TWI869349B - Light-shielding film, method for manufacturing light-shielding film, optical element, solid-state imaging element, headlight unit - Google Patents

Abstract

The light-shielding film of the present invention has a black layer containing a black color material and an oxygen blocking layer formed on the black layer. The oxygen blocking layer is a single layer composed of an inorganic material, and the thickness of the oxygen blocking layer is 10-500 nm. The manufacturing method of the light-shielding film has a process of 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 to form a black layer, and a process of forming the oxygen blocking layer on the black layer.

Description

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

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

In the color filter used in liquid crystal display devices, a light-shielding film called a black matrix is provided 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 Assistants) are equipped with small and thin camera units. In solid-state imaging elements such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors, a light-shielding film is provided for the purpose of preventing noise and improving image quality.

It is known that there is a technology for setting an oxygen blocking layer on a light-shielding film and a colored pixel 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 blocking layer covering the black matrix and the color filter layer and containing at least an oxygen blocking compound, and a mixed layer containing a dye and an oxygen blocking compound between the color filter layer and the oxygen blocking layer on a substrate.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2011-248197

The inventors of the present invention have studied the black matrix with an oxygen blocking layer described in Patent Document 1 and found that the light resistance and moisture resistance of the black matrix (light shielding film) may not be fully satisfied.

Therefore, the subject of the present invention is to provide a light-shielding film with excellent light resistance and moisture resistance. In addition, the subject of the present invention is also to provide a light-shielding film manufacturing method, optical element, solid-state imaging element and headlight unit.

As a result of in-depth research, the inventor found that the above-mentioned problem can be solved by the following structure, and completed the present invention.

[1] A light-shielding film comprising a black layer containing a black colorant 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 has a thickness of 10 to 500 nm.

[2] The light-shielding film as described in [1], wherein the black color material contains at least one metal nitride selected from the group consisting of titanium, vanadium, zirconium and niobium.

[3] The light-shielding film as described in [1], wherein the black colorant contains carbon black, a benzofuranone compound or a perylene compound.

[4] A light-shielding film as described in 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] A light-shielding film as described in any one of [1] to [4], wherein the oxygen blocking layer contains silicon oxide.

[6] A light shielding film as described in 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 to 100.

[7] The light-shielding film as described in any one of [1] to [6], wherein the oxygen permeability of the oxygen barrier layer is less than 10 ml/(m ² ˙day˙atm).

[8] A light-shielding film as described in any one of [1] to [7], wherein the oxygen blocking layer substantially does not contain particles.

[9] A method for manufacturing a light-shielding film, comprising: coating a light-shielding composition containing a black colorant, a resin, a polymerizable compound, and a polymerization initiator on a support, and curing the obtained coating to form a black layer; and forming an oxygen blocking layer on the black layer, wherein the oxygen blocking layer is a single layer composed of an inorganic material, wherein the thickness of the oxygen blocking layer is 10 to 500 nm.

[10] A method for manufacturing a light-shielding film as described in [9], wherein the process for forming the above-mentioned oxygen blocking layer includes a process for vapor deposition of inorganic materials.

唑前驅物及該等的共聚物的群組中之至少1種的鹼可溶性樹脂。 [11] The method for manufacturing a light-shielding film as described in [9] or [10], wherein the resin comprises a material selected from the group consisting of a polyimide precursor, a polyphenylene glycol

At least one alkali-soluble resin selected from the group consisting of azole precursors and copolymers thereof.

[12] A method for producing a light-shielding film as described in any one of [9] to [11], wherein the light-shielding composition contains at least two polymerizable compounds.

[13] A method for producing a light-shielding film as described in any one of [9] to [12], wherein the polymerization initiator is a compound represented by the formula (C-13) described below.

[14] A method for producing a light-shielding film as described in any one of [9] to [13], wherein the resin contains a resin having an ethylenically unsaturated group.

[15] An optical element comprising a light-shielding film as described in any one of [1] to [8].

[16] A solid-state imaging device comprising a light-shielding film as described in any one of [1] to [8].

[17] A headlight unit, which is a headlight unit for a vehicle, comprising: a light source; and a shading portion for shielding at least a portion of the light emitted from the light source, wherein the shading portion includes the shading film described in any one of [1] to [8].

According to the present invention, a light-shielding film with excellent light resistance and moisture resistance can be provided. In addition, the present invention can provide a light-shielding film manufacturing method, an optical element, a solid-state imaging element, and a headlight unit.

10: Headlight unit

12: Light source

14: Light shielding part

16: Lens

20: Matrix

22: Shading film

23: Opening

30: Lighting pattern

30a: Edge

31: Region

32: Lighting pattern

32a: Edge

33: Notch

100: Solid-state imaging device

101: Solid-state imaging device

102: Camera Department

103: Cover with glass

104: Spacer

105: Laminated 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 body

114, 115: Light-shielding 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: Read out the fence pole

208: Vertical transmission path

209: Component separation area

210: Gate insulation film

211: Vertical transfer electrode

212: Shading film

213, 214: Insulation film

215: Flattening film

300: Infrared sensor

310: Solid-state imaging device

311: Infrared absorption filter

312: Color filter

313: Infrared transmission filter

314: Resin film

315: Micro lens

316: Flattening film

FIG1 is a schematic cross-sectional view showing an example of the structure of a solid-state imaging device.

FIG2 is a schematic cross-sectional view showing an enlarged view of the imaging unit of the solid-state imaging device shown in FIG1.

Figure 3 is a schematic cross-sectional view showing an example of the structure of an infrared sensor.

FIG4 is a schematic diagram showing an example of the structure of a headlight unit.

FIG5 is a schematic three-dimensional diagram showing an example of the structure of the light shielding portion of the headlight unit.

FIG6 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.

The present invention is described in detail below.

The description of the constituent elements described below is sometimes completed based on representative implementations of the present invention, but the present invention is not limited to such implementations.

In addition, in this manual, the numerical range represented by "~" indicates that the range includes the numerical values written before and after "~" as the lower limit and upper limit.

In addition, in the description of groups (atomic groups) in this specification, the description without mentioning substitution and unsubstituted includes groups without substituents and groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups).

In addition, "actinic rays" or "radiation" in this specification refers to, for example, far ultraviolet rays, extreme ultraviolet rays (EUV: Extreme ultraviolet lithography), X-rays, and electron beams. In addition, in this specification, light refers to actinic rays and radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure based on far ultraviolet rays, X-rays, and EUV light, 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)acryl" means acryl and methacryl. 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 billion", and "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 the GPC (Gel Permeation Chromatography) method.

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

[Shading film]

The light-shielding film of the present invention has a black layer containing a black color material and an oxygen blocking layer disposed on the black layer.

The above oxygen blocking layer is a single layer composed of inorganic materials.

The thickness of the above oxygen blocking layer is 10~500nm.

Furthermore, the light-shielding film of the present invention can be manufactured by the following manufacturing method, which comprises a process of coating a light-shielding composition containing a black colorant, a resin, a polymerizable compound, and a polymerization initiator on a support, and curing the obtained coating to form a black layer, and a process of forming an oxygen blocking layer on the above black layer.

[Black layer]

The black layer included in the light-shielding film of the present invention contains a black colorant.

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 above-mentioned light-shielding composition.

[Light-blocking composition]

The light-shielding composition (hereinafter, also simply described as "composition") used to form the black layer is explained. 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 colorant.

As the black color material, one or more selected from the group consisting of black pigments and black dyes can be cited.

Black color materials can be used alone or in combination of two or more.

The content of the black color material in the black layer is not particularly limited. For example, it can be 20-80% by mass relative to the total mass of the black layer. From the perspective 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 greater than 30% by mass, and more preferably greater than 50% by mass. Furthermore, from the perspective 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, more preferably less than 70% by mass, and more preferably less than 65% by mass.

For example, the content of the black colorant in the light-shielding composition can be 20-80% by mass relative to the total solid content of the light-shielding composition. From the perspective of better heat resistance of the light-shielding film, it is better to be greater than 20% by mass, more preferably 30% by mass or more, and more preferably 50% by mass or more. From the perspective of better moisture resistance of the light-shielding film, the content of the black colorant in the light-shielding composition is better than 80% by mass, more preferably 70% by mass or less, and more preferably 65% by mass or less relative to the total solid content of the light-shielding composition.

In addition, in this specification, the "total solid content" of a composition refers to the components that form a layer or film by curing, etc. When the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. In addition, as long as it is a component that forms a film, the liquid component is also regarded as a solid component.

That is, by adjusting the content of the black colorant relative to the total solid content of the light-shielding composition, the content of the black colorant in the black layer can be adjusted to a desired value.

In addition, multiple colorants that cannot be used as black color materials alone can be combined to adjust the overall color to black and use it as a black color material.

For example, a plurality of pigments that have colors other than black when they are alone can be combined to be used as a black pigment. Similarly, a plurality of dyes that have colors other than black when they are alone can be combined to be used as a black dye, and a pigment that has a color other than black when it is alone and a dye that has a color other than black when it is alone can be combined to be used as a black dye.

In this manual, black color material refers to a color material that absorbs in the entire wavelength range of 400~700nm.

More specifically, for example, a black color material that meets the evaluation criteria Z described below is preferred.

First, prepare a composition containing a colorant, a transparent resin matrix (acrylic resin, etc.) and a solvent, wherein the colorant content relative to the total solid content is 60 mass %. Apply the obtained composition on a glass substrate until the film thickness of the dried coating becomes 1 μm, thereby forming a coating. Use a spectrophotometer (Hitachi, LTD. UV-3600, etc.) to evaluate the light-shielding property of the dried coating. If the maximum transmittance of the dried coating in the wavelength range of 400 to 700 nm is less than 10%, it can be determined that the above colorant is a black colorant that meets the evaluation standard Z.

(Black pigment)

As the black pigment, various known black pigments can be used. The black pigment may be an inorganic pigment or an organic pigment.

From the perspective of the black layer's superior light resistance, black color materials are preferably black pigments.

As black pigments, pigments that appear black alone are preferred, and pigments that appear black alone and absorb infrared rays are even better.

Among them, black pigments that absorb infrared rays have absorption in the infrared region (preferably 650-1300nm). Black pigments that have extremely strong absorption in the 675-900nm wavelength region are also preferred.

There is no particular restriction on the particle size of the black pigment. From the perspective of achieving a better balance between operability and the stability of the composition over time (black pigment does not settle), 5~100nm is preferred, 5~50nm is more preferred, and 5~30nm is even more preferred.

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 using a transmission electron microscope (TEM). As a transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.

The maximum length (Dmax: the maximum length between two points on the particle image outline) and the maximum vertical length (DV-max: the shortest length between two lines parallel to the maximum length when the image is sandwiched) of the particle image obtained using a transmission electron microscope are measured, and the average value (Dmax×DV-max) ^1/2 is taken as the particle size. The particle size of 100 particles is measured using this method, and the arithmetic average is taken as the average primary particle size of the particles.

˙Inorganic pigments

As an inorganic pigment, there is no particular limitation as long as it has light-shielding properties and contains particles of inorganic compounds, and known inorganic pigments can be used.

From the perspective of low reflectivity and better light-shielding properties of the black layer, inorganic pigments are preferred as black color materials.

As inorganic pigments, metal oxides, metal nitrides and metal oxynitrides containing one or more metal elements selected from the group consisting of metal elements of Group 4 such as titanium (Ti) and zirconium (Zr), metal elements of Group 5 such as vanadium (V) and niobium (Nb), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn) and silver (Ag) can be cited.

As the above-mentioned metal oxides, metal nitrides and metal oxynitrides, particles mixed with other atoms can be used. For example, metal nitride particles containing atoms selected from elements of groups 13 to 17 of the periodic table (preferably oxygen atoms and/or sulfur atoms) can be used.

As the manufacturing method of the above-mentioned metal nitride, metal oxide or metal oxynitride, there is no particular limitation as long as it can obtain a black pigment with the desired physical properties, and a known manufacturing method such as a gas phase reaction method can be used. As the gas phase reaction method, electric furnace method and hot plasma method can be cited, but from the perspective of less impurities mixed, easy uniform particle size, and high productivity, the hot plasma method is preferred.

The above-mentioned metal nitride, metal oxide or metal oxynitride can be subjected to surface modification treatment. For example, the surface modification treatment can be carried out using a surface treatment agent having both a silicon group and an alkyl group. Examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., LTD.) and the like.

Among them, from the perspective of being able to suppress undercutting when forming a black layer, a nitride or oxynitride of at least one metal selected from the group including titanium, vanadium, zirconium and niobium is more preferred. In addition, from the perspective of better light resistance and moisture resistance of the light-shielding film, it is more preferred that the black color material contains an oxynitride of at least one metal selected from the group including titanium, vanadium, zirconium and niobium, and it is particularly preferred that it contains titanium oxynitride (titanium black).

Titanium black is a black particle containing titanium oxynitride. Titanium black can be surface-modified as needed for purposes such as 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 a water-repellent substance as shown in Japanese Patent Publication No. 2007-302836.

As a method for producing titanium black, there are methods of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (Japanese Patent Publication No. 49-005432), reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing atmosphere containing hydrogen (Japanese Patent Publication No. 57-205322), high-temperature reducing titanium dioxide or titanium hydroxide in the presence of ammonium (Japanese Patent Publication No. 60-065069, Japanese Patent Publication No. 61-201610), and attaching a vanadium compound to titanium dioxide or titanium hydroxide and high-temperature reducing in the presence of ammonium (Japanese Patent Publication No. 61-201610), etc., but it is not limited to these.

There is no particular restriction on the particle size of titanium black, but 10 to 45 nm is preferred, and 12 to 20 nm is more preferred. There is no particular restriction on the specific surface area of titanium black, but in order to achieve a specified performance of water repellency after surface treatment with a water repellent, the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 5 to 150 m ² /g, and more preferably 20 to 100 m ² /g.

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

It is also preferred that the light-shielding composition contains titanium black as a dispersed body containing titanium black and Si atoms. In this form, titanium black is contained as a dispersed body in the composition. The content ratio of Si atoms to Ti atoms in the dispersed body (Si/Ti) is preferably 0.05 to 0.5, and more preferably 0.07 to 0.4, in terms of mass conversion. The dispersed body includes both titanium black in the form of primary particles and in the form of aggregates (secondary particles).

Furthermore, if the Si/Ti ratio of the dispersed body is too small, when the coating film using the dispersed body is patterned by photolithography, it is easy for residues to remain in the removed part. If the Si/Ti ratio of the dispersed body is too large, the light shielding ability tends to decrease.

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

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

In the dispersed body containing titanium black and Si atoms, the titanium black can be used as the above-mentioned one. In addition, in the dispersed body, for the purpose of adjusting dispersibility, coloring, etc., titanium black can be combined with one or more black pigments including composite oxides of multiple metals selected from Cu, Fe, Mn, V and Ni, cobalt oxide, iron oxide, carbon black, and aniline black as the dispersed body. In this case, it is preferred that the dispersed body including titanium black accounts for more than 50% by mass of all the dispersed bodies.

The light-shielding composition preferably contains zirconium nitride or zirconium oxynitride. It is preferred that zirconium nitride or zirconium oxynitride is 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 damaging the light-shielding property of the pigment (light-shielding pigment), and it is easy to prevent the deterioration of the light-shielding composition. Preferable specific examples of inorganic compounds include titanium dioxide, zirconium oxide, silicon dioxide, aluminum oxide, etc., silicon dioxide, aluminum oxide. It is also preferred to use a combination of titanium black and zirconium nitride, titanium black and zirconium oxynitride, titanium black and silicon dioxide coated zirconium nitride, and titanium black and aluminum oxide coated zirconium nitride.

Carbon black can also be cited as an inorganic pigment.

From the perspective of excellent light-shielding properties and light resistance, especially better suppression of changes in optical properties after light resistance testing, it is preferred that the black color material contain carbon black.

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

As carbon black, carbon black produced by a known method such as an oil furnace method can be used, or commercially available products can be used. Specific examples of commercially available carbon black products 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 preferred. Surface treatment can improve the surface state of carbon black particles and improve the dispersion stability in the composition. Examples of surface treatment include resin-based coating treatment, surface treatment for introducing acidic groups, and surface treatment based on silane coupling agents.

As carbon black, carbon black that has been coated with a resin is preferred. By coating the surface of 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 reducing leakage current, etc. Therefore, it is preferred to use the black layer for applications that require insulation.

As the coating resin, epoxy resin, polyamide, polyamide imide, novolac resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkylbenzene resin, polystyrene, polycarbonate, polybutylene terephthalate and modified polyphenylene ether can be cited.

From the perspective of the black layer's superior light-shielding and insulation properties, the coating resin content is preferably 0.1-40% by mass, and more preferably 0.5-30% by mass, relative to the total of carbon black and coating resin.

˙Organic pigments

As an organic pigment, there is no particular limitation as long as it has light-shielding properties and contains particles of organic compounds, and any known organic pigment can be used.

Specific examples of organic pigments include benzofuranone compounds, methine azo compounds, perylene compounds, and azo compounds.

From the perspective of better moisture resistance of the light-shielding film, it is preferred that the black color material contain a benzofuranone compound or a perylene compound.

(Benzofuranone compounds)

The benzofuranone compound is a compound having a benzofuran-2(3H)-one structure or a benzofuran-3(2H)-one structure in the molecule and is colored black by absorbing light of a wavelength of visible light.

As benzofuranone compounds, compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, and Japanese Patent Publication No. 2012-515234 can be cited.

Furthermore, as the benzofuranone compound, a compound represented by any one of the general formulas (63) to (68) is preferred.

[Chemical formula 1]

In the general formulae (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 and having 1 to 20 fluorine atoms. R ²⁰⁸ , R ²⁰⁹ , R ²¹⁴ , R ²¹⁵ , R ²²⁰ and R ²²¹ each independently represents 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 having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 4 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms. 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 via 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 carbon atoms or an aryl group having 6 to 15 carbon atoms. a, b, c, d, e and f each independently represent an integer of 0 to 4. In the general formulae (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 an alkyl group having 1 to 6 carbon atoms having 1 to 12 fluorine atoms. In addition, ^R251 and ^R252 are each independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 4 to 7 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms. In addition, ^R210 , ^R211 , ^R216 , ^R217 , ^R222 , and ^R223 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 above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, and aryl group may have heteroatoms, and may be unsubstituted or substituted.

