KR102660236B1 - Light-shielding film, manufacturing method of light-shielding film, optical element, solid-state imaging device, headlight unit - Google Patents

Abstract

The light-shielding film has a black layer containing a black colorant, and an oxygen blocking layer formed on the black layer. The oxygen blocking layer is a single layer made of an inorganic material, and the thickness of the oxygen blocking layer is 10 to 500 nm. The method for producing a light-shielding film includes the steps of applying a light-shielding composition containing a black colorant, a resin, a polymerizable compound, and a polymerization initiator onto a support, curing the obtained coating film, and forming a black layer, and forming a black layer on the black layer. A process for forming an oxygen blocking layer is provided.

Description

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

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

Color filters used in liquid crystal display devices are equipped with a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.

Additionally, currently, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units. Solid-state imaging devices such as charge coupled device (CCD) image sensors and complementary metal-oxide semiconductor (CMOS) image sensors are provided with a light shielding film for the purpose of preventing noise generation and improving image quality.

In such color filters, there is a known technology for providing an oxygen blocking layer on the light-shielding film and the colored pixels. For example, in Patent Document 1, on a substrate, a black matrix, a color filter layer, an oxygen barrier layer covering the black matrix and the color filter layer and containing at least an oxygen barrier compound, and between the color filter layer and the oxygen barrier layer. A color filter is disclosed, comprising a mixed layer containing a dye and an oxygen-blocking compound.

Patent Document 1: Japanese Patent Publication No. 2011-248197

As a result of examining the black matrix provided with the oxygen blocking layer described in Patent Document 1, the present inventors found that the light resistance and moisture resistance of the black matrix (light shielding film) may not be sufficiently satisfied.

Therefore, the present invention aims to provide a light-shielding film excellent in light resistance and moisture resistance. In addition, the present invention also aims to provide a method for manufacturing a light-shielding film, an optical element, a solid-state imaging element, and a headlight unit.

As a result of intensive study, the present inventor found that the above-described problem could be solved by the following configuration, and completed the present invention.

〔One〕

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 made of an inorganic material, and the oxygen blocking layer has a thickness of 10 to 500 nm. Sunshade.

〔2〕

The light-shielding film according to [1], wherein the black colorant contains an oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium, and niobium.

〔3〕

The light-shielding film according to [1], wherein the black colorant contains carbon black, a benzofuranone compound, or a perylene compound.

〔4〕

The light-shielding film according to any one of [1] to [3], wherein the content of the black colorant is 20 to 80% by mass with respect to the total mass of the black layer.

〔5〕

The light-shielding film according to any one of [1] to [4], wherein the oxygen blocking layer contains silicon oxide.

〔6〕

The light-shielding film according to any one of [1] to [5], wherein the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is 2 to 100.

〔7〕

The light-shielding film according to any one of [1] to [6], wherein the oxygen permeability of the oxygen blocking layer is 10 ml/(m ² ·day·atm) or less.

〔8〕

The light-shielding film according to any one of [1] to [7], wherein the oxygen blocking layer does not substantially contain particles.

〔9〕

A step of applying a light-shielding composition containing a black colorant, a resin, a polymerizable compound, and a polymerization initiator onto a support, curing the resulting coating film to form a black layer, and forming an oxygen blocking layer on the black layer. A manufacturing method of a light-shielding film comprising a forming process, wherein the oxygen blocking layer is a single layer made of an inorganic material, and the oxygen blocking layer has a thickness of 10 to 500 nm.

〔10〕

The method for producing a light-shielding film according to [9], wherein the step of forming the oxygen blocking layer includes the step of depositing an inorganic material.

〔11〕

The method for producing a light-shielding film according to [9] or [10], wherein the resin contains an alkali-soluble resin containing at least one selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and copolymers thereof. .

〔12〕

The method for producing a light-shielding film according to any one of [9] to [11], wherein the light-shielding composition contains at least two types of polymerizable compounds.

〔13〕

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

〔14〕

The method for producing a light-shielding film according to any one of [9] to [13], wherein the resin contains a resin having an ethylenically unsaturated group.

〔15〕

An optical element containing the light-shielding film according to any one of [1] to [8].

〔16〕

A solid-state imaging device containing the light-shielding film according to any one of [1] to [8].

〔17〕

A headlight unit of a vehicle lamp, comprising a light source and a light-shielding portion that blocks at least part of the light emitted from the light source, wherein the light-shielding portion contains the light-shielding film according to any one of [1] to [8]. Headlight unit.

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

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

Hereinafter, the present invention will be described in detail.

The description of the structural requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

In addition, in this specification, the numerical range indicated using "~" means a range containing the numerical values written before and after "~" as the lower limit and upper limit.

In addition, in the notation of groups (atomic groups) in this specification, notations that do not describe substitution or unsubstitution include groups containing a substituent as well as groups that do not contain a substituent. For example, “alkyl group” includes not only an alkyl group that does not contain a substituent (unsubstituted alkyl group), but also an alkyl group that contains a substituent (substituted alkyl group).

In addition, “actinic rays” or “radiation” in this specification means, for example, deep ultraviolet rays, extreme ultraviolet lithography (EUV), X-rays, and electron rays. In addition, in this specification, “light” means actinic rays and radiation. Unless otherwise specified, “exposure” in this specification includes not only exposure with deep ultraviolet rays, X-rays, and EUV light, but also drawing with particle beams such as electron beams and ion beams.

In addition, in this specification, "(meth)acrylate" refers to acrylate and methacrylate. In this specification, “(meth)acrylic” refers to acrylic and methacrylic. In this specification, “(meth)acryloyl” represents acryloyl and methacryloyl. In this specification, “(meth)acrylamide” refers to acrylamide and methacrylamide. In this specification, “monomer” and “monomer” have the same meaning.

In this specification, “ppm” means “parts-per-million (10 ^-6 )”, “ppb” means “parts-per-billion (10 ^-9 )”, and “ppt” means “ It means “parts-per-trillion(10 ^-12 )”.

In addition, in this specification, the weight average molecular weight (Mw) is a polystyrene conversion value determined by GPC (Gel Permeation Chromatography) method.

In this specification, the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mmID x 15 cm) as columns, and THF (tetrahydrofuran) as an eluent. It is based on how to use .

[light shield]

The light-shielding film of the present invention includes a black layer containing a black colorant and an oxygen blocking layer provided on the black layer.

The oxygen blocking layer is a single layer made of an inorganic material.

