating film 215: Flattening film 300: infrared sensor 310: solid-state image sensor 311: infrared absorption filter 312: color filter 313: infrared transmission filter 314: Resin film 315: Micro lens 316: Flattening film

Fig. 1 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device. Fig. 2 is a schematic cross-sectional view showing an enlarged view of an imaging unit included in the solid-state imaging device shown in Fig. 1. Fig. 3 is a schematic cross-sectional view showing a configuration example of an infrared sensor. Fig. 4 is a schematic diagram showing a configuration example of the headlight unit. Fig. 5 is a schematic perspective view showing a configuration example of the light shielding portion of the headlight unit. Fig. 6 is a schematic diagram showing an example of a light distribution pattern based on a headlight unit. Fig. 7 is a schematic diagram showing another example of a light distribution pattern based on a headlight unit.

Claims (17)

A light-shielding film, which has: Black layer containing black color material; and The oxygen blocking layer formed on the black layer, The oxygen blocking layer is a single layer made of inorganic materials, The thickness of the oxygen blocking layer is 10 to 500 nm. The light-shielding film according to claim 1, wherein The black color material contains oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium and niobium. The light-shielding film according to claim 1, wherein The black color material contains carbon black, benzofuranone compound or perylene compound. The light-shielding film according to claim 1, wherein The content of the black color material is 20 to 80% by mass relative to the total mass of the black layer. The light-shielding film according to claim 1, wherein The oxygen blocking layer contains silicon oxide. The light-shielding film according to any one of claims 1 to 5, wherein The ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is 2-100. The light-shielding film according to any one of claims 1 to 5, wherein the oxygen transmission rate of the oxygen blocking layer is 10 ml/(m ² •day•atm) or less. The light-shielding film according to any one of claims 1 to 5, wherein The oxygen blocking layer contains substantially no particles. A method for manufacturing a light-shielding film, which includes: The process of coating a light-shielding composition containing black color material, resin, polymerizable compound and polymerization initiator on the support, and curing the obtained coating film to form a black layer; and The process of forming an oxygen blocking layer on the black layer, The oxygen blocking layer is a single layer made of inorganic materials, The thickness of the oxygen blocking layer is 10 to 500 nm. The method of manufacturing a light-shielding film according to claim 9, wherein The process of forming the oxygen blocking layer includes a process of vapor deposition of inorganic materials. The method of manufacturing a light-shielding film according to claim 9 or 10, wherein The resin includes an alkali-soluble resin containing at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and copolymers of these. The method of manufacturing a light-shielding film according to claim 9 or 10, wherein The light-shielding composition contains at least two types of polymerizable compounds. The method of manufacturing a light-shielding film according to claim 9 or 10, wherein the polymerization initiator is a compound represented by the following formula (C-13), [Chemical formula 1]

. The method of manufacturing a light-shielding film according to claim 9 or 10, wherein The resin contains a resin having an ethylenically unsaturated group. An optical element containing the light-shielding film according to any one of claims 1 to 8. A solid-state imaging device containing the light-shielding film according to any one of claims 1 to 8. A headlight unit, which is a headlight unit of a vehicle lamp, and the headlight unit has: Light source; and The light shielding part shields at least a part of the light emitted from the light source, The light-shielding part contains the light-shielding film according to any one of claims 1 to 8.

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