In the general formulae (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 and having 1 to 20 fluorine atoms. 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 having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 4 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms. 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 via 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 carbon atoms or an aryl group having 6 to 15 carbon atoms. a, b, c, d, e and f each independently represent an integer of 0 to 4. In the general formulae (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 having 1 to 12 fluorine atoms. In addition, ^R271 and ^R272 are each independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 4 to 7 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms. In addition, ^R257 , ^R258 , ^R263 , ^R264 , ^R269 , and ^R270 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 above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, and aryl group may have heteroatoms, and may be unsubstituted or substituted.

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

(Perylene compounds)

Perylene compounds are compounds that have a perylene structure in their molecules and are colored black by absorbing light of visible wavelengths.

As perylene compounds, compounds described in Japanese Patent Publication No. 62-001753 and Japanese Patent Publication No. 63-026784 can be cited.

Furthermore, as the perylene compound, a perylene compound represented by any one of the general formulas (69) to (71) is preferred.

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 a hydrogen atom, 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 to 5. 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 6 carbon atoms. In addition, ^R224 and ^R225 are each independently preferably 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. ^R273 and ^R274 are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkylene group, alkoxy group, acyl group, and alkyl group may have heteroatoms and may be unsubstituted or substituted.

Perylene compounds can be obtained, for example, as C.I. 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 (all of the above trade names are manufactured by BASF).

(Black Dye)

As black dyes, dyes that can produce black alone can be used, for example, pyrazole azo compounds, pyrrole methylene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzal compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazole imine compounds can be used.

In addition, as black dyes, reference can be made to compounds described in Japanese Patent Publication No. 64-090403, Japanese Patent Publication No. 64-091102, Japanese Patent Publication No. 1-094301, Japanese Patent Publication No. 6-011614, Japanese Patent Publication No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 505950, Japanese Patent Publication No. 5-333207, Japanese Patent Publication No. 6-035183, Japanese Patent Publication No. 6-051115, and Japanese Patent Publication No. 6-194828, etc., and the contents are incorporated into this specification.

As specific examples of such black dyes, dyes specified in the colorimetric index (C.I.) of Solvent Black 27 to 47 can be cited, and dyes specified in the C.I. of Solvent Black 27, 29 or 34 are preferred.

In addition, as commercially available products of such black dyes, there are Spilon Black MH, Black BH (the above, manufactured by Hodogaya Chemical Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (the above, manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Savinyl Black RLSN (the above, manufactured by Clariant Chemicals), KAYASET Black K-R, K-BL (the above, manufactured by Nippon Kayaku Co., Ltd.), etc.

In addition, as a black dye, a pigment polymer can be used. As a pigment polymer, compounds described in Japanese Patent Publication No. 2011-213925 and Japanese Patent Publication No. 2013-041097 can be cited. In addition, a polymerizable dye having polymerizability in the molecule can also be used. As a commercial product, for example, the RDW series manufactured by Wako Pure Chemical Industries, LTD. can be cited.

Furthermore, as described above, a plurality of dyes having colors other than black when used alone can be combined to be used as black dyes. As such coloring dyes, for example, in addition to color dyes (color dyes) such as R (red), G (green), and B (blue), dyes described in paragraphs 0027 to 0200 of Japanese Patent Application Laid-Open No. 2014-042375 can also be used.

From the perspective of being able to suppress undercutting when forming a black layer, the black color material preferably contains a nitride or oxynitride of at least one metal selected from the group including titanium, vanadium, zirconium and niobium. From the perspective of better light resistance and moisture resistance of the light-shielding film, it is more preferable to contain an oxynitride of at least one metal selected from the group including titanium, vanadium, zirconium and niobium, and it is particularly preferable to contain titanium oxynitride (titanium black).

In addition, the black color material preferably contains carbon black, benzofuranone compounds or perylene compounds.

(Colorant)

The light-shielding composition may contain a colorant other than the black colorant. The light-shielding properties of the black layer (light-shielding film) can be adjusted by using both the black colorant and one or more colorants. Also, for example, when the black layer is used as a light-attenuating film, it is easy to evenly attenuate each wavelength of light containing a wide-wavelength component.

As coloring agents, pigments and dyes other than the above-mentioned black color materials can be cited.

When the composition contains a colorant, the combined content of the black colorant and the colorant relative to the total mass of the solid components of the composition is preferably 10 to 90 mass %, more preferably 30 to 70 mass %, and even more preferably 40 to 60 mass %.

In addition, when the black layer formed by the light-shielding composition is used as a light-attenuating film, it is also preferred that the combined content of the black colorant and the colorant is less than the above-mentioned preferred range.

In addition, the mass ratio of the colorant content to the black colorant content (colorant content/black colorant content) is preferably 0.1~9.0.

(Infrared absorber)

The composition may contain an infrared absorber.

Infrared absorbers refer to compounds that have absorption in the infrared region (preferably 650-1300nm). As infrared absorbers, compounds with extremely high absorption in the wavelength range of 675-900nm are preferred.

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

Phthalocyanine compounds, naphthalocyanine compounds, ammonium compounds, cyanine compounds, aromatic acid cyanine compounds and croconium compounds can use compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Publication No. 2010-111750, and the contents are introduced into this specification. For example, cyanine compounds can refer to "Functional Pigments, Okawara Nobuyuki/Matsuoka Ken/Kitao Teijiro/Hirajima Tsuneaki, Kodansha Scientific Ltd.", and the contents are introduced into this application specification.

As a coloring agent having the above-mentioned spectral characteristics, the compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Publication No. 07-164729 and/or the compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Publication No. 2002-146254, and the near-infrared absorbing particles disclosed in paragraphs 0034 to 0067 of Japanese Patent Publication No. 2011-164583, which include microcrystals containing oxides of Cu and/or P and have a number average agglomerated particle size of 5 to 200 nm, can also be used.

As the compound having 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 preferred.

Furthermore, the infrared absorber is preferably a compound that dissolves at least 1% by mass in water at 25°C, and more preferably a compound that dissolves at least 10% by mass in water at 25°C. By using such compounds, solvent resistance is improved.

The pyrrolopyrrole compounds can refer to 0049 to 0062 of Japanese Patent Publication No. 2010-222557, and the contents are incorporated into this specification. The 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 Publication No. 2014-059550, paragraphs 0013 to 0091 of International Publication No. 2012/169447, and paragraphs 0017 to 0018 of Japanese Patent Publication No. 2014-088063. Paragraphs 0019 to 0033 of Japanese Patent Application No. 15-176046, paragraphs 0053 to 0099 of Japanese Patent Application No. 2014-063144, paragraphs 0085 to 0150 of Japanese Patent Application No. 2014-052431, paragraphs 0076 to 0124 of Japanese Patent Application No. 2014-044301, and paragraphs 0045 to 007 of Japanese Patent Application No. 2012-008532 8. Paragraphs 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172102, paragraphs 0029 to 0067 of Japanese Patent Application Laid-Open No. 2015-172004, paragraphs 0029 to 0085 of Japanese Patent Application Laid-Open No. 2015-040895, paragraphs 0022 to 0036 of Japanese Patent Application Laid-Open No. 2014-126642, paragraphs 0036 of Japanese Patent Application Laid-Open No. 2014-148567 0011~0017, paragraphs 0010~0025 of Japanese Patent Publication No. 2015-157893, paragraphs 0013~0026 of Japanese Patent Publication No. 2014-095007, paragraphs 0013~0047 of Japanese Patent Publication No. 2014-080487, and paragraphs 0007~0028 of Japanese Patent Publication No. 2013-227403, etc., the contents are introduced into this specification.

<Resin>

The light-shielding composition contains a resin. Examples of the resin include a dispersible resin and an alkali-soluble resin.

The content of the resin in the composition is not particularly limited. It is preferably 3 to 60% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass relative to the total solid content of the composition. The resin may be used alone or in combination of two or more. For example, the dispersible resin described below and the alkali-soluble resin described below may be used in combination as the resin. When two or more resins are used in combination, the total content within the above range is preferred.

In addition, resin refers to a component that is dissolved in a composition and has a molecular weight greater than 2000. When the molecular weight of the resin is polydisperse, the weight average molecular weight of the resin is greater than 2000.

(Dispersed resin)

It is preferred that the light-shielding composition contains a dispersing resin. In addition, in this specification, the dispersing resin refers to a compound different from the alkali-soluble resin described later.

There is no particular restriction on the content of the dispersing resin in the composition. Relative to the total solid content of the composition, 2-40% by mass is preferred, 5-30% by mass is more preferred, and 10-20% by mass is even more preferred.

The dispersing resin may be used alone or in combination of two or more. When two or more dispersing resins are used in combination, the one with a total content within the above range is preferred.

In addition, the mass ratio of the content of the dispersing resin (preferably a grafted polymer) to the content of the black color material in the composition (content of the dispersing resin/content of the black color material) is preferably 0.05~1.00, more preferably 0.05~0.35, and even more preferably 0.20~0.35.

As the dispersing resin, for example, a known dispersant can be appropriately selected for use. Among them, a polymer compound is preferred.

As dispersing resins, there can be cited polymer dispersants (for example, polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic acid copolymers, naphthalenesulfonic acid formalin condensates), polyoxyethylene alkyl phosphates, polyoxyethylene alkylamines, and pigment derivatives.

Polymer compounds can be further classified into linear polymers, terminal-modified polymers, grafted polymers, and block polymers according to their structures.

˙Polymer compounds

The polymer compound is adsorbed on the surface of the dispersed body such as the black pigment and other pigments used in combination as needed (hereinafter, the black pigment and other pigments are simply recorded as "pigments"), and plays a role in preventing the dispersed body from re-agglomerating. Therefore, terminal modified polymers, grafted polymers (containing polymer chains) or block polymers containing a fixing site on the pigment surface are preferred.

The above-mentioned polymer compound may contain a hardening group.

Examples of curing groups include groups having ethylenically unsaturated bonds (hereinafter also described as "ethylenically unsaturated groups") (e.g. (meth)acryloyl, vinyl, and styrene groups) and cyclic ether groups (e.g. epoxy, cyclobutyl, etc.), but are not limited to these.

Among them, as a curing group, from the perspective of being able to control polymerization in a free radical reaction, an ethylenic unsaturated group is preferred, and a (meth)acrylic group is more preferred.

From the perspective of improving the light resistance, moisture resistance, and heat resistance of the light-shielding film, it is preferred that the light-shielding composition contain a dispersed resin having a curable group (preferably an ethylenically unsaturated group).

As a dispersion resin having a curable group, for example, a polymer compound containing a structural unit having a curable group (preferably an ethylenically unsaturated group such as a (meth)acryl group) can be cited. In addition, in this specification, "structural unit" and "repeating unit" have the same meaning.

For example, a curable group may be introduced into the end of a graft chain of a structural unit containing the following graft chain. More specifically, in a structural unit constituting a polymer compound, a curable group (preferably an ethylenically unsaturated group such as a (meth)acrylic group) may be introduced into a part or all of one or more units derived from (meth)acrylic acid and/or other addition polymerizable vinyl monomers.

In the polymer compound, the content of the structural unit having a curable group is preferably 2 to 90 mass % relative to the total mass of the polymer compound, and more preferably 5 to 30 mass %.

It is preferred that the resin having a curable group contains at least one selected from the group including polyester structure and polyether structure. In this case, the main chain may contain a polyester structure and/or a polyether structure. When the above-mentioned resin contains a structural unit containing a graft chain as described later, the above-mentioned polymer chain may contain a polyester structure and/or a polyether structure.

As the above-mentioned resin, it is more preferable that the above-mentioned polymer chain contains a polyester structure.

It is preferred that the polymer compound contains a structural unit containing a grafted chain. In addition, in this specification, "structural unit" and "repeating unit" have the same meaning.

The polymer compound containing the structural unit containing the grafted chain has an affinity with the solvent due to the grafted chain, so the dispersibility of the pigment and the dispersion stability after time (stability over time) are excellent. In addition, due to the presence of the grafted chain, the polymer compound containing the structural unit containing the grafted chain has an affinity with the polymerizable compound or other resins that can be used in combination.

As a result, it is less likely to generate residue during alkaline development.

If the graft chain becomes longer, the stereo repulsion effect increases and the dispersibility of the pigment etc. is improved. On the other hand, if the graft chain is too long, the adsorption force to the pigment etc. decreases and the dispersibility of the pigment etc. tends to decrease. Therefore, in the graft chain, the number of atoms other than hydrogen atoms is preferably 40 to 10,000, the number of atoms other than hydrogen atoms is more preferably 50 to 2,000, and the number of atoms other than hydrogen atoms is further preferably 60 to 500.

The graft chain refers to the root of the main chain of the copolymer (the atom bonded to the main chain in the group branching from the main chain) to the end of the group branching from the main chain.

It is preferred that the graft chain contains a polymer structure. Examples of such polymer structures include poly(meth)acrylate structures (e.g., poly(meth)acrylic acid structures), polyester structures, polyurethane structures, polyurea structures, polyamide structures, and polyether structures.

In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility of the pigment, the graft chain preferably contains at least one graft chain selected from the group including polyester structure, polyether structure and poly(meth)acrylate structure, and more preferably contains at least one of the polyester structure and polyether structure.

There is no particular limitation on the macromonomer containing such a graft chain (a monomer having a polymer structure and bonding to the main chain of the copolymer to form a graft chain), and macromonomers containing ethylenically unsaturated groups can be preferably used.

Furthermore, from the perspective of achieving better light resistance, moisture resistance, and heat resistance of the light-shielding film, it is preferred that the polymer compound have a curable group, and it is even more preferred that the polymer compound contain an ethylenically unsaturated group such as a (meth)acrylic group.

As commercially available macromonomers that correspond to the structural units containing the graft chains contained in the polymer compound and can be preferably used for the synthesis of the polymer compound, 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 names, manufactured by NOF CORPORATION) can be used. Among them, AA-6, AA-10, AB-6, AS-6, AN-6 or BLEMMER PME-4000 are preferred.

The above-mentioned dispersed resin preferably contains at least one structure selected from the group including polymethyl acrylate, polymethyl methacrylate and cyclic or chain polyester, more preferably contains at least one structure selected from the group including polymethyl acrylate, polymethyl methacrylate and chain polyester, and further preferably contains at least one structure selected from the group including polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure and polyvalerolactone structure. The dispersed resin may contain the above-mentioned structure alone in one resin, or may contain a plurality of such structures in one resin.

Among them, the polycaprolactone structure refers to a structure containing a ring-opened ε-caprolactone structure as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opened δ-valerolactone structure as a repeating unit.

As a specific example of a dispersing resin containing a polycaprolactone structure, there can be cited a dispersing resin in which j and k are 5 in the following formula (1) and the following formula (2). Also, as a specific example of a dispersing resin containing a polyvalerolactone structure, there can be cited a dispersing agent in which j and k are 4 in the following formula (1) and the following formula (2).

As a specific example of a dispersed resin containing a polymethyl acrylate structure, there can be cited a dispersed resin in which ^X5 in the following formula (4) is a hydrogen atom and ^R4 is a methyl group. Also, as a specific example of a dispersed resin containing a polymethyl methacrylate structure, there can be cited a dispersed resin in which ^X5 in the following formula (4) is a methyl group and ^R4 is a methyl group.

˙Structural units containing grafted chains

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

[Chemical formula 4]

In formulae (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. Preferably, W ¹ , W ² , W ³ and W ⁴ are oxygen atoms.

In formulae (1) to (4), ^X1 , ^X2 , ^X3 , ^X4 and ^X5 each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthetic constraints, ^X1 , ^X2 , ^X3 , ^X4 and ^X5 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.

In formulae (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the structure of the linking group is not particularly limited. As the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ , specifically, the following linking groups (Y-1) to (Y-21) can be cited. In the structures shown below, A and B represent the bonding sites with the left terminal group and the right terminal group in formulae (1) to (4), respectively. Among the structures shown below, (Y-2) or (Y-13) is more preferred from the perspective of simplicity of synthesis.

[Chemical formula 5]

In formulae (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, and specifically, alkyl, hydroxyl, alkoxy, aryloxy, heteroaryloxy, alkylthioether, arylthioether, heteroarylthioether and amino groups can be cited. Among them, as the organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ , a group having a stereo-repelling effect is preferred from the viewpoint of improving dispersibility, and it is more preferred that each of them independently represent an alkyl group or an alkoxy group having 5 to 24 carbon atoms, and it is even more preferred that each of them independently represent a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms. In addition, the alkyl group contained in the alkoxy group may be in a linear, branched or cyclic form.

In formulas (1) to (4), n, m, p, and q are independently integers ranging from 1 to 500.

In formulas (1) and (2), j and k each independently represent an integer of 2 to 8. From the perspective of the stability over time and the developing property of the composition, j and k in formulas (1) and (2) are preferably integers of 4 to 6, and 5 is more preferably.

Furthermore, in formulas (1) and (2), n and m are preferably integers greater than 10, and more preferably integers greater than 20. Furthermore, when the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the repetition number of the polycaprolactone structure and the repetition number of the polyvalerolactone is preferably an integer greater than 10, and more preferably an integer greater than 20.

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

In formula (4), ^R4 represents a hydrogen atom or a monovalent organic group, and the monovalent structure is not particularly limited. As ^R4 , a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group is preferred, and a hydrogen atom or an alkyl group is more preferred. When ^R4 is an alkyl group, as the alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferred, a linear alkyl group having 1 to 20 carbon atoms is more preferred, and a linear alkyl group having 1 to 6 carbon atoms is further preferred. In formula (4), when q is 2 to 500, a plurality of ^X5 and ^R4 present in the graft copolymer may be the same or different from each other.

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

As the structural unit represented by formula (1), from the viewpoint of the temporal stability and developing properties of the composition, the structural unit represented by the following formula (1A) is more preferable.

Furthermore, as the structural unit represented by formula (2), from the viewpoint of the temporal stability and developing properties of the composition, the structural unit represented by the following formula (2A) is more preferable.

In formula (1A), ^X1 , ^Y1 , ^Z1 and n have the same meanings as ^X1 , ^Y1 , ^Z1 and n in formula (1), and the preferred ranges are also the same. In formula (2A), ^X2 , ^Y2 , ^Z2 and m have the same meanings as ^X2 , ^Y2 , ^Z2 and m in formula (2), and the preferred ranges are also the same.

Furthermore, as the structural unit represented by formula (3), from the perspective of the temporal stability and developing properties of the composition, the structural unit represented by the following formula (3A) or formula (3B) is more preferred.