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

In addition, the light-shielding film of the present invention includes the steps of applying a light-shielding composition containing a black colorant, a resin, a polymerizable compound, and a polymerization initiator onto a support, curing the obtained coating film, and forming a black layer, and forming the black layer. It can be manufactured by a manufacturing method including a step of forming an oxygen blocking layer on the 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 depending on the production method, but is, for example, a black layer (including a patterned black layer) obtained by curing a coating film formed using the light-shielding composition.

[Light-blocking composition]

The light-shielding composition (hereinafter also simply referred to as “composition”) used to form the black layer will be described. The light-shielding composition contains at least a black colorant, a resin, a polymerizable compound, and a polymerization initiator.

<Black color material>

The light-shielding composition contains a black colorant.

As a black colorant, one or more types selected from the group consisting of black pigments and black dyes can be mentioned.

One type of black colorant may be used alone, or two or more types may be used.

The content of the black colorant in the black layer is not particularly limited, and may be, for example, 20 to 80 mass% with respect to the total mass of the black layer. Since the heat resistance of the light shielding film is more excellent, the content of the black colorant is preferably more than 20% by mass, more preferably 30% by mass or more, and still more preferably 50% by mass or more, relative to the total mass of the black layer. In addition, the content of the black colorant is preferably less than 80% by mass, more preferably 70% by mass or less, and even more preferably 65% by mass or less, relative to the total mass of the black layer, because the moisture resistance of the light shielding film is more excellent. do.

In addition, the content of the black colorant in the light-shielding composition may be, for example, 20 to 80% by mass relative to the total solid content of the light-shielding composition, and since the heat resistance of the light-shielding film is more excellent, relative to the total solid content of the light-shielding composition, More than 20 mass% is preferable, 30 mass% or more is more preferable, and 50 mass% or more is still more preferable. Moreover, the content of the black colorant in the light-shielding composition is preferably less than 80% by mass, more preferably 70% by mass or less, and 65% by mass relative to the total solid content of the light-shielding composition, since the moisture resistance of the light-shielding film is more excellent. % or less is more preferable.

In addition, in this specification, the "total solid content" of the composition refers to the component that forms a layer or film by curing, etc., and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components except the solvent. do. In addition, if it is a component that forms a film, the liquid component is also considered a solid component.

That is, by adjusting the content of the black colorant with respect 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.

Additionally, a black colorant may be obtained by combining multiple colorants that cannot be used alone as a black colorant and adjusting the overall color to be black.

For example, a plurality of pigments having a color other than black may be combined and used individually as a black pigment. Likewise, a plurality of dyes having a color other than black alone may be combined to form a black dye, or a pigment having a color other than black alone may be combined with a dye having a color other than black alone to form a black dye. You can also use it as .

In this specification, black colorant means a colorant that absorbs over the entire range of wavelengths from 400 to 700 nm.

More specifically, for example, a black colorant that satisfies the evaluation criterion Z described below is preferable.

First, a composition containing a colorant, a transparent resin matrix (acrylic resin, etc.), and a solvent is prepared, and the content of the colorant relative to the total solid content is 60% by mass. The obtained composition is applied on a glass substrate so that the dried coating film has a film thickness of 1 μm to form a coating film. The light-shielding property of the dried coating film is evaluated using a spectrophotometer (UV-3600, manufactured by Shimadzu Seisakusho Co., Ltd., etc.). If the maximum transmittance of the dried coating film at a wavelength of 400 to 700 nm is less than 10%, the colorant can be judged to be a black colorant suitable for evaluation criterion 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.

The black colorant is preferably a black pigment because the light resistance of the black layer is more excellent.

As a black pigment, a pigment that independently expresses black is preferable, and a pigment that independently expresses black and absorbs infrared rays is more preferable.

Here, the black pigment that absorbs infrared rays has absorption in the wavelength range of, for example, the infrared range (preferably a wavelength of 650 to 1300 nm). A black pigment having maximum absorption in the wavelength range of 675 to 900 nm is also desirable.

The particle size of the black pigment is not particularly limited, but is preferably 5 to 100 nm, more preferably 5 to 50 nm, and more preferably 5 to 100 nm in terms of a better balance between handling properties and stability over time of the composition (black pigment does not sediment). 30nm is more preferable.

In addition, in this specification, “particle size” means the average primary particle size of particles measured by the following method. The average primary particle diameter 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 can be used.

The maximum length of the particle image obtained using a transmission electron microscope (Dmax: maximum length at two points on the outline of the particle image), and the vertical length of the maximum length (DV-max: two straight lines parallel to the maximum length) When an image was placed in between, the shortest length connecting two straight lines vertically was measured, and the average value of the rise (Dmax x DV-max) ^1/2 was taken as the particle diameter. The particle diameters of 100 particles were measured using this method, and the arithmetic mean value was taken as the average primary particle diameter of the particles.

·Inorganic pigment

The inorganic pigment is not particularly limited as long as it has light-shielding properties and contains particles containing an inorganic compound, and any known inorganic pigment can be used.

Since the black layer has excellent low reflectivity and light-shielding properties, inorganic pigments are preferable as black colorants.

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

As the above-mentioned metal oxide, metal nitride, and metal oxynitride, particles in which other atoms are mixed may be further used. For example, metal nitride-containing particles that further contain atoms selected from elements in groups 13 to 17 of the periodic table (preferably oxygen atoms and/or sulfur atoms) can be used.

The method for producing the above-described metal nitride, metal oxide, or metal oxynitride is not particularly limited, as long as a black pigment with desired physical properties is obtained, and known production methods such as a gas phase reaction method can be used. Examples of the gas phase reaction method include the electric furnace method and the thermal plasma method, but the thermal plasma method is preferable because there is little mixing of impurities, the particle size is likely to be constant, and productivity is high.

The above metal nitride, metal oxide or metal oxynitride may be subjected to surface modification treatment. For example, surface modification treatment may be performed with a surface treatment agent containing 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.).

Among them, nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium, and niobium is more preferable because it can suppress the occurrence of undercut when forming a black layer. . In addition, the black colorant more preferably contains an oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium, and niobium, since the light resistance and moisture resistance of the light shielding film are more excellent, and titanium acid Those containing nitride (titanium black) are particularly preferred.

Titanium black is black particles containing titanium oxynitride. The surface of titanium black can be modified as needed for purposes such as improving dispersibility and suppressing cohesion. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can be coated with a water-repellent material as shown in Japanese Patent Application Publication No. 2007-302836. processing is also possible.

Methods for producing titanium black include a method of reducing a mixture of titanium dioxide and metal titanium by heating in a reducing atmosphere (Japanese Patent Application Publication No. 49-005432), and a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride with hydrogen. A method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Application Laid-Open No. 60-065069, Japanese Patent Application Publication No. 61) -201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Application Laid-Open No. 61-201610), etc., but are not limited to these.