[Chemical formula 7]

In formula (3A) or (3B), X ³ , Y ³ , Z ³ and p have the same meanings as X ³ , Y ³ , Z ³ and p in formula (3), and the preferred ranges are also the same.

As a structural unit containing a grafted chain, it is more preferable that the polymer compound contains a 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 preferably 2 to 90 mass % and more preferably 5 to 30 mass % relative to the total mass of the polymer compound. If the structural unit containing the graft chain is included within this range, the dispersibility of the pigment is high and the developing property when forming a cured film is good.

˙Hydrophobic structural unit

Furthermore, it is preferred that the polymer compound contains a hydrophobic structural unit that is different from the structural unit containing the grafted chain (that is, not equivalent to the structural unit containing the grafted chain). In the present invention, the hydrophobic structural unit is a structural unit that does not contain an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) with a ClogP value of 1.2 or more, and is more preferably a structural unit derived from a compound with a ClogP value of 1.2 to 8. In this way, the effect of the present invention can be more effectively demonstrated.

The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. The program provides the "calculated logP" value calculated by the fragment approach of Hansch, Leo (see the following reference). The fragment approach divides the chemical structure into partial structures (fragments) according to the chemical structure of the compound, and calculates the logP value of the compound by summing up the logP contribution assigned to the fragment. The details are described in the following reference. In this manual, the ClogP value calculated by the program CLOGP v4.82 is used.

A.J.Leo, Comprehensive Medicinal Chemistry, Vol.4, C.Hansch, P.G.Sammnens, J.B.Taylor and C.A.Ramsden, Eds., p.295, Pergamon Press, 1990 C.Hansch & A.J.Leo.SUbstituent Constants For Correlation Analysis in Chemistry and Biology.John Wiley & Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

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

logP=log(Coil/Cwater)

In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase.

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

It is preferred that the polymer compound contains, as a hydrophobic structural unit, one or more structural units selected from the structural units derived from monomers represented by the following formulae (i) to (iii).

[Chemical formula 8]

In the above formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.).

R ¹ , R ² and R ³ are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, more preferably hydrogen atoms or methyl groups. R ² and R ³ are further preferably hydrogen atoms.

X represents an oxygen atom (-O-) or an imine group (-NH-), and an oxygen atom is preferred.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group), a divalent aromatic group (e.g., an arylene group, a substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ -, wherein R ³¹ is an aliphatic group, an aromatic group, or a heterocyclic group), a 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 to 20, more preferably 1 to 15, and even more preferably 1 to 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 the substituent include halogen atoms, aromatic groups, and heterocyclic groups.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. In addition, the aromatic group may have a substituent. Examples of the substituent 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 another heterocyclic ring, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thio group (=S), an imino group (=NH), a substituted imino group (=NR ³² , wherein R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

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

As Z, there can be mentioned an aliphatic group (e.g., an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (e.g., an aryl group, a substituted aryl group, an arylene group, a substituted arylene group), a heterocyclic group, and a combination thereof. These groups may contain an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ -, wherein R ³¹ is an aliphatic group, an aromatic group, or a heterocyclic group), or a 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 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group also includes polycyclic alkyl groups and cross-linked cyclic alkyl groups. Examples of the ring-aggregated alkyl groups include bicyclohexyl, perhydronaphthyl, biphenyl, and 4-cyclohexylphenyl. Examples of the cross-linked cyclic hydrocarbon ring include: bicyclic hydrocarbon rings such as pinane, bornane, norpinane, norbornane, and bicyclic octane rings (bicyclic [2.2.2] octane ring, bicyclic [3.2.1] octane ring, etc.); tricyclic hydrocarbon rings such as homobledanes, adamantane, tricyclic [5.2.1.0 ^2,6 ] decane, and tricyclic [4.3.1.1 ^2,5 ] undecane ring; tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane and perhydro-1,4-methylene-5,8-methylenenaphthalene ring and other four-ring hydrocarbon rings. In addition, the cross-linked ring hydrocarbon ring also includes a condensed ring hydrocarbon ring, for example, perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene and perhydrophthalene ring, which are condensed rings with multiple 5-8 membered cycloalkane hydrocarbon rings.

Compared with unsaturated aliphatic groups, aliphatic groups are preferably saturated aliphatic groups. In addition, aliphatic groups may have substituents. Examples of substituents include halogen atoms, aromatic groups, and heterocyclic groups. Among them, aliphatic groups do not have acid groups as substituents.

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

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 another heterocyclic ring, an aliphatic ring or an aromatic ring. In addition, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thio group (=S), an imino group (=NH), a substituted imino group (=NR ³² , wherein R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. The heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.), Z or LZ. Wherein, 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 preferred, and a hydrogen atom is more preferred.

The monomer represented by the above formula (i) is preferably a compound wherein ^R1 , ^R2 and ^R3 are hydrogen atoms or methyl groups, L is a single bond or an alkylene group or a divalent linking group containing an oxyalkylene structure, X is an oxygen atom or an imine group, and Z is an aliphatic group, a heterocyclic group or an aromatic group.

Furthermore, as the monomer represented by the above formula (ii), the compound wherein 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 preferred. Furthermore, as the monomer represented by the above formula (iii), the compound wherein R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferred.

Representative examples of compounds represented by formula (i) to (iii) include free radical polymerizable compounds selected from acrylates, methacrylates, styrenes, etc.

In addition, as examples of representative compounds represented by formula (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of Japanese Patent Application No. 2013-249417, and such contents are incorporated into this specification.

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

˙Functional groups that can interact with pigments, etc.

The polymer compound can introduce functional groups that can interact with pigments (such as black pigments). It is preferred that the polymer compound also contains structural units containing functional groups that can interact with pigments.

Examples of functional groups that can interact with the pigment include acid groups, base groups, coordination groups, and reactive functional groups.

When the polymer compound has an acid group, an alkaline group, a coordinating group or a reactive functional group, it is preferred to contain a structural unit having an acid group, a structural unit having an alkaline group, a structural unit having a coordinating group or a reactive structural unit respectively.

In particular, if the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be endowed with developing properties for pattern formation based on alkali development.

That is, if an alkali-soluble group is introduced into the polymer compound, the polymer compound as a dispersing resin that helps disperse the pigment in the above 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 part is improved.

Furthermore, if the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be easily soluble in the solvent and the coating properties are also improved.

This is presumably because the acid groups in the structural units containing acid groups are easy to interact with pigments, etc., so that the polymer compound can stably disperse the pigments, etc., and the viscosity of the polymer compound in which the pigments, etc. are dispersed becomes lower, and the polymer compound itself can also be easily and stably dispersed.

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

Acid groups that can interact with pigments and the like include carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups. At least one of the carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups is preferred, and carboxylic acid groups are more preferred. Carboxylic acid groups have good adsorption power to pigments and the like, and high dispersibility.

That is, it is preferred that the polymer compound also contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

A polymer compound may have one or more structural units containing acid groups.

The polymer compound may or may not contain a structural unit containing an acid group, but when it does, the content of the structural unit containing an acid group is preferably 5 to 80% by mass relative to the total mass of the polymer compound, and from the perspective of suppressing the damage to the image intensity based on alkali development, 10 to 60% by mass is more preferred.

As functional groups that can interact with pigments, there are primary amine groups, secondary amine groups, tertiary amine groups, heterocyclic groups containing N atoms, and amide groups. From the perspective of good adsorption to pigments and high dispersibility, the preferred alkali group is the tertiary amine group. The polymer compound can contain one or more of these alkali groups.

The polymer compound may or may not contain a structural unit containing an alkali group, but when it does, the content of the structural unit containing an alkali group is preferably 0.01 to 50% by mass relative to the total mass of the polymer compound, and from the perspective of suppressing the development resistance, 0.01 to 30% by mass is more preferable.

Examples of the coordinating group and reactive functional group that can interact with pigments include acetoacetyloxy, trialkoxysilyl, isocyanate, acid anhydride, and acyl chloride. From the perspective of good adsorption to pigments and high dispersibility of pigments, the preferred functional group is acetoacetyloxy. The polymer compound may have one or more of these groups.

The polymer compound may or may not contain a structural unit containing a coordination group or a structural unit containing a reactive functional group, but when contained, the content of such structural units is preferably 10-80% by mass relative to the total mass of the polymer compound, and 20-60% by mass is more preferably considered from the perspective of suppressing the development resistance.

When the polymer compound contains functional groups capable of interacting with pigments, etc. in addition to the grafted 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 the functional groups are introduced. However, it is preferred that the polymer compound contains one or more structural units selected from structural units derived from monomers represented by the following formulas (iv) to (vi).

In formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.).

In formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and more preferably hydrogen atoms or methyl groups. In general formula (iv), R ¹² and R ¹³ are further preferably hydrogen atoms.

_X1 in formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.

In addition, Y in formula (v) represents a methine group or a nitrogen atom.

In formulae (iv) to (v), _L1 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 formula (i) above.

_L1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, _L1 may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a _{polyoxypropylene structure is preferred. The polyoxyethylene structure is represented by -(OCH2CH2 )} n-, wherein n is preferably an integer greater than 2, and more preferably an integer of 2 to 10.

In formulae (iv) to (vi), _Z1 represents, in addition to the graft chain, a functional group capable of interacting with a pigment, etc., preferably a carboxylic acid group or a tertiary amine group, and more preferably a carboxylic acid group.

In formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.), -Z ₁ or L ₁ -Z ₁ . L ₁ and Z ₁ have the same meanings as L ₁ and Z ₁ above, 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 preferred, and a hydrogen atom is more preferred.

The monomer represented by formula (iv) is preferably a compound wherein R ¹¹ , R ¹² and R ¹³ are independently a hydrogen atom or a methyl group, L ₁ is an alkylene group or a divalent linking group containing an oxyalkylene structure, X ₁ is an oxygen atom or an imine group, and Z ₁ is a carboxylic acid group.

Furthermore, as the monomer represented by formula (v), a compound wherein 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), a compound in which R ¹⁴ , R ¹⁵ and R ¹⁶ are 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 is preferred.

Representative examples of monomers (compounds) represented by formulas (iv) to (vi) are shown below.

Examples of the monomer include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule (e.g., 2-hydroxyethyl methacrylate) and succinic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in 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 acid. The reaction products of the compound containing addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, the reaction products of the compound containing addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol and 4-hydroxybenzyl acryloyl, etc.

From the perspective of interaction with pigments, stability over time, and permeability to developer, the content of the structural unit containing a functional group capable of interacting with pigments is preferably 0.05-90 mass %, more preferably 1.0-80 mass %, and even more preferably 10-70 mass % relative to the total mass of the polymer compound.

˙Other structural units

Furthermore, for the purpose of improving various properties such as image strength, the polymer compound may further have a structural unit containing a grafted chain, a hydrophobic structural unit, and other structural units having various functions different from the structural unit containing a functional group capable of forming an interaction with a pigment, etc. (for example, a structural unit containing a functional group having an affinity for the solvent described below, etc.) without impairing the effect of the invention.

As such other structural units, for example, structural units derived from free radical polymerizable compounds selected from acrylonitrile and methacrylonitrile can be cited.

The polymer compound can use one or more of these other structural units, and the content thereof is preferably 0-80% by mass, and more preferably 10-60% by mass, relative to the total mass of the polymer compound. The content within the above range can maintain sufficient pattern formation.

˙Physical properties of polymer compounds

The acid value of the polymer compound is preferably 0~250mgKOH/g, more preferably 10~200mgKOH/g, further preferably 30~180mgKOH/g, and particularly preferably 70~120mgKOH/g.

If the acid value of the polymer compound is below 160 mgKOH/g, the pattern peeling during development when the cured film is formed can be more effectively suppressed. If the acid value of the polymer compound is above 10 mgKOH/g, the alkali developability is better. If the acid value of the polymer compound is above 20 mgKOH/g, the sedimentation of the pigment etc. can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability of the composition can be further improved.

In this specification, for example, the acid value can be calculated from the average content of acid groups in a compound. Also, if the constituent components of the resin, that is, the content of the structural unit containing the acid group, 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, further preferably 6,000 to 100,000, and particularly preferably 10,000 to 50,000.

The polymer compound can be synthesized according to known methods.

Specific examples of polymer compounds include "DA-7301" manufactured by Kusumoto Chemicals, LTD., "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid groups), 111 (phosphoric acid-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)" manufactured by BYK Chemie, and "BYK-P104, P105 (polymer Unsaturated polycarboxylic acid)", EFKA "EFKA4047, 4050~4010~4165 (polyurethane series), EFKA4330~4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyamide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", Ajinomoto Fine-Techno Co., Inc.'s "AJISPER PB821, PB822, PB880, PB881", KYOEISHA CHEMICAL Co., LTD.'s "FLOREN TG-710 (urethane oligomer)", "Polyflow No.50E, No.300 (acrylic copolymer)", Kusumoto Chemicals, LTD.'s "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725", Kao Corporation's "DEMOL RN, N (naphthalenesulfonic acid formalin condensation), MS, C, SN-B (aromatic sulfonic acid formalin condensation)", "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN 86 (stearylamine acetate)", "SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer containing a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer)" manufactured by The Lubrinzol Corporation, "Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikkol Chemicals CO., LTD., Hinoakuto T-8000E manufactured by Kawaken Fine Chemicals CO., LTD., etc., Shin-Etsu Chemical Co., LTD., "W001: Cationic Surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester and other nonionic surfactants, "W004, W005, W017" and other anionic surfactants, "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450" manufactured by MORISHITA & CO., LTD., "Disperse Aid 6, Disperse Aid 6" manufactured by SAN NOPCO LIMITED 8, Disperse Aid 15, Disperse Aid 9100" and other polymer dispersants, Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION, and Ionet (trade name) S-20 manufactured by Sanyo Chemical Industries, LTD., etc. In addition, Acrybase FFS-6752 and Acrybase FFS-187 can also be used.

In addition, it is also preferred to use an amphoteric resin containing an acid group and an alkaline group. Amphoteric resins having an acid value of 5 mgKOH/g or more and an amine value of 5 mgKOH/g or more are preferred.

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

These polymer compounds may be used alone or in combination of two or more.

In addition, as specific examples of polymer compounds, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of Japanese Patent Application No. 2013-249417, and such contents are incorporated into this specification.

Furthermore, as a dispersing resin, in addition to the above-mentioned polymer compounds, the graft copolymers in paragraphs 0037 to 0115 of Japanese Patent Publication No. 2010-106268 (corresponding to paragraphs 0075 to 0133 of US2011/0124824) can also be used, and such contents can be cited and introduced into this specification.

In addition to the above, the polymer compound containing a component having a side chain structure formed by bonding an acidic group through a linking group described in paragraphs 0028 to 0084 of Japanese Patent Publication No. 2011-153283 (corresponding to paragraphs 0075 to 0133 of US2011/0279759) can also be used, and such contents can be cited and introduced into this specification.

Furthermore, as the dispersing resin, the resin described in paragraphs 0033 to 0049 of Japanese Patent Application No. 2016-109763 can also be used, and the contents are incorporated into this specification.

(Alkaline soluble resin)

The composition preferably contains an alkali-soluble resin. In this specification, the alkali-soluble resin refers to a resin containing a group that promotes alkali solubility (alkali-soluble group, such as acid group such as carboxylic acid group), and refers to a resin different from the dispersing resin described above.

There is no particular limitation on the content of the alkali-soluble resin in the composition. It is preferably 1 to 30% by mass relative to the total solid content of the composition, more preferably 2 to 20% by mass, and even more preferably 5 to 15% by mass.

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

As alkali-soluble resins, there can be cited resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic acid/(meth)acrylamide copolymer resins, epoxy resins, and polyimide resins.

As a specific example of the alkali-soluble resin, there is a copolymer resin of an unsaturated carboxylic acid and an ethylenically unsaturated compound.

The unsaturated carboxylic acid is not particularly limited, and examples thereof include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acids such as itaconic acid, succinic acid, and fumaric acid, or their anhydrides; and polycarboxylic acid monoesters such as mono(2-(meth)acryloyloxyethyl)phthalate; etc.

As copolymerizable ethylenically unsaturated compounds, methyl (meth)acrylate and the like can be cited. In addition, compounds described in paragraph 0027 of Japanese Patent Publication No. 2010-097210 and paragraphs 0036 to 0037 of Japanese Patent Publication No. 2015-068893 can also be used, and the above contents are introduced into this specification.

In addition, a copolymerizable ethylenically unsaturated compound and a compound containing an ethylenically unsaturated group in the side chain can 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 can be obtained by, for example, allowing the carboxylic acid group of an acrylic resin containing a carboxylic acid group to undergo an addition reaction with a glyoxypropyl 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 preferred.

As the above-mentioned curing group, the curing group that can contain the above-mentioned polymer compound can be cited in the same manner, and the preferred range is also the same.

As the alkali-soluble resin containing a curable group, an alkali-soluble resin having a curable group in a side chain is preferred. As alkaline soluble resins containing a curable group, there are 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 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (such as ACA230AA), PLACCEL CF200 series (all manufactured by Daicel Corporation.), Ebecry13800 (manufactured by DAICEL-ALLNEX LTD.), and ACRYCURE RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.).

As the alkali-soluble resin, for example, free radical polymers containing carboxylic acid groups in the side chains described in Japanese Patent Publication No. 59-044615, Japanese Patent Publication No. 54-034327, Japanese Patent Publication No. 58-012577, Japanese Patent Publication No. 54-025957, Japanese Patent Publication No. 54-092723, Japanese Patent Publication No. 59-053836 and Japanese Patent Publication No. 59-071048 can be used; European Patent No. Acetal-modified polyvinyl alcohol-based adhesive resin containing an alkali-soluble group as described in Gazette No. 993966, European Patent No. 1204000 and Japanese Patent Publication No. 2001-318463; polypyrrolidone; polyethylene oxide; alcohol-soluble nylon and the reaction product of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, i.e., polyether; and polyimide resin described in International Publication No. 2008/123097; etc.

As the alkali-soluble resin, for example, the compounds described in paragraphs 0225 to 0245 of Japanese Patent Application No. 2016-075845 can also be used, and the above contents are incorporated into this specification.

As an alkali-soluble resin, a polyimide precursor can also be used. A polyimide precursor is a resin obtained by allowing a compound containing an acid anhydride group to undergo addition polymerization with a diamine compound at 40-100°C.