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

Examples of commercially available products of titanium black include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (brand name, Mitsubishi Materials Co., Ltd.), Tilack D (brand name, Ako Kasei Co., Ltd.) MT-150A (brand name, manufactured by Daica Co., Ltd.), etc.

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

In addition, if the Si/Ti of the dispersant is too small, when a coating film using the dispersion is patterned by photolithography, etc., residue is likely to remain in the removal area, and if the Si/Ti of the dispersion is too large, the light-shielding ability tends to decrease. This happens.

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

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

In the dispersant containing titanium black and Si atoms, the titanium black described above can be used. In addition, in this dispersant, for the purpose of adjusting dispersibility, colorability, etc., along with titanium black, complex oxides of a plurality of metals selected from Cu, Fe, Mn, V and Ni, cobalt oxide, iron oxide, and carbon. Black pigments such as black and aniline black may be used together as a dispersant, either one type or in combination of two or more types. In this case, it is preferable that the dispersant made of titanium black occupies 50% by mass or more of the total dispersant.

The light-shielding composition also preferably contains zirconium nitride or zirconium oxynitride. It is preferable 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 impairing the light-shielding property of the pigment (light-shielding pigment), making it easier to prevent deterioration of the light-shielding composition. Preferred specific examples of the inorganic compound include titanium dioxide, zirconia, silica, and alumina. Examples of the inorganic compound include silica and alumina. It is also preferable to use it in combination with titanium black and zirconium nitride, titanium black and zirconium oxynitride, titanium black and silica-coated zirconium nitride, and titanium black and alumina-coated zirconium nitride.

Examples of the inorganic pigment include carbon black.

The black colorant preferably contains carbon black because it is excellent in light blocking properties and is particularly excellent in suppressing fluctuations in optical properties after a light fastness test.

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

As carbon black, carbon black manufactured by a known method such as an oil furnace method may be used, or a commercially available product may be used. Specific examples of commercially available carbon black include organic pigments such as C.I. Pigment Black 1, and inorganic pigments such as C.I. Pigment Black 7.

As carbon black, surface-treated carbon black is preferable. By surface treatment, the surface state of the carbon black particles can be modified, and the dispersion stability in the composition can be improved. Examples of surface treatment include coating treatment with a resin, surface treatment to introduce an acidic group, and surface treatment with a silane coupling agent.

As carbon black, carbon black coated with resin is preferable. By coating the surfaces of carbon black particles with an insulating resin, the light-shielding properties and insulating properties of the black layer can be improved. Additionally, the reliability of the image display device can be improved by reducing the leakage current. For this reason, it is suitable for cases where the black layer is used in applications requiring insulation.

Examples of the coating resin include epoxy resin, polyamide, polyamideimide, novolak resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkylbenzene resin, polystyrene, polycarbonate, and polybutylene tere. Phthalates and modified polyphenylene oxide can be mentioned.

The content of the coating resin is preferably 0.1 to 40% by mass, and more preferably 0.5 to 30% by mass, relative to the total of carbon black and the coating resin, because the black layer has excellent light-shielding properties and insulating properties.

·Organic pigments

The organic pigment is not particularly limited as long as it has light-shielding properties and contains particles containing an organic compound, and any known organic pigment can be used.

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

The black color material preferably contains a benzofuranone compound or a perylene compound because the moisture resistance of the light shielding film is more excellent.

(benzofuranone compound)

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

Examples of the benzofuranone compound include compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, and Japanese Patent Publication No. 2012-515234.

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

[Formula 1]

In general formulas (63) to (65), R ²⁰⁶ , R ²⁰⁷ , R ²¹² , R ²¹³ , R ²¹⁸ and R ²¹⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom. It represents an alkyl group having 1 to 10 carbon atoms and having 1 to 20 carbon atoms. R ²⁰⁸ , R ²⁰⁹ , R ²¹⁴ , R ²¹⁵ , R ²²⁰ and R ²²¹ are each independently 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 Represents R ²⁵² , and R ²⁵¹ and R ²⁵² are each independently an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, a cycloalkenyl group with 4 to 10 carbon atoms, or 2 carbon atoms. It represents an alkyne group of ~10. A plurality of R ²⁰⁸ , R ²⁰⁹ , R ²¹⁴ , R ²¹⁵ , R ²²⁰ or R ²²¹ may be directly bonded, or may form a ring with 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 with 1 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. a, b, c, d, e and f each independently represent an integer of 0 to 4. In general formulas (63) to (65), R ²⁰⁶ , R ²⁰⁷ , R ²¹² , R ²¹³ , R ²¹⁸ and R ²¹⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom. An alkyl group having 1 to 12 carbon atoms and having 1 to 6 carbon atoms is preferable. In addition, R ²⁵¹ and R ²⁵² are each independently an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 4 to 7 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, a cycloalkenyl group with 4 to 7 carbon atoms, or an alkyl group with 2 to 6 carbon atoms. In-diary is preferable. Moreover, R ²¹⁰ , R ²¹¹ , R ²¹⁶ , R ²¹⁷ , R ²²² and R ²²³ are each independently preferably a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 10 carbon atoms. The alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group may have a hetero atom and may be either unsubstituted or substituted.

[Formula 2]

In general formulas (66) to (68), R ²⁵³ , R ²⁵⁴ , R ²⁵⁹ , R ²⁶⁰ , R ²⁶⁵ and R ²⁶⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom. It represents an alkyl group having 1 to 10 carbon atoms and having 1 to 20 carbon atoms. R ²⁵⁵ , R ²⁵⁶ , R ²⁶¹ , R ²⁶² , R ²⁶⁷ and R ²⁶⁸ are each independently 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 represents, and R ²⁷¹ and R ²⁷² each independently represent an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, a cycloalkenyl group with 4 to 10 carbon atoms, or 2 carbon atoms. It represents an alkyne group of ~10. A plurality of R ²⁵⁵ , R ²⁵⁶ , R ²⁶¹ , R ²⁶² , R ²⁶⁷ or R ²⁶⁸ may be directly bonded or may form a ring with 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 with 1 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. a, b, c, d, e, and f each independently represent integers from 0 to 4. In general formulas (66) to (68), R ²⁵³ , R ²⁵⁴ , R ²⁵⁹ , R ²⁶⁰ , R ²⁶⁵ and R ²⁶⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom. An alkyl group having 1 to 12 carbon atoms and having 1 to 6 carbon atoms is preferable. In addition, R ²⁷¹ and R ²⁷² are each independently an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 4 to 7 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, a cycloalkenyl group with 4 to 7 carbon atoms, or an alkyl group with 2 to 6 carbon atoms. In-diary is preferable. Moreover, R ²⁵⁷ , R ²⁵⁸ , R ²⁶³ , R ²⁶⁴ , R ²⁶⁹ and R ²⁷⁰ are each independently preferably a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 10 carbon atoms. The alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group may have a hetero atom and may be either unsubstituted or substituted.