As a polyimide precursor, for example, a resin containing a repeating unit represented by formula (1) can be cited. As a structure of a polyimide precursor, for example, an amide structure represented by the following formula (2), and a polyimide precursor containing an amide structure represented by the following formula (3) formed by ring closure of a part of the amide structure and the following formula (4) formed by ring closure of all the amides can be cited.

In addition, in this specification, polyimide precursors having an amide structure are sometimes referred to as polyamide.

[Chemical formula 13]

In the above formulae (1) to (4), _R1 represents a tetravalent organic group having 2 to 22 carbon atoms, _R2 represents a divalent organic group having 1 to 22 carbon atoms, and n represents 1 or 2.

As specific examples of the polyimide precursor, there can be cited compounds described in paragraphs 0011 to 0031 of Japanese Patent Application No. 2008-106250, compounds described in paragraphs 0022 to 0039 of Japanese Patent Application No. 2016-122101, and compounds described in paragraphs 0061 to 0092 of Japanese Patent Application No. 2016-068401, and the above contents are incorporated into this specification.

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

As the polyimide resin containing an alkali-soluble group, there is no particular limitation, and a polyimide resin containing a known alkali-soluble group can be used. As the above-mentioned polyimide resin, for example, the resin described in paragraph 0050 of Japanese Patent Publication No. 2014-137523, the resin described in paragraph 0058 of Japanese Patent Publication No. 2015-187676, and the resin described in paragraphs 0012 to 0013 of Japanese Patent Publication No. 2014-106326 can be cited, and the above contents are introduced into this specification.

唑前驅物。 As an alkali-soluble resin, polyphenylene glycol can also be used.

Azole prodrug.

唑前驅物係由含有羥基之二胺及二羧酸衍生物合成之樹脂。 Polyphenylene

Azole prodrugs are resins synthesized from diamines and dicarboxylic acid derivatives containing hydroxyl groups.

Examples of diamines containing a hydroxyl group include aromatic diamines having a phenolic hydroxyl group such as diaminophenol compounds. Specific examples of diamines containing a hydroxyl group include 3,3-dihydroxybenzidine and 3,3'-dihydroxy-4,4'-diaminodiphenyl ether.

Examples of dicarboxylic acid derivatives include dicarboxylic acid chloride, dicarboxylic acid esters, and other dicarboxylic acid derivatives, and aromatic dicarboxylic acid derivatives are preferred. Specific examples of dicarboxylic acid derivatives include isophthalic acid chloride and terephthalic acid chloride.

唑前驅物的具體例，可舉出聚羥基醯胺、聚胺基醯胺、聚醯胺及聚醯胺醯亞胺。 As polyphenylene

Specific examples of the azole prodrug include polyhydroxyamide, polyaminoamide, polyamide and polyamideimide.

唑前驅物的具體例，例如，可舉出日本特開2003-121997號公報的段落0049~0062中記載之化合物、國際公開第2017/057281號說明書的段落0050~0057中記載之化合物、國際公開第2016/043203號說明書的段落0015~0043中記載之化合物等，上述內容引入本說明書中。 As polyphenylene

Specific examples of azole prodromal compounds include, for example, compounds described in paragraphs 0049 to 0062 of Japanese Patent Application Publication No. 2003-121997, compounds described in paragraphs 0050 to 0057 of International Publication No. 2017/057281, and compounds described in paragraphs 0015 to 0043 of International Publication No. 2016/043203, and the above contents are incorporated into this specification.

唑前驅物的共聚物係具有聚醯胺酸酯結構單元及羥基聚醯胺結構單元之共聚物，例如，可舉出具有聚醯胺酸酯結構單元及羥基聚醯胺結構單元的交互共聚結構之共聚物。 Polyimide precursor and polybenzo

The copolymer of the azole precursor is a copolymer having a polyamic acid ester structural unit and a hydroxypolyamide structural unit. For example, a copolymer having an alternating copolymerization structure of a polyamic acid ester structural unit and a hydroxypolyamide structural unit can be cited.

唑前驅物及該等的共聚物的群組中之至少1種為較佳，聚醯亞胺樹脂為更佳。 As an alkali-soluble resin, from the viewpoint of better light resistance and heat resistance of the light-shielding film, it is selected from polyimide precursors, polybenzoic acid

At least one of the group consisting of azole promotors and copolymers thereof is preferred, and polyimide resin is more preferred.

In addition, as alkali-soluble resins, [benzyl (meth)acrylate/(meth)acrylic acid/other addition-polymerizable vinyl monomers as required] copolymers and [allyl (meth)acrylate/(meth)acrylic acid/other addition-polymerizable vinyl monomers as required] copolymers have an excellent balance of film strength, sensitivity, and developing properties and are preferred in this respect.

The above-mentioned other addition polymerizable vinyl monomers may be one type or two or more types.

From the perspective of better moisture resistance of the black layer, it is preferred that the copolymer have a curable group, and it is even more preferred that the copolymer contain an ethylenically unsaturated group such as a (meth)acryl group.

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

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

Examples of the above-mentioned ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).

In the general formula (ED1), ^R1 and ^R2 each independently represent a hydrogen atom or a carbonyl group having 1 to 25 carbon atoms.

In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For specific examples of the general formula (ED2), reference may be made to the description of Japanese Patent Publication No. 2010-168539.

As a specific example of the ether dimer, for example, reference can be made to paragraph 0317 of Japanese Patent Publication No. 2013-029760, which is incorporated into this specification. The ether dimer may be only one type or may be two or more types.

There is no particular restriction on the acid value of the alkali-soluble resin. Generally, 30~500mgKOH/g is preferred, and 50~200mgKOH/g or above is more preferred.

<Polymerizable compounds>

The light-shielding composition contains a polymerizable compound.

In this specification, the polymerizable compound refers to a compound that polymerizes under the action of the polymerization initiator described below, and refers to a component different from the above-mentioned dispersible resin and alkali-soluble resin.

There is no particular limitation on the content of the polymerizable compound in the composition, but 5 to 35% by mass relative to the total solid content of the composition is preferred, 10 to 30% by mass is more preferred, and 15 to 25% by mass is further preferred. The polymerizable compound may be used alone or in combination of two or more. 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 preferably below 2000.

As polymerizable compounds, compounds containing ethylenically unsaturated groups are preferred.

That is, it is preferred that the light-shielding composition contains a low molecular weight compound containing an ethylenically unsaturated group as a polymerizable compound.

As polymerizable compounds, compounds containing one or more ethylenic unsaturated bonds are preferred, compounds containing two or more are more preferred, compounds containing three or more are further preferred, and compounds containing five or more are particularly preferred. The upper limit is, for example, 15 or less. Examples of ethylenic unsaturated groups include vinyl, (methyl)aryl, and (methyl)acryloyl.

As polymerizable compounds, for example, compounds described in paragraph 0050 of Japanese Patent Publication No. 2008-260927 and paragraph 0040 of Japanese Patent Publication No. 2015-068893 can be used, and the above contents are introduced into this specification.

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

The polymerizable compound is preferably a 3-15-functional (meth)acrylate compound, and a 3-6-functional (meth)acrylate compound is more preferred.

It is also preferred that the polymerizable compound is a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100°C or more at normal pressure. For example, reference can be made to the compounds described in paragraph 0227 of Japanese Patent Publication No. 2013-029760 and paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970, and the contents are incorporated into this specification.

The polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth)acryloyl groups mediate ethylene glycol residues or propylene glycol residues (for example, manufactured by Sartomer Company). Inc. SR454, SR499) are preferred. Such 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 trade names, manufactured by Nippon Kayaku Co., Ltd.) can be used.

The following shows the state of the preferred polymerizable compound.

It is preferred that the light-shielding composition contains at least two polymerizable compounds.

Among them, from the perspective of better heat resistance and moisture resistance of the light-shielding film, it is preferred that the compound has a similar structure and contains two or more polymerizable compounds with different numbers of ethylenic unsaturated groups, and the compound with fewer ethylenic unsaturated groups contains at least one hydroxyl group. The reason why the heat resistance and moisture resistance of the light-shielding film are improved by using two or more polymerizable compounds is not clear, but the reasons are speculated as follows: By using a polymerizable compound with a hydroxyl group, the compatibility with the alkali-soluble resin is improved, the polymerizable compound is evenly distributed in the black layer, and the black layer is uniformly cured as a whole.

As such a mixture of two or more compounds having similar structures and different numbers of ethylenically unsaturated groups, for example, a mixture of compounds represented by the formula (Z-1), formula (Z-4) or formula (Z-5) described below, having different numbers of ethylenically unsaturated groups (preferably (meth)acryloyl groups) at the terminals, and a mixture of compounds in which the compound having the fewer number of ethylenically unsaturated groups contains at least one hydroxyl group.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As a polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxyl compound and an unsaturated carboxylic acid is preferred, and a polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxyl compound is more preferred. Among the esters, the aliphatic polyhydroxyl compound is pentaerythritol and/or dipentaerythritol, which is further preferred. As commercially available products, for example, ARONIX TO-2349, M-305, M-510, and M-520 manufactured by TOAGOSEICO., LTD. can be cited.

The acid value of the polymerizable compound containing an acid group is preferably 0.1~40mgKOH/g, and more preferably 5~30mgKOH/g. If the acid value of the polymerizable compound is 0.1mgKOH/g or more, the developing and dissolving properties are good, and if it is 40mgKOH/g or less, it is advantageous in manufacturing and/or handling. Furthermore, the photopolymerization performance is good and the curing property is excellent.

Regarding polymerizable compounds, compounds containing caprolactone structure are also preferred.

As compounds containing a caprolactone structure, there are no particular restrictions as long as they contain a caprolactone structure in the molecule. For example, ε-caprolactone modified multifunctional (meth)acrylates obtained by esterifying polyols such as trihydroxymethylethane, ditrihydroxymethylethane, trihydroxymethylpropane, ditrihydroxymethylpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol or trihydroxymethylmelamine with (meth)acrylic acid and ε-caprolactone can be cited. Among them, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

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 rest are groups represented by the following formula (Z-3).

[Chemical formula 17]

In formula (Z-2), ^R1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.

In formula (Z-3), ^R1 represents a hydrogen atom or a methyl group, and "*" represents a bond.

Polymerizable compounds containing a caprolactone structure are commercially available, for example, from Nippon Kayaku CO., LTD. as the KAYARAD DPCA series, DPCA-20 (in the above formulas (Z-1) to (Z-3), m=1, the number of groups represented by the formula (Z-2)=2, and all ^R1s are hydrogen atoms), DPCA-30 (in the above formulas (Z-1) to (Z-3), m=1, the number of groups represented by the formula (Z-2)=3, and all ^R1s are hydrogen atoms), DPCA-60 (in the above formulas (Z-1) to (Z-3), m=1, the number of groups represented by the formula (Z-2)=6, and all ^R1s are hydrogen atoms), DPCA-120 (in the above formulas (Z-1) to (Z-3), m=2, the number of groups represented by the formula (Z-2)=6, and all R1s are hydrogen atoms). ¹ is a compound in which all of the atoms are hydrogen atoms), etc. In addition, as a commercially available product of a polymerizable compound containing a caprolactone structure, M-350 (trade name) (trihydroxymethylpropane triacrylate) manufactured by TOAGOSEI CO., LTD. can also be cited.

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

[Chemical formula 19]

In formulae (Z-4) and (Z-5), E represents -((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)-, y represents an integer of 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom or a carboxylic acid group.

In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m represents an integer from 0 to 10, and the total number of m's is an integer from 0 to 40.

In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n represents an integer from 0 to 10, and the total number of each n is an integer from 0 to 60.

In formula (Z-4), m is preferably an integer between 0 and 6, and more preferably an integer between 0 and 4.

Furthermore, the total of each m is preferably an integer between 2 and 40, more preferably an integer between 2 and 16, and even more preferably an integer between 4 and 8.

In formula (Z-5), n is preferably an integer between 0 and 6, and an integer between 0 and 4 is more preferably.

Furthermore, the sum of n is preferably an integer between 3 and 60, more preferably an integer between 3 and 24, and even more preferably an integer between 6 and 12.

In the formula (Z-4) or (Z-5), it is preferred that the terminal of -((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)- in the oxygen atom side is bonded to X.

The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, the compound in which all six Xs in formula (Z-5) are acryl groups, the compound in which all six Xs in formula (Z-5) are acryl groups, and the compound in which at least one of the six Xs is a hydrogen atom are preferably a mixture. Such a structure can improve the heat resistance and moisture resistance of the light-shielding film, and can also improve the developing property.

Furthermore, the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.

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.

There is no limitation on the polymerizable compound containing the cardo skeleton, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD.) and Ogsol (manufactured by Osaka Gas Chemicals Co., LTD.).

It is also preferred that the polymerizable compound contains an isocyanuric acid skeleton as a central core. As an example of such a polymerizable compound, NKEsterA-9300 (manufactured by Shin Nakamura Chemical Co., LTD.) can be cited.

The content of ethylenically unsaturated groups in the polymerizable compound (the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g/mol) of the polymerizable compound) is preferably 5.0 mmol/g or more. There is no particular upper limit, but it is usually 20.0 mmol/g or less.

<Polymerization initiator>

It is preferred that the light-shielding composition contains a polymerization initiator.

There is no particular limitation on the polymerization initiator, and a known polymerization initiator can be used. As the polymerization initiator, for example, photopolymerization initiators and thermal polymerization initiators can be cited, and photopolymerization initiators are preferred. In addition, as the polymerization initiator, so-called free radical polymerization initiators are preferred.

The content of the polymerization initiator in the composition is not particularly limited, but preferably 0.5-20 mass % relative to the total solid content of the composition, more preferably 1.0-10 mass %, and even more preferably 1.5-8 mass %. The polymerization initiator may be used alone or in combination of two or more. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

(Thermal polymerization initiator)

As thermal polymerization initiators, for example, azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalononitrile, and dimethyl-(2,2')-azobis(2-methyl propionate) [V-601], and organic peroxides such as benzoyl peroxide, lauryl peroxide, and potassium persulfate can be cited.

As specific examples of polymerization initiators, for example, the polymerization initiators described in "Ultraviolet Curing System" by Kato Kiyoshi (published by General Technology Center Co., Ltd.: 1989), pages 65 to 148, etc. can be cited.

(Photopolymerization initiator)

It is preferred that the above composition contains a photopolymerization initiator.

As a photopolymerization initiator, there is no particular limitation as long as it can initiate the polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As a photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from the ultraviolet region to the visible light region is preferred. In addition, the polymerization initiator can be an activator that generates active free radicals by reacting with a light-excited photosensitizer, or can be an initiator that initiates cationic polymerization depending on the type of polymerizable compound.

Furthermore, it is preferred that the photopolymerization initiator contains at least one compound having an absorption coefficient of at least 50 moles in the range of 300-800 nm (330-500 nm is more preferred).

The content of the photopolymerization initiator in the composition is not particularly limited, but preferably 0.5 to 20 mass % relative to the total solid content of the composition, more preferably 1.0 to 10 mass %, and even more preferably 1.5 to 8 mass %. The photopolymerization initiator may be used alone or in combination of two or more. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

As photopolymerization initiators, for example, halogenated hydrocarbon derivatives (for example, compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenones, etc. can be cited.

As a specific example of a photopolymerization initiator, for example, reference can be made to paragraphs 0265 to 0268 of Japanese Patent Publication No. 2013-029760, which is incorporated into this specification.

More specifically, as the photopolymerization initiator, for example, the aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent Publication No. 4225898 can also be used.

As hydroxyacetophenone compounds, for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (trade names, all manufactured by BASF) can be used.

As aminoacetophenone compounds, for example, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names, all manufactured by BASF) can be used. As aminoacetophenone compounds, compounds described in Japanese Patent Publication No. 2009-191179 whose absorption wavelength matches a long-wave light source such as a wavelength of 365 nm or a wavelength of 405 nm can also be used.

As the acylphosphine compound, commercially available products IRGACURE-819 and IRGACURE-TPO (trade names, both manufactured by BASF) can be used.

(Oxime compounds)

As a photopolymerization initiator, an oxime ester polymerization initiator (oxime compound) is more preferred. In particular, oxime compounds have high sensitivity and high polymerization efficiency, and it is easy to increase the content of the colorant in the composition, so they are preferred.

As specific examples of oxime compounds, compounds described in Japanese Patent Publication No. 2001-233842, compounds described in Japanese Patent Publication No. 2000-080068, or compounds described in Japanese Patent Publication No. 2006-342166 can be used.

Examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

In addition, compounds described in J.C.S.Perkin II (1979) pp.1653-1660, J.C.S.Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japanese Patent Publication No. 2000-066385, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2004-534797, and Japanese Patent Publication No. 2006-342166 can also be cited.

Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF) or IRGACURE-OXE04 (manufactured by BASF) 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 (carbazole-oxime ester skeleton-containing photoinitiator (manufactured by ADEKA CORPORATION) can also be used.

In addition, as oxime compounds other than those described above, compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole; compounds described in U.S. Patent Publication No. 7626957 in which a hetero substituent is introduced into the benzophenone site; compounds described in Japanese Patent Publication No. 2010-015025 and U.S. Patent Publication No. 2009-2 Compounds described in the specification of No. 92039; ketoxime compounds described in the International Publication No. 2009-131189 pamphlet; and compounds described in the specification of U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule; compounds described in Japanese Patent Publication No. 2009-221114 having a maximum absorption at 405nm and good sensitivity to g-ray light sources; etc.

For example, you can refer to paragraphs 0274 to 0275 of Japanese Patent Publication No. 2013-029760, which is incorporated into this manual.

Specifically, as the oxime compound, the 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) form, an oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

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

In formula (OX-1), as the monovalent substituent represented by R, a monovalent non-metallic atomic group is preferred.

As monovalent non-metallic atomic groups, alkyl, aryl, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic, alkylthiocarbonyl and arylthiocarbonyl groups can be cited. Moreover, these groups can have more than one substituent. Moreover, the aforementioned substituents can be further substituted by other substituents.

As substituents, halogen atoms, aryloxy groups, alkoxycarbonyl groups or aryloxycarbonyl groups, acyloxy groups, acyl groups, alkyl groups and aryl groups can be cited.

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 preferred, and an aryl group or a heterocyclic group is more preferred. These groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.

In formula (OX-1), as the divalent organic group represented by A, an alkylene group, a cycloalkylene group or an alkynylene group having 1 to 12 carbon atoms is preferred. Such groups may have one or more substituents. As substituents, the above-mentioned substituents can be exemplified.