The benzofuranone compound is available as, for example, Irgaphor Black S0100CF (trade name, manufactured by BASF).

(perylene compound)

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

Examples of perylene compounds include compounds described in Japanese Patent Application Laid-Open No. 62-001753 and Japanese Patent Application Publication No. 63-026784.

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

[Formula 3]

In general formulas (69) to (71), X ⁹² , X ⁹³ , X ⁹⁴ and X ⁹⁵ each independently represent an alkylene group having 1 to 10 carbon atoms. R ²²⁴ and R ²²⁵ each independently represent hydrogen, a hydroxy group, an alkoxy group with 1 to 6 carbon atoms, or an acyl group with 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 general formulas (69) to (71), each of X ⁹² , X ⁹³ , X ⁹⁴ and X ⁹⁵ is preferably an alkylene group having 1 to 6 carbon atoms. Moreover, R ²²⁴ and R ²²⁵ are each independently preferably a hydrogen atom, a hydroxy group, an alkoxy group with 1 to 4 carbon atoms, or an acyl group with 2 to 4 carbon atoms. R ²⁷³ and R ²⁷⁴ are each independently preferably hydrogen or an alkyl group having 1 to 6 carbon atoms. The alkylene group, alkoxy group, acyl group and alkyl group may have a hetero atom and may be unsubstituted or substituted.

Perylene compounds include, for example, C.I. Pigment Black 21, 30, 31, 32, 33 and 34, and Paliogen Black S0084, K0084, L0086, K0086, EH0788 and FK4281 (all product names, BASF). It is available as.

(black dye)

As the black dye, a dye that independently expresses black can be used, for example, pyrazolazo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, and oxonol compounds. , pyrazolotriazolazo compounds, pyridonazo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazolazometaine compounds can be used.

Additionally, as black dyes, Japanese Patent Application Laid-Open No. 64-090403, Japanese Patent Application Publication No. 64-091102, Japanese Patent Application Laid-Open No. 1-094301, Japanese Patent Application Publication No. 6-011614, and Japanese Patent Application Publication No. 2592207. , U.S. Patent Publication No. 4808501, U.S. Patent Publication No. 5667920, U.S. Patent Publication No. 0505950, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Publication No. 6-035183, Japanese Patent Application Publication No. 6-051115, and compounds described in Japanese Patent Application Laid-Open No. Hei 6-194828, etc., the contents of which are incorporated herein by reference.

Specific examples of these black dyes include dyes specified by the color index (C.I.) of Solvent Black 27 to 47, and dyes specified by C.I. of Solvent Black 27, 29 or 34 are preferable.

Additionally, commercially available products of these black dyes include Spillon Black MH, Black BH (above, manufactured by Hodogaya Kagaku Kogyo Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (above, manufactured by Orient Kagaku Kogyo Co., Ltd.), and Savinyl Black. Dyes such as RLSN (above, manufactured by Clariant Corporation), KAYASET Black K-R, and K-BL (above, manufactured by Nippon Kayaku Co., Ltd.) can be mentioned.

Additionally, a dye multimer may be used as the black dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. Additionally, a polymerizable dye having a polymerizable group in the molecule may be used, and commercially available products include, for example, the RDW series manufactured by Wako Pure Chemical Industries, Ltd.

In addition, as described above, a plurality of dyes having a color other than black may be used individually as a black dye in combination. Such colored dyes include, for example, chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), as well as those described in paragraphs 0027 to 0200 of Japanese Patent Application Laid-Open No. 2014-042375. Dyes can also be used.

The black coloring material contains a nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium, and niobium because it can suppress the occurrence of undercut when forming a black layer. It is more preferable to contain an oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium, and niobium because the light resistance and moisture resistance of the light shielding film are more excellent, and titanium oxynitride (Titanium Black) is particularly preferred.

Moreover, it is preferable that the black colorant contains carbon black, a benzofuranone compound, or a perylene compound.

(coloring agent)

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

As colorants, pigments and dyes other than the black colorants mentioned above can be mentioned.

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

In addition, when the black layer formed from the light-shielding composition is used as a light attenuation film, it is preferable that the total content of the black colorant and the colorant is less than the above suitable range.

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

(infrared absorber)

The composition may further contain an infrared absorber.

An infrared absorber refers to a compound having absorption in the wavelength range of the infrared range (preferably a wavelength of 650 to 1300 nm). As an infrared absorber, a compound having maximum absorption in the wavelength range of 675 to 900 nm is preferable.

Colorants having such spectral characteristics include, for example, pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, and squarylium compounds. , naphthalocyanine compounds, quaterylene compounds, dithiol metal complex compounds, and croconium compounds.

As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Application Laid-Open No. 2010-111750 may be used. , this content is incorporated herein. For cyanine compounds, see, for example, "Functional pigments, Makoto Ogawara/Masaru Matsuoka/Daijiro Kitao/Tsuneaki Hirashima, Kodansha Scientific", the contents of which are incorporated in this specification.

As a colorant having the above spectral properties, the compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Laid-Open No. 07-164729 and/or the compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Application Laid-Open No. 2002-146254, Japanese Patent Application Laid-Open No. 2011-164583. Near-infrared absorbing particles consisting of crystallites of oxides containing Cu and/or P disclosed in paragraphs 0034 to 0067 of this issue and having a number average aggregate particle diameter of 5 to 200 nm may also be used.

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

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

For pyrrolopyrrole compounds, paragraphs 0049 to 0062 of Japanese Patent Application Laid-Open No. 2010-222557 can be referred to, and this content is incorporated herein by reference. Cyanine compounds and squaryllium compounds are described in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of Japanese Patent Application Publication No. 2014-059550, and International Publication No. 2014/059550. Paragraphs 0013 to 0091 of Publication No. 2012/169447, paragraphs 0019 to 0033 of Japanese Patent Application Publication No. 2015-176046, paragraphs 0053 to 0099 of Japanese Patent Application Publication No. 2014-063144, and paragraphs 0085 to 01 of Japanese Patent Application Publication No. 2014-052431. 50 , paragraphs 0076 to 0124 of Japanese Patent Publication No. 2014-044301, paragraphs 0045 to 0078 of Japanese Patent Publication No. 2012-008532, paragraphs 0027 to 0067 of Japanese Patent Publication No. 2015-172102, paragraph 002 of Japanese Patent Publication No. 2015-172004. 9 ~0067, paragraphs 0029-0085 of Japanese Patent Application Publication No. 2015-040895, paragraphs 0022-0036 of Japanese Patent Application Publication No. 2014-126642, paragraphs 0011-0017 of Japanese Patent Application Publication No. 2014-148567, paragraphs 0011-0017 of Japanese Patent Application Publication No. 2015-157893 Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of Japanese Patent Application Publication No. 2014-095007, paragraphs 0013 to 0047 of Japanese Patent Application Publication No. 2014-080487, and paragraphs 0007 to 0028 of Japanese Patent Application Publication No. 2013-227403. , this content is incorporated herein.