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

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

[Chemical formula 21]

In formula (1), ^R1 and ^R2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms; when ^R1 and ^R2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorenyl group; ^R3 and ^R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms; and X represents a direct bond or a carbonyl group.

In formula (2), R ¹ , R ² , R ³ and R ⁴ have the same meanings as R ¹ , R ² , R ³ and R ⁴ in formula (1); 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, a halogen atom or a hydroxyl group; R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group; and a represents an integer of 0 to 4.

In formula (3), ^R1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms; ^R3 and ^R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms; and X represents a direct bond or a carbonyl group.

In formula (4), R ¹ , R ³ and R ⁴ have the same meanings as R ¹ , R ³ and R ⁴ in formula (3); 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, a halogen atom or a hydroxyl group; R ⁶ represents an alkyl group having 1 to ²⁰ carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group; and a represents an integer of 0 to 4.

In the above formula (1) and formula (2), ^R1 and ^R2 are preferably methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. ^R3 is preferably methyl, ethyl, phenyl, tolyl or xylyl. ^R4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. ^R5 is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond.

In the above formulae (3) and (4), ^R1 is preferably methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. ^R3 is preferably methyl, ethyl, phenyl, tolyl or xylyl. ^R4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. ^R5 is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond.

As specific examples of compounds represented by formula (1) and formula (2), for example, compounds described in paragraphs 0076 to 0079 of Japanese Patent Application Publication No. 2014-137466 can be cited. This content is incorporated into this specification.

The following are specific examples of oxime compounds that can be preferably used in the above composition. Among the oxime compounds shown below, the oxime compound represented by formula (C-13) is more preferred.

In addition, as oxime compounds, for example, compounds listed in Table 1 of International Publication No. 2015-036910 can also be used, and the above contents are introduced into this specification.

[Chemical formula 23]

[Chemical formula 24]

It is preferred that the oxime compound has a maximum absorption in the wavelength region of 350-500nm, more preferred that it has a maximum absorption in the wavelength region of 360-480nm, and even more preferred that the absorbance at wavelengths of 365nm and 405nm is higher.

From the perspective of sensitivity, the molar absorption coefficient of the oxime compound at 365nm or 405nm is preferably 1,000~300,000, more preferably 2,000~300,000, and even more preferably 5,000~200,000.

The molar absorbance of the compound can be measured by a known method, for example, by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), preferably using ethyl acetate at a concentration of 0.01 g/L.

Photopolymerization initiators may be used in combination of two or more types as needed.

Furthermore, as a photopolymerization initiator, for example, compounds described in paragraph 0052 of Japanese Patent Publication No. 2008-260927, paragraphs 0033 to 0037 of Japanese Patent Publication No. 2010-097210, and paragraph 0044 of Japanese Patent Publication No. 2015-068893 can also be used, and the above contents are incorporated into this specification.

<Polymerization inhibitor>

The composition may contain a polymerization inhibitor.

系聚合抑制劑(例如，啡噻

、2-甲氧基啡噻

等)；等。 The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used. Examples of the polymerization inhibitor include phenolic polymerization inhibitors (e.g., p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4-methoxynaphthol, etc.); hydroquinone polymerization inhibitors; Inhibitors (e.g., hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); quinone-based polymerization inhibitors (e.g., benzoquinone, etc.); free radical-based polymerization inhibitors (e.g., 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, etc.); nitrobenzene-based polymerization inhibitors (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenthiophene.

Polymerization inhibitors (e.g., phenthiophene

2-methoxyphenthiophene

etc.

Among them, from the perspective of having a more excellent effect of the composition, phenol-based polymerization inhibitors or free radical polymerization inhibitors are preferred.

The polymerization inhibitor is effective when used with a resin containing a curing group.

The content of the polymerization inhibitor in the composition is not particularly limited. Relative to the total solid content of the composition, 0.0001~0.5 mass% is preferred, 0.001~0.2 mass% is more preferred, and 0.008~0.05 mass% is further preferred. A polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.

In addition, the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition (content of the polymerization inhibitor/content of the polymerizable compound (mass ratio)) is preferably greater than 0.0005, more preferably 0.0006~0.02, and even more preferably 0.0006~0.005.

<Ultraviolet absorber>

The composition may contain an ultraviolet absorber. This can make the shape of the pattern of the black layer more fine.

As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based and triazine-based ultraviolet absorbers can be used. As specific examples thereof, compounds in paragraphs 0137 to 0142 of Japanese Patent Publication No. 2012-068418 (corresponding to paragraphs 0251 to 0254 of US2012/0068292) can be used, and such contents can be cited and introduced into this specification.

In addition, diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., trade name, UV-503) etc. can also be preferably used.

As ultraviolet absorbers, compounds exemplified in paragraphs 0134 to 0148 of Japanese Patent Application Publication No. 2012-032556 can be cited.

The content of the ultraviolet absorber relative to the total solid content of the composition is preferably 0.001~15 mass %, more preferably 0.01~10 mass %, and even more preferably 0.1~5 mass %.

<Silane coupling agent (adhesive)>

The composition may contain a silane coupling agent. When a black layer is formed on a substrate, the silane coupling agent functions as a bonding agent that improves the bonding between the substrate and the black layer.

Silane coupling agents refer to compounds containing hydrolyzable groups and other functional groups in the molecule. In addition, hydrolyzable groups such as alkoxy groups are bonded to silicon atoms.

The hydrolyzable group refers to a substituent that directly bonds to a silicon atom and can form a siloxane bond by a hydrolysis reaction and/or a condensation reaction. Examples of the hydrolyzable group include halogen atoms, alkoxy groups, acyloxy groups, and alkenyloxy groups. When the hydrolyzable group contains carbon atoms, it is preferred that the carbon number is 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferred.

Furthermore, when a black layer is formed on a substrate, in order to improve the adhesion between the substrate and the black layer, it is preferred that the silane coupling agent does not contain fluorine atoms and silicon atoms (except for silicon atoms bonded by hydrolyzable groups), and it is preferred that the silane coupling agent does not contain fluorine atoms, silicon atoms (except for silicon atoms bonded by hydrolyzable groups), alkylene groups substituted by silicon atoms, straight-chain alkyl groups with more than 8 carbon atoms, and branched-chain alkyl groups with more than 3 carbon atoms.

Silane coupling agents may contain ethylenically unsaturated groups such as (meth)acryloyl groups. When containing ethylenically unsaturated groups, the number is preferably 1 to 10, and more preferably 4 to 8. In addition, silane coupling agents containing ethylenically unsaturated groups (e.g. compounds with a molecular weight of less than 2000 containing hydrolyzable groups and ethylenically unsaturated groups) do not meet the above-mentioned polymerizable compounds.

The content of the silane coupling agent in the above composition is preferably 0.1-10 mass % relative to the total solid content in the composition, more preferably 0.5-8 mass % and even more preferably 1.0-6 mass %.

The above composition may contain one silane coupling agent alone or two or more. When the composition contains two or more silane coupling agents, the total amount thereof may be within the above range.

As silane coupling agents, for example, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, vinyl trimethoxysilane and vinyl triethoxysilane can be cited.

<Surfactant>

The composition may contain a surfactant. The surfactant helps to improve the spreadability of the composition.

When the above composition contains a surfactant, the content of the surfactant is preferably 0.001-2.0 mass % relative to the total solid content of the composition, more preferably 0.005-0.5 mass % and even more preferably 0.01-0.1 mass %.

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

Examples of surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based 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 improve the coating properties of the coated 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 uniform thickness film with less uneven thickness can be formed better.

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

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

Block polymers can also be used as fluorine-based surfactants. As specific examples, the compounds described in Japanese Patent Publication No. 2011-089090 can be cited.

<Solvent>

It is preferred that the composition contains a solvent.

There is no particular limitation on the solvent, and any known solvent can be used.

There is no particular limitation on the content of the solvent in the composition. The solid content of the composition is preferably 10 to 90% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass.

The solvent may be used alone or in combination of two or more. When two or more solvents are used in combination, it is preferred to adjust the total solid content of the composition to within the above range.

As the solvent, for example, water and organic solvents can be cited.

(Organic solvent)

Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropyl Alcohol, methoxyethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, but not limited thereto.

(water)

When the composition contains water, its content relative to the total mass of the composition is preferably 0.001~5.0 mass %, more preferably 0.01~3.0 mass %, and even more preferably 0.1~1.0 mass %.

Among them, if the water content is less than 3.0 mass% (preferably less than 1.0 mass%) relative to the total mass of the composition, it is easy to suppress the deterioration of the viscosity stability of the components in the composition due to hydrolysis, etc., and if it is more than 0.01 mass% (preferably more than 0.1 mass%), it is easy to improve the sedimentation stability over time.

<Other optional ingredients>

The composition may further contain any other components other than the above components. For example, sensitizers, co-sensitizers, crosslinkers, hardening accelerators, thermosetting accelerators, fillers, plasticizers, diluents and grease-sensitizing agents, etc., and further, adhesion promoters and other auxiliary agents (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, stripping promoters, antioxidants, fragrances, interfacial tension modifiers and chain transfer agents, etc.) and other well-known additives may be added as needed.

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

<Method for producing light-shielding composition>

Regarding the composition, it is preferred to first prepare a color material composition containing a black color material, and then mix the obtained color material composition with other ingredients to form a composition.

It is preferred to prepare a color material composition by mixing a black color material, a resin (preferably a dispersing resin) and a solvent. It is also preferred to make the color material composition contain a polymerization inhibitor.

The color material composition can be prepared by mixing the above-mentioned components by a known mixing method (e.g., a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer or a wet disperser).

When preparing the light-shielding composition, each component can be blended at once, or each component can be dissolved or dispersed in a solvent and then blended in sequence. In addition, there is no particular restriction on the order of input and operating 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 a filter, any filter that has been used for filtering purposes can be used without particular restrictions. For example, filters based on fluororesins such as PTFE (polytetrafluoroethylene), polyamine resins of nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight) can be cited. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

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

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

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

It is preferred that the composition does not contain impurities such as metals, metal salts containing halides, acids, bases, etc. As for the content of impurities contained in such materials, 1 mass ppm or less is preferred, 1 mass ppb or less is more preferred, 100 mass ppt or less is further preferred, 10 mass ppt or less is particularly preferred, and substantially no impurities (below the detection limit of the measuring device) are the best.

In addition, the above impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Electric Corporation, Agilent 7500cs model).

[Formation of black layer]

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

The method for forming the black layer preferably includes the following process.

˙Film forming process

˙Hardening process

˙Development process

Below, each process is explained.

<Film forming process>

In the coating formation process, a light-shielding composition is applied to a support to form a coating (composition layer) before curing (exposure). As a support, for example, a substrate for solid-state imaging elements can be used, in which an imaging element (light-receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (such as a silicon substrate). In addition, as needed, a lower coating layer can be provided on the support to improve the close contact with the upper layer, prevent the diffusion of substances, and flatten the substrate surface.

As a coating method for the composition on the support, various coating methods such as slit coating, inkjet coating, rotary coating, cast coating, roll coating, and screen printing can be applied. As for the film thickness of the coating, 0.1~10μm is preferred, 0.2~5μm is more preferred, and 0.2~3μm is further preferred. The coating applied on the support can be dried (pre-baked) at a temperature of 50~140°C for 10~300 seconds using a heating plate, an oven, etc.

<Hardening process>

In the curing process, the coating film formed in the coating film forming process is exposed by irradiating actinic rays or radiation, and the light-irradiated coating film is cured.

There is no particular limitation on the method of light irradiation, but it is preferred to irradiate light through a mask having a patterned opening.

Exposure is preferably performed by irradiation with radiation. As radiation that can be used for exposure, ultraviolet rays such as g-rays, h-rays, and i-rays are particularly preferred, and as a light source, a high-pressure mercury lamp is preferred. The irradiation intensity is preferably 5 to 1500 mJ/ ^cm2 , and more preferably 10 to 1000 mJ/ ^cm2 .

In addition, when the composition contains a thermal polymerization initiator, the coating can be heated during the above-mentioned curing process. There is no particular restriction on the heating temperature, but 80~250℃ is preferred. There is no particular restriction on the heating time, but 30~300 seconds is preferred.

In addition, during the curing process, when the coating is heated, the post-baking process described below can also be performed. In other words, during the curing process, when the coating is heated, the method for manufacturing the black layer does not need to include the post-baking process.

<Development process>

The developing process is a process for developing the above-mentioned coating after exposure. Through this process, the coating that was not irradiated with light during the curing process is dissolved, leaving only the light-cured part, thereby obtaining a patterned black layer.

There is no particular restriction on the type of developer used in the development process, but alkaline developers that do not cause damage to the imaging elements and circuits on the substrate are preferred.

The developing temperature is, for example, 20 to 30°C.

The developing time is, for example, 20 to 90 seconds. In order to better remove the residue, in recent years, it has also been implemented for 120 to 180 seconds. Furthermore, in order to further improve the residue removal performance, sometimes the process of shaking out the developer every 60 seconds and further resupplying the developer is repeated several times.

As an alkaline developer, an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10 mass % (preferably 0.01 to 5 mass %) is preferred.

Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among which organic bases are preferred).

In addition, when used as an alkaline developer, it is usually washed with water after development.

<Post-baking>

After the hardening process, it is better to perform post-heat treatment (post-baking). Post-baking is a heat treatment after the development for complete hardening. The heating temperature is preferably below 240℃, and 220℃ is more preferably below. There is no special lower limit. If efficient and effective treatment is considered, 50℃ or above is better, and 100℃ or above is more preferably.

Post-baking can be performed continuously or in batches using heating mechanisms such as heating plates, flow ovens (hot air circulation dryers) or high-frequency heaters.

The above post-baking is preferably carried out in an atmosphere of low oxygen concentration. The oxygen concentration is preferably below 19 volume %, more preferably below 15 volume %, further preferably below 10 volume %, particularly preferably below 7 volume %, and optimally below 3 volume %. There is no particular lower limit, but it is actually above 10 volume ppm.

Alternatively, the process can be changed to baking after the above heating, and hardening can be completed by UV (ultraviolet light) irradiation.

At this time, it is preferred that the above composition further contains a UV curing agent. The UV curing agent is preferably a UV curing agent that can cure at an exposure wavelength shorter than 365nm, which is the exposure wavelength of the polymerization initiator added for the lithography process based on the usual i-ray exposure. As an example of a UV curing agent, Ciba IRGACURE 2959 (trade name) can be cited. When UV irradiation is performed, it is preferred that the coating is a material that cures at a wavelength below 340nm. There is no special restriction on the lower limit of the wavelength, and it is usually above 220nm. In addition, the exposure amount of UV irradiation is preferably 100~5000mJ, more preferably 300~4000mJ, and even more preferably 800~3500mJ. In order to perform low-temperature curing more effectively, the UV curing process is preferably performed after the curing process. It is better to use an ozone-free mercury lamp as the exposure light source.

[Physical properties of the black layer]

From the perspective of having excellent light-shielding properties, the optical density (OD: Optical Density) of the black layer per 1.0μm thickness in the wavelength range of 400~1200nm is preferably 1.7 or more, 2.0 or more is more preferably, and 2.1 or more is even more preferably. In addition, there is no particular upper limit, but it is usually better to be 10 or less.

In addition, in this specification, the optical density per 1.0μm thickness in the wavelength range of 400~1200nm is 2.0 or more, which means that the optical density per 1.0μm thickness in the entire wavelength range of 400~1200nm is 2.0 or more.

In addition, the optical density of the black layer (light shielding film) can be measured as follows: first, a black layer (light shielding film) is formed on a glass substrate, and then measured using a spectrophotometer U-4100 (trade name, manufactured by Hitachi High-Technologies Corporation.) integrating sphere type light receiving unit, and the thickness of the measurement site is also measured, and the optical density of each specified thickness is calculated.

The thickness of the black layer is preferably 0.1~4.0μm, and more preferably 1.0~2.5μm. In addition, depending on the application, the black layer can be a thin film or a thick film within this range.

Furthermore, when the black layer is used as a light attenuation film, the light shielding property can be adjusted by using a thinner film (e.g., 0.1 to 0.5 μm) than the above range. At this time, the optical density per 1.0 μm thickness in the wavelength range of 400 to 1200 nm is preferably 0.1 to 1.5, and more preferably 0.2 to 1.0.

[Oxygen barrier layer]

The oxygen blocking layer is a layer formed on the black layer, and has the function of blocking oxygen from passing through the black layer from the side opposite to the contact surface with the black layer.

As the oxygen barrier layer, a layer having an oxygen permeability in the thickness direction (hereinafter, also simply described as "oxygen permeability") of 50 ml/(m ² ˙day˙atm) or less can be cited, a layer having an oxygen permeability of 10 ml/(m ² ˙day˙atm) or less is preferred, a layer having an oxygen permeability of 1.5 ml/(m ² ˙day˙atm) or less is more preferred, and a layer having an oxygen permeability of 1.0 ml/(m ² ˙day˙atm) or less is further preferred. The lower limit of the oxygen permeability is preferably 0.001 ml/(m ² ˙day˙atm).

The oxygen permeability can be measured, for example, using an oxygen permeability measuring device (Model 8001, manufactured by ILLINOIS).

The oxygen blocking layer is a single layer composed of inorganic materials.

In this specification, "single layer" means a layer whose composition of the material constituting the layer is uniform in the thickness direction and the in-plane direction. Therefore, for example, a laminate of layer A composed of inorganic material a and layer B composed of inorganic material b having a composition different from that of inorganic material a does not include the oxygen blocking layer specified in this specification even if either layer A or layer B has the function of blocking oxygen.

Furthermore, "composed of inorganic materials" means that the content of carbon atoms in the material constituting the oxygen barrier layer is 5% by mass or less relative to the total mass of the oxygen barrier layer. Preferably, the content of the above carbon atoms is 2.5% by mass or less relative to the total mass of the oxygen barrier layer. Furthermore, the lower limit of the content of the above carbon atoms is not particularly limited and can be below the detection limit.

After a smooth surface is formed in the oxygen barrier layer by grinding or cutting, the formed smooth surface is analyzed using an electron probe microanalyzer (EPMA: Electron Probe Micro Analyzer) (for example, "JXA-8530F" (trade name) manufactured by JEOL Ltd.) to measure the content of carbon atoms in the material constituting the oxygen barrier layer.