<Suzy>

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

The content of the resin in the composition is not particularly limited, but is preferably 3 to 60% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass, relative to the total solid content of the composition. One type of resin may be used individually, or two or more types may be used together. For example, as the resin, a dispersion resin described later and an alkali-soluble resin described later may be used together. When using two or more types of resin together, it is preferable that the total content is within the above range.

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

(dispersion resin)

The light-shielding composition preferably contains a dispersion resin. In addition, in this specification, dispersion resin means a compound different from the alkali-soluble resin described later.

The content of the dispersion resin in the composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 20% by mass, based on the total solid content of the composition.

Dispersion resin may be used individually by 1 type, or 2 or more types may be used together. When two or more types of dispersion resins are used together, it is preferable that the total content is within the above range.

Moreover, the mass ratio of the content of the dispersion resin (preferably a graft-type polymer) to the content of the black colorant in the composition (content of the dispersion resin/content of the black colorant) is preferably 0.05 to 1.00, and is 0.05 to 0.05. 0.35 is more preferable, and 0.20 to 0.35 is more preferable.

As the dispersion resin, for example, a known dispersant can be appropriately selected and used. Among them, high molecular compounds are preferable.

As a dispersion resin, a polymer dispersant (e.g., polyamideamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly(meth)acrylate, (meth)acrylate, ) Acrylic copolymer, naphthalene sulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, and pigment derivatives.

Polymeric compounds can be further classified into straight-chain polymers, terminal-modified polymers, graft-type polymers, and block-type polymers based on their structures.

·Polymer compounds

The polymer compound adsorbs to the surface of dispersants such as black pigments and other pigments used in combination depending on the purpose (hereinafter, black pigments and other pigments are collectively referred to as "pigments"), and re-agglomerates the dispersants. It acts to prevent. Therefore, terminal-modified polymers, graft-type (containing polymer chains) polymers, or block-type polymers containing anchor sites for the pigment surface are preferred.

The polymer compound may have a curable group.

Examples of the curable group include groups containing an ethylenically unsaturated bond (hereinafter also referred to as “ethylenically unsaturated group”) (e.g., (meth)acryloyl group, vinyl group, and styryl group, etc.), and Cyclic ether groups (for example, epoxy groups, oxetane groups, etc.) may be included, but are not limited to these.

Among them, since polymerization can be controlled by radical reaction, as the curable group, an ethylenically unsaturated group is preferable and a (meth)acryloyl group is more preferable.

The light-shielding composition preferably contains a dispersion resin having a curable group (more preferably an ethylenically unsaturated group) because the light-shielding film has better light resistance, moisture resistance, and heat resistance.

Examples of the dispersion resin containing a curable group include a polymer compound having a structural unit with a curable group (more preferably an ethylenically unsaturated group such as a (meth)acryloyl group). Additionally, in this specification, “structural unit” has the same meaning as “repeating unit.”

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

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

The resin containing the curable group preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and/or a polyether structure, and as described later, when the resin contains a structural unit containing a graft chain, the polymer chain may have a polyester structure. , and/or may contain a polyether structure.

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

It is preferable that the polymer compound contains a structural unit containing a graft chain. Additionally, in this specification, “structural unit” has the same meaning as “repeating unit.”

Since the polymer compound containing a structural unit containing such a graft chain has affinity for a solvent due to the graft chain, it is excellent in dispersibility of pigments and the like and dispersion stability over time (stability over time). Additionally, due to the presence of a graft chain, a polymer compound containing a structural unit containing a graft chain has affinity with a polymerizable compound or other resins that can be used in combination. As a result, it becomes difficult for residues to be generated due to alkali phenomenon.

As the graft chain becomes longer, the steric repulsion effect increases and the dispersibility of pigments etc. improves. On the other hand, if the graft chain is excessively long, the adsorption capacity for pigments, etc. decreases, and the dispersibility of pigments, etc. tends to decrease. For this reason, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and more preferably 60 to 500 atoms excluding hydrogen atoms. .

Here, the graft chain refers to the origin of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the terminal of the group branched from the main chain.

The graft chain preferably contains a polymer structure, and examples of such polymer structures include poly(meth)acrylate structure (e.g., poly(meth)acrylic structure), polyester structure, and polyurethane. structures, polyurea structures, polyamide structures, and polyether structures.

In order to improve the interaction between the graft chain and the solvent and thereby increase the dispersibility of pigments, etc., the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure. It is preferable that it is a graft chain containing a species, and it is more preferable that it is a graft chain containing at least one of a polyester structure and a polyether structure.

The macromonomer containing such a graft chain (a monomer that has a polymer structure and bonds to the main chain of the copolymer to form a graft chain) is not particularly limited, but a macromonomer containing an ethylenically unsaturated group can be suitably used. .

In addition, the polymer compound preferably contains a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth)acryloyl group, because the light resistance, moisture resistance, and heat resistance of the light shielding film are more excellent.

Commercially available macromonomers that are suitably used in the synthesis of polymer compounds corresponding to the structural unit containing the graft chain contained in the polymer compound include AA-6, AA-10, AB-6, AS-6, and AN-6. , AW-6, AA-714, AY-707, AY-714, AK-5, AK-30 and AK-32 (all brand names, manufactured by Toa Gosei Corporation), 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 43 PAPE-600B (all brand names, Nichiyusa) 1) is used. Among these, AA-6, AA-10, AB-6, AS-6, AN-6, or Blemmer PME-4000 are preferred.

The dispersion resin preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate, and cyclic or linear polyester, and includes polymethyl acrylate, polymethyl methacrylate, And it is more preferable to contain at least one structure selected from the group consisting of chain polyesters, and the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. It is more preferable to contain at least one structure selected from: The dispersion resin may contain the above structures alone in one resin, or may contain two or more of these structures in one resin.