The thickness of the oxygen barrier layer is 10~500nm.

By setting the thickness of the oxygen blocking layer within the above range, a light-shielding film with a better balance between light resistance and moisture resistance can be manufactured. More specifically, if the thickness of the oxygen blocking layer is 10nm or more, the effect of suppressing the change of the film thickness and optical properties (transmittance and reflectivity) of the light-shielding film after the light resistance test is improved, and if the thickness of the oxygen blocking layer is 500nm or less, the effect of suppressing the black layer from peeling off from the substrate after the moisture resistance test is improved.

The reason why the moisture resistance is improved if the thickness of the oxygen barrier layer is less than 500nm is not clear, but the reason is speculated as follows: If the thickness of the oxygen barrier layer is greater than 500nm, after the moisture resistance test, the stress generated by the difference in shrinkage rate between the black layer with the oxygen barrier layer and the substrate becomes stronger, causing the black layer to peel off from the substrate.

Furthermore, when the thickness of the oxygen blocking layer is less than 500nm, when a light shielding film including a black layer and an oxygen blocking layer is set on a device, interference between reflected light on the surface of the black layer and reflected light on the surface of the oxygen blocking layer can be reduced, and degradation of device performance can be prevented.

From the perspective of better moisture resistance and heat resistance of the light-shielding film, the thickness of the oxygen barrier layer is preferably greater than 50nm and less than 250nm, and 70~200nm is even better.

In addition, the ratio of the thickness of the black layer to the thickness of the oxygen barrier layer (black layer thickness/oxygen barrier layer thickness) can be 2 to 100. From the perspective of better moisture resistance and heat resistance of the light-shielding film, 7 to 30 is better, and 10 to 25 is even better.

There is no particular limitation on the inorganic material constituting the oxygen blocking layer, and examples thereof include metal oxides, metal nitrides, and metal oxynitrides.

As the metal contained in the inorganic material, silicon, titanium, aluminum, indium, tin, niobium, zirconium, tantalum, tantalum and zinc can be cited, 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, tantalum oxide, aluminum oxide, and zinc oxide. Silicon oxide and silicon nitride are preferred. From the perspective of superior light resistance and moisture resistance of the light-shielding film, silicon oxide is preferred.

In addition, the oxygen blocking layer of the present invention is a single layer composed of inorganic materials and does not contain any organic components.

When the oxygen blocking layer contains an organic component, the organic component contained inside is decomposed due to light irradiation on the oxygen blocking layer, and the oxygen blocking ability is reduced. In contrast, the single layer composed of inorganic materials, that is, the oxygen blocking layer of the present invention, can prevent such a reduction in oxygen blocking ability.

In addition, in this specification, the oxygen barrier layer "does not substantially contain organic components" means that the content of carbon atoms in the material constituting the oxygen barrier layer is less than 5% by mass relative to the total mass of the oxygen barrier layer. The content of carbon atoms in the material constituting the oxygen barrier layer is measured using an electron probe microanalyzer by the above method.

From the perspective of better heat resistance, it is better for the oxygen barrier layer to contain substantially no particles. This is because when the oxygen barrier layer contains particles, the composition of the material constituting the layer becomes uneven, resulting in regions with different thermal contraction properties. Therefore, the oxygen barrier layer is more distorted in a high temperature environment, and the heat resistance is reduced.

In addition, from the perspective of making the surface smoother and improving the in-plane uniformity of reflectivity, it is better for the oxygen barrier layer to contain substantially no particles.

In addition, the above-mentioned "particles" refer to particles of a substance having a composition different from that of the inorganic material constituting the oxygen blocking layer, and the particle size thereof is greater than 10 nm.

The content of particles in the oxygen barrier 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 barrier layer is polished or cut to form a smooth surface. Thereafter, the distribution of the elemental composition on the formed smooth surface is measured using an electron probe microanalyzer to obtain a mapping image of the elemental composition. In the obtained mapping image, the region where the particles exist is determined based on the difference in elemental composition and the continuous phase. Next, the sum of the areas of the particle regions is divided by the observed area to obtain the area ratio occupied by the particles in the observed surface. Next, the area ratio is converted into a volume ratio (area ratio raised to the power of 3/2), and then converted into a mass ratio based on the elemental composition, thereby obtaining the content of particles relative to the total amount of the oxygen barrier layer.

For example, when silicon oxide particles exist in an oxygen barrier layer composed of silicon oxide (SiO ₂ ), the outline of the silicon oxide particles will appear in the mapping image due to the silanol groups (SiOH) existing on the surface of the silicon oxide particles, so the presence of the particles can be confirmed. In this way, according to the above method, the content of the particles can be measured based on the difference in the composition of the continuous phase and the particles in the oxygen barrier layer.

In addition, in this specification, the oxygen barrier layer "substantially contains no particles" means that the content of particles in the oxygen barrier layer measured by the above method is less than 5 mass% or less than the detection limit relative to the total mass of the oxygen barrier layer.

[Formation of oxygen barrier layer]

There is no particular limitation on the method of forming the oxygen blocking layer, and the known film forming method of inorganic materials can be used.

As film forming methods, there can be cited vapor deposition-based methods such as sputtering, vacuum deposition, ion beam assisted vapor deposition, ion plating, and plasma CVD (chemical vapor deposition), as well as wet methods such as spin coating, dip coating, casting, slit coating, and spray coating.

Among them, from the perspective of easier thin film formation, it is better to form the oxygen barrier layer by vapor deposition, and from the perspective of easier thickness control and better adhesion to the object, that is, the black layer, it is better to form the oxygen barrier layer by sputtering.

There is no particular limitation on the sputtering method, and it may be a known method such as a pulse sputtering method, an AC sputtering method, and a digital sputtering method.

For example, when an oxygen blocking layer is formed by sputtering, a substrate with a black layer formed on the surface is placed in a chamber with a mixed gas atmosphere of an inert gas and a reactive gas (such as oxygen or nitrogen), and a target is selected in a manner to form a desired composition to form an oxygen blocking layer.

In addition, the type of inert gas is not particularly limited, and inert gases such as argon or helium can be used. In addition, the reactive gas can be selected according to the composition of the oxygen barrier layer to be formed.

The pressure in the chamber based on the mixed gas of inert gas and reactive gas is not particularly limited, and can be below 1.0Pa, and preferably below 0.5Pa. The lower limit of the pressure in the chamber based on the mixed gas of inert gas and reactive gas is not particularly limited, for example, 0.1Pa or more is preferred.

In addition, when the oxygen barrier layer is formed by sputtering, the thickness of the oxygen barrier layer can be adjusted by adjusting the discharge power or film formation time.

[Manufacturing of light-shielding film]

There is no particular limitation on the manufacturing method of the light-shielding film of the present invention.

The light-shielding film of the present invention can be manufactured by the following manufacturing method, which comprises a process of 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 to form a black layer, and a process of forming an oxygen blocking layer on the above black layer.

As the above-mentioned "process for forming a black layer", the method described in the above-mentioned "formation of a black layer" can be applied, and as the above-mentioned "process for forming an oxygen barrier layer", the method described in the above-mentioned "formation of an oxygen barrier layer" can be applied.

[Properties and uses of light-shielding 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 can be a thin film or a thick film within this range.

The reflectivity of the light-shielding film is preferably less than 5%, more preferably less than 3%, and even more preferably less than 2%.

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

The above-mentioned light-shielding film can also be used for micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). In addition to optical filters and optical films used in micro LED and micro OLED, the above-mentioned light-shielding film is also suitable for components that have light-shielding or anti-reflection functions.

As examples of micro LED and micro OLED, the examples described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890 can be cited.

The above-mentioned light-shielding film is also preferably used as an optical filter and an optical film for quantum dot sensors and quantum dot solid-state imaging devices. In addition, it is suitable as a component that imparts light-shielding function and anti-reflection function. As examples of quantum dot sensors and quantum dot solid-state imaging devices, examples described in the specification of U.S. Patent Application Publication No. 2012/037789 and the brochure of International Publication No. 2008/131313 can be cited.

[Optical element, 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 elements.

As described above, the light-shielding film of the present invention has excellent 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 an optical element. The optical element of the present invention is an optical element having the above-mentioned light-shielding film. Examples of the optical element include optical elements used in optical machines such as cameras, binoculars, microscopes, and semiconductor exposure devices.

Among them, as the above-mentioned optical element, a solid-state imaging element mounted on a camera is preferred.

Furthermore, the solid-state imaging element of the present invention is a solid-state imaging element having the above-mentioned light-shielding film.

There is no particular limitation on the form of a solid-state imaging element including a light-shielding film. For example, a light-receiving element including a plurality of photodiodes and polysilicon that constitute a light-receiving area of a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) is provided on a substrate, and a light-shielding film is provided on the light-receiving element forming surface side of the support (e.g., a portion other than the light-receiving portion and/or a pixel for adjusting color, etc.) or on the opposite side of the forming surface.

Furthermore, when the light-shielding film is used as a light-attenuating film, for example, if the light-attenuating film is arranged so that a portion of 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 is equipped with the above-mentioned solid-state imaging element.

Referring to FIG. 1 and FIG. 2, the configuration examples of the solid-state imaging device and the solid-state imaging element are described. In addition, in FIG. 1 and FIG. 2, in order to make each part clear, the mutual ratio of thickness and/or width is ignored and a part is exaggerated.

FIG1 is a schematic cross-sectional view showing an example of the structure of a solid-state imaging device including the solid-state imaging element of the present invention.

As shown in FIG1 , the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Furthermore, a lens layer 111 is stacked on the cover glass 103 via a spacer 104. The lens layer 111 is composed of a support body 113 and a lens material 112. The lens layer 111 may be formed as a single body by the support body 113 and the lens material 112. If stray light is incident on the peripheral area of the lens layer 111, the focusing effect of the lens material 112 is weakened due to the diffusion of light, and the light reaching the imaging unit 102 is reduced. In addition, noise caused by stray light is also generated. Therefore, a light shielding film 114 is provided on the peripheral area of the lens layer 111 to shield light. The light shielding film of the present invention can be used as the above-mentioned light shielding film 114.

The solid-state imaging element 101 performs photoelectric conversion on the optical image formed on the imaging part 102 which is its light receiving surface and outputs it as an image signal. The solid-state imaging element 101 has a stacked substrate 105 having two stacked substrates. The stacked substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 of the same size, and the circuit substrate 107 is stacked on the back of the chip substrate 106.

There is no particular limitation on the material of the substrate used as the chip substrate 106, and any known material can be used.

The imaging unit 102 is provided at the center of the surface of the chip substrate 106. In addition, a light shielding film 115 is provided in the peripheral area of the imaging unit 102. The light shielding film 115 shields the scattered light incident on the peripheral area, thereby preventing the generation of dark current (noise) from the circuit in the peripheral area. 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 chip substrate 106. The electrode pads 108 are electrically connected to the imaging unit 102 via signal lines (bonding wires are also acceptable) not shown and provided on the surface of the chip substrate 106.

On the back of the circuit substrate 107, external connection terminals 109 are provided approximately below each electrode pad 108. Each external connection terminal 109 is connected to the electrode pad 108 via a through electrode 110 vertically penetrating the multilayer substrate 105. In addition, each external connection terminal 109 is connected to a control circuit for controlling the drive of the solid-state imaging element 101 and an image processing circuit for performing image processing on the imaging signal output from the solid-state imaging element 101 via wiring not shown.

FIG2 is a schematic cross-sectional view of the imaging unit 102. As shown in FIG2, the imaging unit 102 is composed of a light receiving element 201, a color filter 202, a micro lens 203 and other components disposed 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 chip substrate 106 can be used. A p-well layer 206 is formed on the surface of the substrate 204. In the p-well layer 206, light-receiving elements 201 including an n-type layer and generating and accumulating signal charges by photoelectric conversion are arranged in a square lattice.

On one side of the light receiving element 201, a vertical transmission path 208 including an n-type layer is formed through a readout gate portion 207 on the surface layer of the p-well layer 206. On the other side of the light receiving element 201, a vertical transmission path 208 belonging to an adjacent pixel is formed through an element separation 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 region 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. A vertical transmission electrode 211 including polycrystalline silicon or amorphous silicon is formed on the gate insulating film 210 in a manner covering the vertical transmission path 208, the readout gate portion 207, and substantially directly above the element isolation region 209. The vertical transmission electrode 211 functions as a driving electrode for driving the vertical transmission path 208 to perform charge transmission and a readout electrode for driving the readout gate portion 207 to perform signal charge reading. The signal charge is transmitted from the vertical transmission path 208 to the horizontal transmission path (not shown) and the output section (floating diffusion amplifier) in sequence, and then output as a voltage signal.

A light shielding film 212 is formed on the vertical transmission electrode 211 to cover the surface thereof. The light shielding film 212 has an opening directly above the light receiving element 201 and shields the area outside the opening. 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, and the intermediate layer includes: an insulating film 213 including BPSG (borophospho silicate glass), an insulating film (passivation film) 214 including P-SiN, and a planarization film 215 including a transparent resin. The color filter 202 is formed on the intermediate layer.

[Image display device]

The image display device of the present invention is equipped with the light-shielding film of the present invention.

As an embodiment of an image display device having a light-shielding film, for example, a color filter including a light-shielding film as a black matrix can be used in an image display device.

Next, the black matrix and the color filter containing the black matrix are explained, and then, as a specific example of an image display device, a liquid crystal display device containing such a color filter is explained.

[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.

As the black matrix, the above-mentioned ones can be cited; the black edge provided at the periphery of the image display device such as the liquid crystal display device; the black part in the form of a grid and/or a straight line between the red, blue and green pixels; the black pattern in the form of dots and/or lines used for light shielding of TFT (thin film transistor); etc. The definition of the black matrix is described in, for example, Taihei Kanno, "Dictionary of Terms for Liquid Crystal Display Manufacturing Devices", 2nd edition, NIKKAN KOGYO SHIMBUN, LTD., 1996, p. 64.

In order to improve the display contrast and prevent the degradation of image quality caused by light leakage current when using a thin film transistor (TFT) active matrix driven liquid crystal display device, it is preferred that the black matrix has high light shielding properties (measured in optical density OD of 3 or more).

There is no particular limitation on the method for manufacturing the black matrix, and the black matrix can be manufactured by the same method as the method for manufacturing the above-mentioned light-shielding film. Specifically, the composition is applied to the substrate to form a coating, and after exposure and development to form a patterned black layer, an oxygen blocking layer is formed on the black layer, thereby manufacturing the black matrix. In addition, the thickness of the light-shielding film used as the black matrix is preferably 0.1~4.0μm.

There is no particular restriction on the material of the substrate, but it is preferred that the transmittance of visible light (wavelength 400-800nm) is 80% or more. Specifically, such materials include sodium calcium glass, alkali-free glass, quartz glass, borosilicate glass, and other glasses; plastics such as polyester resins and polyolefin resins; etc. From the perspective of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferred.

<Color filter>

It is also preferred that the light-shielding film of the present invention is included in the color filter.

There is no particular limitation on the form of the color filter including the light-shielding film, and a color filter having a substrate and the above-mentioned black matrix can be cited. That is, a color filter having red, green, and blue colored pixels formed in the opening of the above-mentioned black matrix formed on the substrate can be exemplified.

A color filter containing a black matrix can be manufactured, for example, by the following method.

First, a coating containing a composition containing a pigment corresponding to each coloring pixel of the color filter is formed at the opening of the patterned black matrix formed on the substrate. In addition, there is no particular limitation on the composition for each color, and a known composition can be used. Among the compositions described in this manual, it is preferable to use a composition in which the black color material is replaced with a coloring agent corresponding to each pixel.

Next, the coating is exposed through a mask having a pattern corresponding to the opening of the black matrix. Then, after removing the unexposed portion by developing, baking is performed to form colored pixels at the opening of the black matrix. For example, by performing a series of operations using color compositions containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be manufactured.

<LCD display device>

It is also preferred that the light-shielding film of the present invention is included in a liquid crystal display device. There is no particular limitation on the form of the light-shielding film included in the liquid crystal display device, and a form of a color filter including the black matrix described above can be cited.

As a liquid crystal display device of this embodiment, for example, there can be cited a form having a pair of substrates arranged opposite to each other and a liquid crystal compound sealed between the substrates. As the above-mentioned substrate, a substrate for a black matrix has been described.

As a specific form of the above-mentioned liquid crystal display device, for example, a laminated body including polarizer/substrate/color filter/transparent electrode layer/alignment film/liquid crystal layer/alignment film/transparent electrode layer/TFT (Thin Film Transistor) element/substrate/polarizer/backlight unit in order from the user side can be cited.

In addition, as liquid crystal display devices, they are not limited to the above, and for example, the liquid crystal display devices described in "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., LTD. in 1990)" and "Display Devices (written by Junaki Ibuki, published by Sangyo Tosho Publishing Co., LTD. in 1989)" can be cited. Another example is the liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (written by Ryuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. in 1994)".

[Infrared sensor]

It is also preferred that the light-shielding film of the present invention is included in the infrared sensor.

The infrared sensor of the above-mentioned embodiment is described using FIG3. FIG3 is a schematic cross-sectional view showing an example of the structure of an infrared sensor having a light-shielding film of the present invention. The infrared sensor 300 shown in FIG3 has a solid-state imaging element 310.

The imaging area disposed on the solid-state imaging element 310 is composed of a combination of an infrared absorption filter 311 and a color filter 312 of the embodiment of the present invention.

The infrared absorption filter 311 is a film that transmits light in the visible light region (e.g., light with a wavelength of 400-700nm) and blocks light in the infrared region (e.g., light with a wavelength of 800-1300nm, preferably light with a wavelength of 900-1200nm, and more preferably light with a wavelength of 900-1000nm). As a colorant, a hardened 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 specific wavelengths in the visible light region, for example, a color filter formed with pixels of red (R), green (G), and blue (B) is used, and its shape is as described above.

Between the infrared transmission filter 313 and the solid-state imaging element 310, a resin film 314 (such as 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 has visible light shielding properties and transmits infrared light of a specific wavelength, and can use a light-shielding film containing a colorant that absorbs light in the visible light region (such as perylene compounds and/or benzofuranone compounds, etc.) and an infrared absorber (such as pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, and polymethine compounds, etc.). The infrared transmission filter 313, for example, shields light with a wavelength of 400 to 830 nm, and preferably transmits light with a wavelength of 900 to 1300 nm.

A microlens 315 is disposed on the incident light hν side of the color filter 312 and the infrared transmission filter 313. A flattening film 316 is formed to cover the microlens 315.

In the form shown in FIG. 3 , a resin film 314 is provided, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, an infrared transmission filter 313 may be formed on the solid-state imaging element 310.

In addition, in the form shown in FIG3 , the film thickness of the color filter 312 is the same as the film thickness of the infrared transmission filter 313, but the film thicknesses of the two may be different.

Furthermore, in the form shown in FIG. 3 , the color filter 312 is disposed at a position closer to the incident light hν side than the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 may be reversed, and the infrared absorption filter 311 may be disposed at a position closer to the incident light hν side than the color filter 312.

In the form shown in FIG3, the adjacent layers include an infrared absorption filter 311 and a color filter 312, but the two filters do not necessarily need to be adjacent, and other layers can be provided between the two filters. In addition to being used as a light-shielding film on the end and/or side of the surface of the infrared absorption filter 311, if used on the inner wall of the infrared sensor device, it can also prevent internal reflection and/or unexpected light from entering the light receiving part to improve sensitivity.

According to the infrared sensor, since image information can be obtained at the same time, motion sensing of objects that are moving can be performed. In addition, according to the infrared sensor, distance information can be obtained, so images containing 3D information can be photographed. Furthermore, the infrared sensor can also be used as a biometric recognition sensor.

Next, the solid-state imaging device that uses the above infrared sensor is described.

The solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light-emitting diode, etc. In addition, for each structure of the solid-state imaging device, reference can be made to paragraphs 0032 to 0036 of Japanese Patent Publication No. 2011-233983, which is incorporated into this specification.

[Headlight unit]

The light-shielding film of the present invention is preferably included in a headlight unit of a lamp for a vehicle such as an automobile. The cured film of the present invention included in the headlight unit is preferably formed into a pattern in order to shield at least a portion of the light emitted from the light source.

The headlight unit of the above-mentioned implementation is described using Figures 4 and 5.

FIG. 4 is a schematic diagram showing an example of the configuration of the headlight unit, and FIG. 5 is a schematic three-dimensional diagram showing an example of the configuration of the light shielding portion of the headlight unit.

As shown in FIG. 4 , the headlight unit 10 has a light source 12, a shading portion 14, and a lens 16, and the light source 12, the shading portion 14, and the lens 16 are arranged in sequence.

As shown in FIG5 , the light shielding portion 14 has a substrate 20 and a light shielding film 22.

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

Furthermore, the structure of the base 20 is not particularly limited as long as it can hold the light-shielding film 22, but it is preferably one that will not be deformed by the heat of the light source 12, for example, it is made of glass.

Figure 5 shows an example of a light distribution pattern, but is not limited to this.

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

The light distribution pattern based on the pattern of the light shielding film 22 is explained.

FIG. 6 is a schematic diagram showing an example of a light distribution pattern based on a headlight unit, and FIG. 7 is a schematic diagram showing another example of a light distribution pattern based on a headlight unit. In addition, the light distribution pattern 30 shown in FIG. 6 and the light distribution pattern 32 shown in FIG. 7 both represent the area irradiated with light. Moreover, 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 FIG6 , the light intensity drops sharply at the edge 30a due to the pattern of the light shielding film 22. For example, the light distribution pattern 30 shown in FIG6 becomes a pattern that does not irradiate light to oncoming vehicles when driving on the left.

Furthermore, the light distribution pattern 32 shown in FIG. 7 can also be set as a pattern in which a part of the light distribution pattern 30 shown in FIG. 6 is cut off. At this time, as with the light distribution pattern 30 shown in FIG. 6, the light intensity drops sharply at the edge 32a, for example, it becomes a pattern that does not irradiate light to the oncoming vehicle when driving on the left. Furthermore, the light intensity also drops sharply at the notch 33. Therefore, in the area corresponding to the notch 33, for example, a sign indicating that the road is turning, uphill, downhill, etc. can be marked. In this way, the safety of driving at night can be improved.

In addition, the light shielding portion 14 is not limited to being fixed and arranged between the light source 12 and the lens 16, but can also be set as a structure that obtains a specific light distribution pattern by being arranged between the light source 12 and the lens 16 as needed by a driving mechanism not shown in the figure.

Furthermore, the shading portion 14 may be used to form a shading member capable of shielding the light from the light source 12.

At this time, it is also possible to set a driving mechanism (not shown) between the light source 12 and the lens 16 as needed to obtain a specific light distribution pattern.

[Implementation example]

The present invention is described in more detail below based on the embodiments. The materials, usage amounts, proportions, processing contents and processing steps shown in the following embodiments can be appropriately changed as long as they do not deviate from the main purpose 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 a color material composition containing the following black color material for use in the preparation of a light-shielding composition.

<Preparation of titanium black dispersion (color material composition A-1)>

100 g of titanium oxide MT-150A (trade name, manufactured by TAYCA CORPORATION) with an average particle size of 15 nm, 25 g of silicon oxide particles AEROGIL (registered trademark) 300/30 (manufactured by EVONIK) with a BET surface area of 300 m ² /g, and 100 g of dispersant Disperbyk 190 (trade name, manufactured by BYK-Chemie GmbH) were weighed and mixed. 71 g of ion-exchanged water was added to the obtained mixture. The obtained mixture was treated for 20 minutes using KURABO MAZERSTAR KK-400W at a rotation speed of 1360 rpm and an autorotation speed of 1047 rpm to obtain a more uniform dispersion. The dispersion was filled into a quartz container and heated to 920°C in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the atmosphere was replaced with nitrogen and ammonium gas was circulated at 100 mL/min for 5 hours at the same temperature to perform a nitriding reduction treatment. After the nitriding reduction treatment, the recovered powder was pulverized with a mill to obtain a powdered titanium black (color material a-1) having a specific surface area of 73 ^m2 /g.

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

In the above formula (X-1), the numbers attached to each repeating unit represent the molar ratio of each repeating unit. In addition, the weight average molecular weight of the above dispersed resin X-1 is 32000.

The obtained dispersion was stirred thoroughly with a stirrer for premixing. The obtained dispersion was dispersed using a disperser NPM Pilot (trade name, manufactured by SHINMARU ENTERPRISES CORPORATION) under the following conditions to obtain a dispersion containing color material a-1, i.e., color material composition A-1.

(Dispersion conditions)

˙Ball diameter: φ0.05mm

˙Microbead filling rate: 65 volume %

˙Grinding circumferential speed: 10m/sec

˙Separator circumferential speed: 11m/s

˙Amount of mixed liquid for dispersion treatment: 15.0g

˙Circulation flow (pump supply): 60kg/hour

˙Processing liquid temperature: 20~25℃

˙Cooling water: tap water (5℃)

˙Volume of bead mill annular channel: 2.2L

˙Number of passes: 84 times

<Preparation of organic pigment dispersion (color material composition A-2)>

An organic pigment containing a benzofuranone compound (trade name "Irgaphor Black S0100CF", manufactured by BASF) (150 parts by mass), a dispersing resin X-1 (75 parts by mass), SOLSPERSE 20000 (pigment derivative, manufactured by Lubrizol Japan Ltd.) (25 parts by mass), and 3-methoxybutyl acetate (MBA) (750 parts by mass) were mixed as color material a-2. The dispersing resin X-1 was the same as that used in the preparation of the dispersion of the color material composition A-2.

The obtained mixture was stirred for 20 minutes using a homogenizer (manufactured by PRIMIX Corporation) to obtain a pre-dispersion liquid. Furthermore, the obtained pre-dispersion liquid was dispersed for 3 hours using an ULTRA APEX MILL (manufactured by KOTOBUKI KOGYOU CO., LTD.) equipped with a centrifugal separator under the following dispersion conditions to obtain a dispersion composition. After the dispersion was completed, the beads and the dispersion liquid were separated using a filter to obtain a dispersion liquid containing color material a-2, i.e., color material composition A-2. The solid content concentration of the obtained dispersion liquid was 25% by mass, and the ratio of color material a-2/resin component (total of dispersion resin X-1 and pigment derivative) was 60/40 (mass ratio).

In addition, SOLSPERSE 20000 has an amine value of 29 mgKOH/g, no acid value, and is a compound with a tertiary amine as a pigment adsorption base.

(Dispersion conditions)

˙Microbeads used: φ0.30mm zirconia beads (YTZ balls, manufactured by Neturen Co., Ltd.)

˙Microbead filling rate: 75 volume %

˙Grinding circumferential speed: 8m/sec

˙Amount of mixed liquid for dispersion treatment: 1000g

˙Circulation flow (pump supply): 13kg/hour

˙Processing liquid temperature: 25~30℃

˙Cooling water: tap water (5℃)

˙Volume of bead mill annular channel: 0.15L

˙Number of passes: 90 times

<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) was used as color material a-3 instead of color material a-2. In addition, a dispersion containing color material a-3, i.e., color material composition A-3, was obtained according to the manufacturing method of the above-mentioned color material composition A-2.

<Preparation of carbon black dispersion (color material composition A-4)>

Carbon black was produced using a conventional oil furnace method. However, as the raw material oil, ethylene bottom oil with low Na, Ca and S content was used and burned using gas fuel. Furthermore, as the reaction stopping water, pure water treated with ion exchange resin was used.

The obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000-6,000 rpm for 30 minutes using a homogenizer to obtain a slurry. The slurry was transferred to a container with a screw-type stirrer and mixed at about 1,000 rpm while adding toluene (600 g) in which epoxy resin "Epikote 828" (manufactured by JER) (60 g) was dissolved little by little into the container. 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 using a 60-mesh metal screen to control water, the separated particles were placed in 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 above were mixed, and PGMEA was added to the obtained mixture until the solid content concentration became 35% by mass. The dispersing resin X-1 was the same as that used in the preparation of the color material composition A-1 above.

The obtained dispersion was stirred thoroughly with a stirrer and pre-mixed. The obtained dispersion was dispersed using ULTRA APEX MILL UAM015 manufactured by KOTOBUKI KOGYOU CO., LTD. under the following conditions to obtain a dispersion composition. After the dispersion was completed, the beads were separated from the dispersion using a filter to obtain a dispersion containing color material a-4, i.e., color material composition A-4.

(Dispersion conditions)

˙Ball diameter: φ0.05mm

˙Microbead filling rate: 75 volume %

˙Grinding circumferential speed: 8m/sec

˙Amount of mixed liquid for dispersion treatment: 500g

˙Circulation flow (pump supply): 13kg/hour

˙Processing liquid temperature: 25~30℃

˙Cooling water: tap water (5℃)

˙Volume of bead mill annular channel: 0.15L

˙Number of passes: 90 times

<Preparation of titanium black dispersion (color material composition A-5)>

A dispersion liquid containing color material a-1, i.e., color material composition A-5, was obtained by using a dispersion resin X-2 having a structure represented by the following formula (X-2) instead of the dispersion resin X-1 and following the method for producing the color material composition A-1.

In the above formula (X-2), the numbers marked on each repeating unit represent the molar ratio of each repeating unit. In addition, the weight average molecular weight of the above dispersed resin X-2 is 33000.

[Alkaline soluble resin]

<Synthesis of alkali-soluble resin B-1>

Under a dry nitrogen stream, 30.03 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.082 mol), 1.24 g of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (0.005 mol), and 2.73 g of 3-aminophenol (0.025 mol) as a capping agent were dissolved in 100 g of N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP"). To the obtained solution, 31.02 g of bis(3,4-dicarboxyphenyl)ether dianhydride (0.10 mol) and 30 g of NMP were added. The obtained solution was stirred at 20°C for 1 hour, and then stirred at 180°C for 4 hours while removing water. After the reaction was completed, the reaction solution was poured into 2L of water and the resulting 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 to synthesize the alkali-soluble resin B-1 (polyimide resin).

<Alkaline 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 Alkaline Soluble Resin B-3>

唑前驅物之樹脂)。 Under nitrogen flow, 0.16 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 41.3 g of diphenyl ether-4,4'-dicarboxylic acid with 43.2 g of 1-hydroxy-1,2,3-benzotriazole 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. Then, 13.1 g of 5-norbornene-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. The precipitate was washed with water three times and then dried in a vacuum dryer at 80°C for 24 hours to obtain an alkali-soluble resin B-3 (including polyphenylene glycol

resin of the precursor of the azole).

[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)

˙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, polymerization initiator C-1 and polymerization initiator C-2 are oxime ester polymerization initiators.

[Chemical formula 28]

[Polymerizable compounds]

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) are used to prepare the composition.

The polymerizable compound D-1 is a mixture of a pentafunctional polymerizable compound and a hexafunctional polymerizable compound, and the mixing ratio is pentafunctional polymerizable compound/hexafunctional polymerizable compound = 30/70 (mass ratio).

In addition, the above-mentioned "functionality" value indicates the number of ethylenically unsaturated groups possessed by one molecule of the polymerizable compound.

[Chemical formula 30]

[Surfactant]

The surfactant represented by the following formula (S-1) is used to prepare the composition.

In addition, the symbols of each repeating unit in formula (S-1) represent the molar ratio of each repeating unit, l+n=14, m=17. In addition, the weight average molecular weight of the surfactant represented by formula (S-1) is 15000.

[Polymerization inhibitor]

As a polymerization inhibitor, p-methoxyphenol is used in the preparation of light-shielding compositions.

[Solvent]

Cyclohexanone is used as a solvent in the preparation of light-shielding compositions.

[Implementation Example 1]

<Preparation of light-shielding composition 1>

The following ingredients were mixed with a stirrer to prepare the light-shielding composition 1 of Example 1.

˙63 parts by weight of the color material composition A-1 prepared in the above method

<Making the black layer>

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

<Formation of oxygen blocking layer E-1>

A mixed gas of argon and oxygen (oxygen: 40 volume %) was introduced into a vacuum chamber of a sputtering apparatus (manufactured by SHINKO SEIKI CO., LTD., trade name "SRV-4300"), and sputtering was performed using a silicon target, thereby forming an oxygen blocking layer E-1 (thickness: 100 nm) made of silicon oxide (SiO ₂ ) on the surface of the black layer produced above.

Thus, a light-shielding film of Example 1 was obtained, in which a black layer and an oxygen blocking layer E-1 were sequentially formed on a substrate.

[Examples 2~6, 8, 9, 14~17]

The light-shielding compositions of each embodiment were prepared according to the method described in Example 1, except that the components used were replaced or the addition amount of the color material composition A-1 was adjusted so that the composition of the light-shielding composition became the composition described in Table 1 and Table 2.

Using the light-shielding compositions obtained above, in addition, according to the method described in Example 1, light-shielding films of Examples 2 to 6, 8, 9 and 14 to 17 were prepared in which a black layer and an oxygen blocking layer were sequentially formed on a substrate.

[Implementation Example 7]

In the sputtering process, a mixed gas of argon and nitrogen (nitrogen: 50 volume %) is introduced into a vacuum chamber for sputtering, thereby forming an oxygen blocking layer E-2 (thickness: 100 nm) composed of silicon nitride (Si ₃ N ₄ ) on the surface of the black layer. In addition, according to the method described in Example 1, a light-shielding film of Example 7 is prepared in which a black layer and an oxygen blocking layer E-2 are sequentially formed on a substrate.

[Examples 10~13]

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

[Comparison Example 1]

<Preparation of composition for forming oxygen barrier layer>

The following ingredients were mixed to prepare a comparative composition 1.

˙Polyvinyl alcohol (PVA): 32.2 parts by mass (trade name: PVA205, manufactured by KURARAY CO., LTD, hydroxylation degree = 88%, polymerization degree 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

<Comparison of the formation of oxygen blocking layer CE-1>

According to the method for making a black layer described in Example 1, a black layer is formed on the substrate.

Using a spin coater, apply composition 1 on the surface of the produced black layer. The amount of composition 1 applied is adjusted so that the thickness of the layer after drying becomes 1000nm. Then, using a heating plate, the coating of resin composition 1 is dried at 100°C for 120 seconds, thereby forming a comparative oxygen blocking layer CE-1 (thickness: 1000nm).

Thus, a light-shielding film of Comparative Example 1 was obtained, in which a black layer and an oxygen blocking layer CE-1 were sequentially formed on a substrate.

[Comparison Example 2]

In the process of forming the oxygen blocking layer, the coating amount of composition 1 was adjusted so that the thickness of the layer after drying became 500nm. In addition, according to the method described in comparative example 1, a light shielding film of comparative example 2 was prepared in which a black layer and an oxygen blocking layer CE-2 were sequentially formed on a substrate.

[Comparison 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. In addition, according to the method described in Comparative Example 1, a light-shielding film of Comparative Example 3 was prepared in which a black layer and an oxygen blocking layer CE-1 were sequentially formed on a substrate.

[Comparison Examples 4~6]

In the sputtering process, the discharge power and film forming time were adjusted to form layers with the thicknesses listed in Table 3. In addition, according to the method listed in Example 1, light shielding films of Comparative Examples 4 to 6 were prepared by sequentially forming a black layer and oxygen blocking layers CE-3 to CE-5 on the substrate.

[Comparison Example 7]

<Preparation of composition for forming oxygen barrier layer>

According to the method described in paragraphs 0032 to 0034 and 0042 (Example 1-1) of Japanese Patent Publication No. 2013-253145, a hydrolyzate of tetramethoxysilane (TMOS) and trifluoropropyltrimethoxysilane (TFPTMS) and silica gel in which bead-like colloidal silica particles are dispersed are mixed to prepare a comparative composition 2.

<Comparison of the formation of oxygen barrier layer CE-6>

In the process of forming the oxygen barrier layer, the comparative composition 2 prepared in the above was used instead of the composition 1 and the coating amount of the comparative composition 2 was adjusted to a thickness of 190 nm after drying. In addition, according to the method described in comparative example 1, a light shielding film of comparative example 7 was prepared in which a black layer and an oxygen barrier layer CE-6 were sequentially formed on a substrate.

In addition, the surface of the oxygen barrier layer CE-6 was polished to form a smooth surface, and then the smooth surface was analyzed using 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 barrier layer CE-6 was 27% by mass relative to the total mass of the oxygen barrier layer.

[Comparison Examples 8~10]

The oxygen blocking layer E-1 was not formed. In addition, according to the methods described in Examples 1, 6 and 5, light shielding films of Comparative Examples 8 to 10 were prepared by forming only a black layer on the substrate.