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

Specific examples of the dispersion resin containing a polycaprolactone structure include resins where j and k are 5 in the following formulas (1) and (2). Moreover, specific examples of the dispersion resin containing a polyvalerolactone structure include resins where j and k in the following formula (1) and the following formula (2) are 4.

Specific examples of the dispersion resin containing a polymethyl acrylate structure include a resin in the following formula (4) wherein X ⁵ is a hydrogen atom and R ⁴ is a methyl group. Moreover, specific examples of the dispersion resin containing a polymethyl methacrylate structure include a resin in which X ⁵ is a methyl group and R ⁴ is a methyl group in the following formula (4).

· Structural unit containing a graft chain

The polymer compound is a structural unit containing a graft chain, and preferably contains a structural unit represented by any of the following formulas (1) to (4), such as the following formula (1A), the following formula (2A), and the following formula: It is more preferable to contain a structural unit represented by any one of (3A), the following formula (3B), and the following formula (4).

[Formula 4]

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

In formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthetic constraints, X ¹ , X ² , X ³ , X ⁴ , ^and Alternatively, a methyl group is more preferable, and a methyl group is more preferable.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly restricted in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the linking groups (Y-1) to (Y-21) below. In the structure shown below, A and B respectively mean binding sites with the left end group and the right end group in formulas (1) to (4). Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of simplicity of synthesis.

[Formula 5]

In formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, but specifically includes an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. I can hear it. Among these, the organic groups represented by Z ¹ , Z ² , Z ³ , and Z ⁴ are preferably groups containing a steric repulsion effect, especially from the viewpoint of improving dispersibility, and are each independently an alkyl group or an alkoxy group having 5 to 24 carbon atoms. The group is more preferable, and especially, each independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is more preferable. Additionally, the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

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

Moreover, in equations (1) and (2), j and k each independently represent an integer of 2 to 8. j and k in formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5, from the viewpoint of the aging stability and developability of the composition.

Moreover, in formulas (1) and (2), n and m are preferably integers of 10 or more, and more preferably 20 or more. In addition, when the dispersion resin contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the repeating numbers of the polycaprolactone structure and the repeating number of the polyvalerolactone structure is preferably an integer of 10 or more, An integer of 20 or more is more preferable.

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

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the structure of this monovalent organic group is not particularly limited. As R ⁴ , a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom or an alkyl group is more preferable. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, and a straight alkyl group having 1 to 20 carbon atoms is more preferable. It is preferable, and a straight-chain alkyl group having 1 to 6 carbon atoms is more preferable. In Formula (4), when q is 2 to 500, multiple X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

Additionally, the polymer compound may contain two or more types of structural units containing graft chains with different structures. In other words, the molecules of the polymer compound may contain structural units represented by formulas (1) to (4) with different structures, and n, m, p, and q in formulas (1) to (4) are When each represents an integer of 2 or more, in formulas (1) and (2), j and k may contain different structures in the side chain, and in formulas (3) and (4), multiple groups exist in the molecule. R ³ , R ⁴ , and X ⁵ may be the same or different from each other.

As the structural unit represented by formula (1), it is more preferable that it is a structural unit represented by the following formula (1A) from the viewpoint of the aging stability and developability of the composition.

Moreover, as the structural unit represented by formula (2), it is more preferable that it is a structural unit represented by the following formula (2A) from the viewpoint of the aging stability and developability of the composition.

[Formula 6]

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

Moreover, as the structural unit represented by formula (3), it is more preferable that it is a structural unit represented by the following formula (3A) or formula (3B) from the viewpoint of the aging stability and developability of the composition.

[Formula 7]

^In formula (3A) or (3B), X ³ , Y ^{3 ,} Z ³ , and p ^have the same meaning as do.

The polymer compound more preferably contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.

In a polymer compound, the content of a structural unit containing a graft chain (e.g., a structural unit represented by the formulas (1) to (4) above) is, in mass conversion, 2 to 90 relative to the total mass of the polymer compound. Mass% is preferable, and 5 to 30 mass% is more preferable. When the structural unit containing the graft chain is contained within this range, the dispersibility of the pigment is high and the developability when forming a black layer is good.

·Hydrophobic structural unit

Additionally, the polymer compound preferably contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (i.e., does not correspond to the structural unit containing the graft chain). However, in this specification, a hydrophobic structural unit is a structural unit that does not have an acid group (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 more preferably a structural unit derived from a compound with a ClogP value of 1.2 to 8. Thereby, the effect of the present invention can be more reliably expressed.

The ClogP value is a value calculated with the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "calculated logP" calculated by the fragment approach of Hansch and Leo (see literature below). The fragment approach is based on the chemical structure of the compound, dividing the chemical structure into partial structures (fragments), and summing the logP contributions assigned to the fragments to estimate the logP value of the compound. The details are described in the following documents. In this specification, 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 refers to the common logarithm of the partition coefficient P (Partition Coefficient), and is a physical property value that quantitatively indicates how a given organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. , and is expressed in the following equation.

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.

When the value of logP increases from 0 to a positive value, oil solubility increases, and when the absolute value increases to a negative value, water solubility increases, which has a negative correlation with the water solubility of organic compounds and the hydrophobicity of organic compounds. It is widely used as a parameter to evaluate .

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

[Formula 8]

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

R ¹ , R ² , and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R ² and R ³ are more preferably hydrogen atoms.

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

L is a single bond or a divalent linking group. As a divalent linking group, a divalent aliphatic group (e.g., alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (e.g. , arylene group, substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ³¹ -, where R ³¹ includes 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 number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The aliphatic group may be either an unsaturated aliphatic group or a saturated aliphatic group, but a saturated aliphatic group is preferable. Additionally, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups, and heterocyclic groups.

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

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

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

As Z, an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group), a heterocyclic group, and these. A combination of . These groups include an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), and a substituted imino group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group, or a heterocyclic group. ), or a carbonyl group (-CO-) may be included.

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The aliphatic group further includes a ring hydrocarbon group and a cross-linked hydrocarbon group, and examples of the ring hydrocarbon group include a bicyclohexyl group, perhydronaphthalenyl group, biphenyl group, and 4-cyclohexylphenyl group. . As a cross-linked hydrocarbon ring, for example, pinane, bornene, nopineine, norbornene, bicyclooctane ring (bicyclo[2.2.2]octane ring, and bicyclo[3.2.1]oxane ring) Bicyclic hydrocarbon rings such as (theine ring, etc.), homobledane, adamantane, tricyclic rings such as tricyclo[5.2.1.0 ^2,6 ]decane and tricyclo[4.3.1.1 ^2,5 ]undecane rings. Hydrocarbon rings and 4-cyclic hydrocarbon rings such as tetracyclo[4.4.0.1 ^{2,5.1 7,10} ]dodecane and perhydro-1,4-methano-5,8-methanonaphthalene rings. I can hear it. In addition, the cross-linked hydrocarbon ring includes condensed cyclic hydrocarbon rings, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrocarbon ring. Condensed rings in which a plurality of 5- to 8-membered cycloalkane rings, such as a hydrophenalene ring, are condensed are also included.