[Evaluation]

Each oxygen barrier layer or each light shielding film obtained in the above process is subjected to the following tests and evaluations.

[Determination of oxygen permeability]

A substrate with a peeling layer was used instead of a substrate with a black layer, and each oxygen barrier layer was formed on the peeling layer. In addition, according to the methods described in Examples 1, 7, and 10 to 13, and Comparative Examples 1, 2, and 4 to 7, laminates were prepared in which a peeling layer and an oxygen barrier layer were sequentially formed on a substrate. Then, the oxygen barrier layer was peeled off from the obtained laminate to prepare an oxygen barrier layer for oxygen permeability evaluation.

The oxygen permeability (ml/(m ² ˙day˙atm)) of the oxygen barrier layer for evaluation prepared in the above was measured using an oxygen permeability measuring device (Model 8001, manufactured by ILLINOIS).

[Evaluation of light resistance]

<Irradiation test>

The light-shielding film obtained in the above was subjected to an irradiation test for 500 hours using a light resistance tester (Super Xenon Weather Meter (trade name) manufactured by Suga Test Instruments Co., Ltd.) under conditions of a light illuminance of 75 W/m ² (300-400 nm) and a humidity of 50% RH.

<Changes in film thickness before and after irradiation test>

The thickness of the light-shielding film before and after the irradiation test was measured using a contact-type film thickness meter. The change rate of the light-shielding film thickness before and after the irradiation test was calculated using the following formula, and the evaluation was performed based on the following viewpoints.

In addition, the "thickness of the light-shielding film" refers to the total thickness of the black layer and the thickness of the oxygen barrier layer, excluding the thickness of the substrate.

Change rate of film thickness (%) = ((Thickness of light-shielding film before irradiation test - Thickness of light-shielding film after irradiation test) / (Thickness of light-shielding film before irradiation test) × 100)

A: The variation rate of film thickness is less than 2%

B: The variation rate of film thickness is greater than 2% and less than 5%

C: The variation rate of film thickness is greater than 5% and less than 10%

D: The variation rate of film thickness is more than 10%

<Changes in transmittance and reflectance before and after irradiation test>

Using a spectrometer V7200 (trade name, manufactured by JASCO Corporation), light was incident on the light shielding film before and after the irradiation test at an incident angle of 5°. From the obtained transmission and reflection spectra, the maximum transmittance (hereinafter referred to as transmittance) in the wavelength range of 350 to 1200 nm and the reflectance at a wavelength of 550 nm were measured.

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)

Reflectivity change rate (%) = ((reflectivity before irradiation test - reflectivity after irradiation test) / reflectivity before irradiation test × 100)

A: The change rate of transmittance and reflectivity are both less than 2%

B: One of the transmittance change rate and reflectance change rate is greater than 2%, and the other is less than 2%

C: The change rate of transmittance and reflectivity are both above 2%

[Evaluation of heat resistance]

The light-shielding film obtained above was placed in an oven and subjected to a heat resistance test at 150°C for 500 hours.

The thickness of the light-shielding film before and after the heat resistance test was measured using a contact-type film thickness meter. The change rate of the light-shielding film thickness before and after the heat resistance test was calculated using the following formula, and the evaluation was performed based on 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 variation rate of film thickness is less than 2%

B: The variation rate of film thickness is greater than 2% and less than 4%

C: The film thickness variation rate is greater than 4% and less than 6%

D: The variation rate of film thickness is more than 6%

[Evaluation of moisture resistance]

The light shielding film obtained in the above was placed in a constant temperature and humidity chamber and subjected to a moisture resistance test for 500 hours at 85°C and 85% RH. The cross section of the line pattern with an opening line width of 50μm was observed on the substrate after the moisture resistance test using a scanning electron microscope (SEM) S-4800 (trade name, manufactured by JEOL Ltd.). Based on the SEM image of the cross section obtained, the presence or absence of pattern peeling was evaluated from the following viewpoints.

A: No peeling was found in any of the patterns.

B: Peeling can be found in less than 20% of the overall pattern.

C: Peeling can be found in a range of more than 20% and less than 50% of the entire pattern.

D: Peeling can be found in more than 50% of the entire pattern.

[result]

Tables 1 to 3 show the compositions of the light-shielding compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 10, and the results of various tests on light-shielding films made using the light-shielding compositions.

In Tables 1 to 3, the "Color material content" column indicates the ratio (mass %) of the content of the black color material to the total solid content of each light-shielding composition.

In Tables 1 to 3, the "Composition" column of "Oxygen barrier layer" indicates that the oxygen barrier layer is 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: Organic layer composed of polysiloxane containing silicon oxide particles

In Tables 1 to 3, the "Thickness" column of "Oxygen Barrier Layer" indicates the thickness (nm) of each oxygen barrier layer measured using a contact film thickness gauge.

In addition, in Tables 1 to 3, the column "Black layer thickness/oxygen barrier layer thickness" indicates the ratio of the black layer thickness measured by a contact film thickness meter to the oxygen barrier layer thickness.

The results shown in Tables 1 to 3 confirm that the light-shielding composition of the present invention can solve the problem of the present invention.

It was confirmed that from the perspective of better moisture resistance of the light-shielding film, 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 perspective of better heat resistance of the light-shielding film, the content of the black color material is preferably 30% by mass or more, and more preferably 50% by mass or more (comparison of Example 1, Examples 14 and 16).

It was confirmed that from the perspective of better moisture resistance of the light-shielding film, it is better for the black color material to contain titanium nitride oxide, benzofuranone compound or perylene compound (comparison of Examples 1, 3, 4 and 5).

Furthermore, it was confirmed that from the perspective of better light resistance of the light-shielding film, it is better for the black color material to contain titanium nitride oxide or carbon black (comparison of Examples 1, 3, 4 and 5).

Furthermore, from the later-described Examples 18 to 20, it was confirmed that from the perspective of superior moisture resistance and light resistance of the light-shielding film, a black color material containing vanadium nitride, niobium nitride, or zirconium nitride is as good as a black color material containing titanium nitride oxide.

It was confirmed that from the perspective of better light resistance, heat resistance and moisture resistance of the light-shielding film, it is better for the dispersed resin to contain ethylene unsaturated groups (comparison between Example 1 and Example 9).

唑前驅物構成之樹脂與聚醯亞胺樹脂同 樣地較佳。 It was confirmed that the alkali-soluble resin is preferably a polyimide resin from the viewpoint of better light resistance and heat resistance of the light-shielding film (comparison between Example 1 and Example 6). In addition, from Example 21 described later, it was confirmed that the alkali-soluble resin is preferably a polyimide resin from the viewpoint of better light resistance and moisture resistance of the light-shielding film.

The resin composed of azole promotors is equally preferred as the polyimide resin.

It was confirmed that from the perspective of better light resistance and heat resistance of the light-shielding film, the polymerization initiator C-1 is the better polymerization initiator (comparison between Example 1 and Example 8).

It was confirmed that from the perspective of better heat resistance and moisture resistance of the light-shielding film, the polymerizable compound D-1 is the better polymerizable compound (comparison between Example 1 and Example 2).

It was confirmed that from the perspective of better light resistance and moisture resistance of the light-shielding film, it is better for the oxygen blocking layer to contain silicon oxide (comparison between Example 1 and Example 7).

It was confirmed that from the perspective of better moisture resistance and heat resistance of the light-shielding film, the thickness of the oxygen blocking layer is preferably greater than 50nm and less than 250nm (comparison between Examples 1, 24 and 25 and Examples 10 and 11).

It was confirmed that from the perspective of better moisture resistance and heat resistance of the light-shielding film, the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is preferably 7 to 30 (comparison between Example 1 and Examples 10 and 11).

[Examples 18~20]

The following color materials a-5 to a-7 were used to replace titanium black (color material a-1), and color material compositions A-6 to A-8 were prepared according to the preparation method of the above color material composition A-1.

˙Color material a-5: Vanadium nitride (trade name "VN-O, made 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 using the method of Example 1 of Japanese Patent Application Publication No. 2017-222559.)

The color material compositions A-6 to A-8 prepared in the above were used to replace the color material composition A- 1. In addition, the light-shielding compositions of Examples 18 to 20 were prepared according to the preparation method of the light-shielding composition 1 of Example 1. The obtained light-shielding compositions were used to replace the light-shielding composition 1. In addition, the light-shielding films of Examples 18 to 20 were prepared in which a black layer and an oxygen blocking layer were sequentially formed on a substrate according to the method described in Example 1. The evaluation results of the light-shielding films of Examples 18 to 20 were all equal to those of Example 1.

Color material a-8 was used instead of titanium black (color material a-1). In addition, the color material composition was prepared according to the preparation method of the above-mentioned color material composition A-1, and the same evaluation as Example 1 was carried out.

˙Color material a-8: silicon dioxide coated zirconium nitride (Japanese Patent Publication No. 2015-117302)

The evaluation results are the same as those of Example 1.

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, 9:1 was used to replace titanium black (color material a-1). In addition, the color material composition was prepared according to the preparation method of the above-mentioned color material composition A-1, and the same evaluation as Example 1 was performed.

The evaluation results are the same as those of Example 1.

In addition, 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, 9:1 was used to replace titanium black (color material a-1). In addition, the color material composition was prepared according to the preparation method of the above-mentioned color material composition A-1, and the same evaluation as Example 1 was performed.

The evaluation results are the same as those of Example 1.

[Example 21]

The light-shielding composition of Example 21 was prepared according to the preparation method of the light-shielding composition 1 of Example 1, except that the alkali-soluble resin B-3 was used instead of the alkali-soluble resin B-1.

The obtained light-shielding composition was used to replace the light-shielding composition 1. In addition, according to the method described in Example 1, a light-shielding film of Example 21 was prepared by sequentially forming a black layer and an oxygen blocking layer on a substrate. The evaluation results of the light-shielding film of Example 21 were all equal to those of Example 1.

[Example 22]

The light-shielding composition of Example 22 was prepared according to the preparation method of the light-shielding composition 1 of Example 1, except that the polymerization initiator C-3 was used instead of the polymerization initiator C-2. The light-shielding film of Example 22, which was formed on the substrate in sequence by sequentially forming a black layer and an oxygen blocking layer, was prepared according to the method described in Example 1, except that the obtained light-shielding composition was used instead of the light-shielding composition 1. The evaluation results of the light-shielding film of Example 22 showed that 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 with a mass ratio of 1:1 was used to replace 6.1 parts by mass of polymerizable compound D-1, and a light-shielding composition of Example 23 was prepared according to the method of Example 1. The obtained light-shielding composition was used to replace light-shielding composition 1, and a light-shielding film of Example 23 was prepared by sequentially forming a black layer and an oxygen blocking layer on a substrate according to the method described in Example 1. The evaluation results of the light-shielding film of Example 23 showed that the moisture resistance was B, and other than that, it was equal to that of Example 1.

[Example 24~25]

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

[Example 26~27]

The light-shielding composition of Example 26 was prepared according to the preparation method of the light-shielding composition 1 of Example 1 except that the polymerization inhibitor was not used. Furthermore, the light-shielding composition of Example 27 was prepared according to the preparation method of the light-shielding composition 1 of Example 1 except that the surfactant was not used. The light-shielding films of Examples 26 and 27, in which a black layer and an oxygen blocking layer were sequentially formed on a substrate, were prepared respectively according to the method described in Example 1, except that the obtained light-shielding compositions were used instead of the light-shielding composition 1. The evaluation results of the light-shielding films of Examples 26 and 27 were equal to those of Example 1.

[Example 28]

<Production of a color filter with a black matrix>

The light-shielding composition 1 of Example 1 was applied to a glass wafer by spin coating to form a composition layer. The glass wafer was then placed on a heating plate and pre-baked at 120° C. for 2 minutes. The composition layer was then exposed to light at an exposure dose of 500 mJ/cm ² using an i-ray stepper through a mask having an island pattern of 0.1 mm.

Next, the exposed composition layer was subjected to rotary immersion development at 23°C for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide to obtain a cured film. The cured film was rinsed using a rotary spray and then cleaned with pure water to form a patterned black layer.

Next, according to the method for forming the oxygen blocking layer E-1 of Example 1, an oxygen blocking layer composed of silicon oxide is formed on the surface of the black layer prepared above, thereby preparing a light shielding film (black matrix) formed by sequentially forming a black layer and an oxygen blocking layer on a glass wafer. The result of using the above black matrix to prepare a color filter has good performance.

[Example 29]

<Production of solid-state imaging device with light-shielding film>

The curable lens composition (a composition of 1 mass % of an arylsulfonium salt derivative (ADEKA CORPORATION, trade name "SP-172") added to a para-resin epoxy resin (Daicel Corporation, trade name "EHPE-3150")) (2 mL) was applied on a 5×5 cm glass substrate (1 mm thick, Schott AG, trade name "BK7"), and the coating was heated at 200°C for 1 minute to cure, thereby forming a lens film capable of evaluating the residue on the lens.

The light-shielding composition 1 of Example 1 was applied to the glass wafer on which the lens film was formed, thereby forming a composition layer. Then, the glass wafer was placed on a heating plate and pre-baked at 120°C for 120 seconds. The thickness of the heated composition layer was 2.0 μm.

Next, the composition layer was exposed to light at an exposure dose of 500 mJ/ ^cm2 using a high-pressure mercury lamp through a mask having a 10 mm hole pattern. The exposed composition layer was then subjected to rotary immersion development at 23°C for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide to obtain a cured film. The cured film was rinsed using a rotary spray and then cleaned with pure water to form a patterned black layer.

Next, according to the method for forming the oxygen blocking layer E-1 of Example 1, an oxygen blocking layer composed of silicon oxide is formed on the surface of the black layer prepared above, thereby preparing a light shielding film in which a black layer and an oxygen blocking layer are sequentially formed on a glass wafer.

On the glass wafer formed with the light shielding film produced in the above, a curable resin layer was formed using a curable composition for lenses (a composition in which 1% by mass of an arylsulfonium salt derivative (produced by ADEKA CORPORATION, trade name "SP-172") was added to an epoxy resin (produced by Daicel Corporation, trade name "EHPE-3150")). Then, the shape was transferred using a quartz mold having a lens shape, and the curable resin layer was cured by exposure with a high-pressure mercury lamp at an exposure dose of 400mJ/ ^cm2 , thereby producing a wafer-level lens array having a plurality of wafer-level lenses.

After cutting the wafer-level lens array, the obtained wafer-level lens is used to make a lens module, and then the imaging element and sensor substrate are installed to produce a solid-state imaging element with the light-shielding film of the present invention.

Among the solid-state imaging devices obtained, the lens opening of the wafer-level lens has no residue and has good transmittance, and the light-shielding film also has high uniformity on the coating surface and high light-shielding properties.

[Example 30]

<Production of headlight unit with shading film>

The light-shielding composition 1 of Example 1 obtained above was applied to a 10 cm square glass substrate using a spin coating method to form a composition layer. The glass substrate was placed on a heating plate and pre-baked at 120°C for 2 minutes.

The obtained composition layer was exposed to light (exposure amount 1000 mJ/cm ² ) through a mask using an i-ray stepper to obtain a cured film having a light distribution pattern as shown in FIG. 6 .

Next, the development process was performed using a developer (Act-8 manufactured by Tokyo Electron Limited). A 0.3% aqueous solution of tetramethylammonium hydroxide was used as the developer, and rotary immersion development was performed at 23°C for 60 seconds. Afterwards, the obtained cured film was rinsed with a rotary spray of pure water, thereby obtaining a black layer with a prescribed light distribution pattern.

Next, according to the method for forming the oxygen blocking layer E-1 of Example 1, an oxygen blocking layer composed of silicon oxide is formed on the surface of the black layer prepared above, thereby preparing a light-shielding film in which a black layer and an oxygen blocking layer are sequentially formed on a glass substrate.

The result of using the obtained shading film, light source and lens to make a headlight unit has good performance.

Claims (15)

A light-shielding film comprises: a black layer containing a black colorant; and an oxygen blocking layer formed on the black layer, wherein the oxygen blocking layer is a single layer composed of an inorganic material, the thickness of the oxygen blocking layer is 10-500 nm, the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is 7-30, and the oxygen permeability of the oxygen blocking layer is less than 10 ml/(m ² ˙day˙atm). The light-shielding film as described in claim 1, wherein the black color material contains at least one metal nitride selected from the group consisting of titanium, vanadium, zirconium and niobium. The light-shielding film as described in claim 1, wherein the black color material contains carbon black, benzofuranone compounds or perylene compounds. The light-shielding film as described in claim 1, wherein the content of the black color material is 20-80% by mass relative to the total mass of the black layer. A light-shielding film as described in claim 1, wherein the oxygen blocking layer contains silicon oxide. A light-shielding film as described in any one of claims 1 to 5, wherein the oxygen blocking layer substantially does not contain particles. A method for manufacturing a light-shielding film comprises: coating a light-shielding composition containing a black colorant, a resin, a polymerizable compound, and a polymerization initiator on a support, and curing the obtained coating to form a black layer; and forming an oxygen blocking layer on the black layer, wherein the oxygen blocking layer is a single layer composed of an inorganic material, the thickness of the oxygen blocking layer is 10-500nm, the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is 7-30, and the oxygen permeability of the oxygen blocking layer is less than 10ml/( ^m2˙day˙atm ). The method for manufacturing a light-shielding film as described in claim 7, wherein the process for forming the oxygen blocking layer includes a process for vapor deposition of inorganic materials. The method for manufacturing a light-shielding film as claimed in claim 7 or 8, wherein the resin comprises a material selected from the group consisting of polyimide precursor, polybenzoic acid,

At least one alkali-soluble resin selected from the group consisting of azole precursors and copolymers thereof. A method for manufacturing a light-shielding film as described in claim 7 or 8, wherein the light-shielding composition contains at least two polymerizable compounds. The method for producing a light-shielding film as described in claim 7 or 8, wherein the polymerization initiator is a compound represented by the following formula (C-13):

A method for manufacturing a light-shielding film as described in claim 7 or 8, wherein the resin contains a resin having an ethylenically unsaturated group. An optical element comprising a light-shielding film as described in any one of claims 1 to 6. A solid-state imaging element comprising a light-shielding film as described in any one of claims 1 to 6. A headlight unit is a headlight unit of a vehicle lighting fixture, the headlight unit comprising: a light source; and a shading portion for shielding at least a portion of light emitted from the light source, the shading portion comprising a shading film as described in any one of claims 1 to 6.