The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Additionally, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups, and heterocyclic groups. However, the aliphatic group does not have an acid group as a substituent.

The number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. Additionally, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups. However, 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. Another heterocycle, aliphatic ring, or aromatic ring may be condensed with the heterocycle. Additionally, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thioxo groups (=S), imino groups (=NH), and substituted imino groups (=NR ³² , where R ³² is an aliphatic group or an aromatic group. or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the formula (iii), R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), and a carbon number of 1 to 6. represents an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), Z, or LZ. Here, L and Z have the same meaning as L and Z above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

As a monomer represented by the above formula (i), R ¹ , R ² , and R ³ are hydrogen atoms or methyl groups, L is a single bond or a divalent linking group containing an alkylene group or oxyalkylene structure, and Compounds in which Z is an atom or an imino group and Z is an aliphatic group, heterocyclic group, or aromatic group are preferred.

Moreover, as the monomer represented by the above formula (ii), a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable. Moreover, as the monomer represented by the above formula (iii), a compound in which R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms or methyl groups, and Z is an aliphatic group, heterocyclic group, or aromatic group is preferable.

Examples of representative compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, and styrenes.

In addition, as examples of representative compounds represented by formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of Japanese Patent Application Laid-Open No. 2013-249417 can be referred to, and these contents are incorporated herein by reference.

In a polymer compound, the content of the hydrophobic structural unit, in terms of mass, is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, relative to the total mass of the polymer compound. When the content is within the above range, sufficient pattern formation is obtained.

·Functional group that can form interactions with pigments, etc.

The polymer compound may introduce a functional group capable of forming an interaction with a pigment or the like (for example, a black pigment). Here, it is preferable that the polymer compound further contains a structural unit containing a functional group capable of forming an interaction with a pigment or the like.

Examples of functional groups capable of forming interactions with pigments, etc. include acid groups, basic groups, coordinating groups, and reactive functional groups.

When the polymer compound contains an acid group, a basic group, a coordination group, or a reactive functional group, a structural unit containing an acid group, a structural unit containing a basic group, a structural unit containing a coordination group, or a reactive structure, respectively. It is desirable to contain units.

In particular, if the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, developability for pattern formation by alkali development can be imparted to the polymer compound.

That is, when an alkali-soluble group is introduced into a polymer compound, the composition contains an alkali-soluble polymer compound as a dispersion resin that contributes to the dispersion of pigments and the like. A composition containing such a polymer compound has excellent light-shielding properties of the black layer formed by exposure, and also improves alkali developability of unexposed areas.

Additionally, if the polymer compound contains a structural unit containing an acid group, the polymer compound becomes more likely to be compatible with the solvent, and coating properties tend to improve.

This means that the acid group in the structural unit containing the acid group easily interacts with the pigment, etc., and the polymer compound stably disperses the pigment, etc., and the viscosity of the polymer compound dispersing the pigment, etc. is low, so that the polymer compound itself It is presumed that this is because it is easy to disperse stably.

However, the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain, or may be a different structural unit, but the structural unit containing an alkali-soluble group as an acid group may have the hydrophobic structure described above. It is a structural unit different from the unit (i.e., it does not correspond to the hydrophobic structural unit described above).

Examples of the acid group, which is a functional group capable of forming an interaction with pigments, etc., include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. At least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferred, and the carboxylic acid group is It is more desirable. The carboxylic acid group has good adsorption capacity for pigments, etc., and also has high dispersibility.

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

The polymer compound may have one or two or more types of structural units containing an acid group.

The polymer compound may or may not contain a structural unit containing an acid group, but when contained, 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, From the point of suppressing damage to the burn intensity caused by alkali phenomenon, 10 to 60% by mass is more preferable.

Examples of basic groups that are functional groups capable of forming interactions with pigments, etc. include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, and amide groups, and preferred basic groups include The group is a tertiary amino group because it has good adsorption capacity for pigments, etc. and also has high dispersibility. The polymer compound may contain one or two or more types of these basic groups.

The polymer compound may or may not contain a structural unit containing a basic group, but if it does, the content of the structural unit containing a basic group is 0.01 to 50% by mass, in terms of mass, relative to the total mass of the polymer compound. is preferable, and from the point of suppressing development inhibition, 0.01 to 30 mass% is more preferable.

Coordinating groups, which are functional groups capable of forming interactions with pigments, etc., and functional groups having reactivity include, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acid chloride. . A preferable functional group is an acetylacetoxy group because it has good adsorption capacity for pigments, etc. and has high dispersibility of pigments, etc. The polymer compound may have one type or two or more types 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 these structural units is calculated as the total of the polymer compound in terms of mass. With respect to the mass, 10 to 80 mass% is preferable, and from the point of suppressing inhibition of developability, 20 to 60 mass% is more preferable.

When the polymer compound contains, in addition to the graft chain, a functional group capable of forming an interaction with pigments, etc., it is sufficient to contain a functional group capable of forming an interaction with the above-mentioned various pigments, etc., and how these functional groups are introduced Although not particularly limited, the polymer compound preferably contains one or more types of structural units selected from structural units derived from monomers represented by the following formulas (iv) to (vi).

[Formula 9]

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), or a carbon number. Represents an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.) with a value of 1 to 6.

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. In formula (iv), R ¹² and R ¹³ are more preferably hydrogen atoms.

X ₁ in formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferable.

Moreover, Y in formula (v) represents a metaphosphorus group or a nitrogen atom.

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

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

In formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with a pigment or the like in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, and more preferably a carboxylic acid group.

In formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), and a carbon number of 1 to 6. Represents an alkyl group (eg, methyl group, ethyl group, propyl group, etc.), -Z ₁ , or L ₁ -Z ₁ . Here, L ₁ and Z ₁ have the same meaning 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 preferable, and a hydrogen atom is more preferable.

As a monomer represented by formula (iv), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or a methyl group, L ₁ is an alkylene group or a divalent linking group containing an oxyalkylene structure, and X ₁ is oxygen. Compounds in which Z 1 is an atom or an imino group and Z ₁ is a carboxylic acid group are preferred.

Moreover, as the monomer represented by formula (v), a compound in which R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a metaphosphoric group is preferable.

Also, as the monomer represented by formula (vi), a compound is preferable where R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z ₁ is a carboxylic acid group.

Below, representative examples of monomers (compounds) represented by formulas (iv) to (vi) are shown.

Examples of monomers 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, and molecules. A reactant between a compound containing an addition polymerizable double bond and a hydroxyl group and phthalic anhydride, a reactant between a compound containing an addition polymerizable double bond and a hydroxyl group within the molecule and tetrahydroxyphthalic anhydride, and a reaction product between a compound containing an addition polymerizable double bond and a hydroxyl group within the molecule and a hydroxyl group within the molecule. Reactants of compounds containing trimellitic anhydride with compounds containing addition polymerizable double bonds and hydroxyl groups in the molecule and reactants of pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4 - Vinyl benzoic acid, vinyl phenol, and 4-hydroxyphenyl methacrylamide can be mentioned.

The content of the structural unit containing a functional group capable of forming an interaction with the pigment, etc. is 0.05 in terms of mass, relative to the total mass of the polymer compound, in terms of interaction with the pigment, etc., stability over time, and permeability to the developing solution. ~90 mass% is preferable, 1.0-80 mass% is more preferable, and 10-70 mass% is more preferable.

·Other structural units

In addition, the polymer compound may form interactions with structural units containing graft chains, hydrophobic structural units, and pigments, etc., for the purpose of improving all performances such as image intensity, as long as it does not impair the effects of the present invention. It may further have other structural units having various functions different from the structural unit containing the functional group (for example, a structural unit containing a functional group having affinity for a solvent, etc., which will be described later).

Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, etc.

The polymer compound may contain one or two or more types of these different structural units, and the content, in terms of mass, is preferably 0 to 80% by mass, and is preferably 10 to 60% by mass, relative to the total mass of the polymer compound. is more preferable. When the content is in the above range, sufficient pattern formation is maintained.

·Physical properties of polymer compounds

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

If the acid value of the polymer compound is 160 mgKOH/g or less, pattern peeling during development when forming a black layer is suppressed more effectively. Moreover, when the acid value of a polymer compound is 10 mgKOH/g or more, alkali developability becomes more favorable. Moreover, if the acid value of the polymer compound is 20 mgKOH/g or more, sedimentation of pigments and the like can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition can be further improved.

In this specification, the acid value can be calculated, for example, from the average content of acid groups in the compound. Additionally, by changing the content of the structural unit containing an acid group, which is a component of the resin, a resin having the desired acid value can be obtained.

The weight average molecular weight of the polymer compound is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, more preferably 6,000 to 100,000, and especially preferably 10,000 to 50,000.

High molecular compounds can be synthesized based on known methods.

Specific examples of polymer compounds include "DA-7301" manufactured by Kusumoto Chemical Industries, Ltd., "Disperbyk-101 (polyamideamine phosphate) manufactured by BYK Chemie, 107 (carboxylic acid ester), 110 (copolymer containing an acid group), and 111 (phosphoric acid-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047 manufactured by EFKA Corporation , 4050~4010~4165 (polyurethane type), EFKA4330~4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 ( Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", "Azisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine Techno Co., Ltd., "Flolene TG-710" manufactured by Kyoeisha Chemical Co., Ltd. (Urethane oligomer)", "Polyflo No. 50E, No. 300 (acrylic copolymer)", "Disparon KS-860, 873SN, 874, #2150 (aliphatic polyhydric carboxylic acid) manufactured by Kusumoto Chemical Industries, Ltd. #7004 (polyetherester), DA-703-50, DA-705, DA-725", Kao's "Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic Sulfonic acid formalin polycondensate)", "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearyl) Amine acetate)", Nippon Lubrizol's "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (contains a functional moiety at the terminal) polymer), 24000, 28000, 32000, 38500 (graft copolymer)", Nikko Chemicals, "Niccol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawa “Hinoact T-8000E” manufactured by Ken Fine Chemical, etc., “Organosiloxane Polymer KP-341” manufactured by Shin-Etsu Chemical, “W001: Cationic Surfactant” manufactured by Yusho, polyoxyethylene lauryl ether, Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan Nonionic surfactants such as fatty acid esters, anionic surfactants such as "W004, W005, W017", Morishita Sankyo's "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", polymer dispersants such as Sannopco's "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100", ADEKA's "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123", and Sanyo Chemical's "Ionet (Product Name) S-20", etc. You can. Additionally, Acribase FFS-6752 and Acribase FFS-187 can also be used.

Additionally, it is also preferable to use an amphoteric resin containing an acidic group and a basic group. The amphoteric resin preferably has an acid value of 5 mgKOH/g or more and an amine value of 5 mgKOH/g or more.

Commercially available products of amphoteric resin include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2010, and DISPERBYK manufactured by Big Chemistry. -2012, DISPERBYK-2025, BYK-9076, Azispur PB821, Azispur PB822, and Azispur PB881 manufactured by Ajinomoto Fine Techno, etc.

These polymer compounds may be used individually by one type, or two or more types may be used together.

In addition, as specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of Japanese Patent Application Laid-Open No. 2013-249417, the contents of which are incorporated herein by reference.

Additionally, as the dispersion resin, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of Japanese Patent Application Laid-Open No. 2010-106268 (corresponding paragraphs 0075 to 0133 of US2011/0124824) can be used, the contents of which are incorporated herein by reference. may be included in this specification.

In addition to the above, a polymer compound containing a component containing a side chain structure formed by bonding an acidic group of paragraphs 0028 to 0084 of Japanese Patent Application Laid-Open No. 2011-153283 (paragraphs 0075 to 0133 of corresponding US2011/0279759) through a linking group. can be used, and these contents can be used by reference and are included in this specification.

In addition, as the dispersion resin, the resin described in paragraphs 0033 to 0049 of Japanese Patent Application Publication No. 2016-109763 can also be used, the contents of which are incorporated herein by reference.

(Alkali soluble resin)

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

The content of the alkali-soluble resin in the composition is not particularly limited, but is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and still more preferably 5 to 15% by mass, relative to the total solid content of the composition. .

Alkali-soluble resin may be used individually as one type, or two or more types may be used in combination. When two or more types of alkali-soluble resins are used together, it is preferable that the total content is within the above range.

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

Specific examples of alkali-soluble resins include copolymer resins of unsaturated carboxylic acids and ethylenically unsaturated compounds.

Unsaturated carboxylic acids are not particularly limited, but include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; Dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or acid anhydrides thereof; and polyhydric carboxylic acid monoesters such as mono(2-(meth)acryloyloxyethyl) phthalate.

Examples of copolymerizable ethylenically unsaturated compounds include methyl (meth)acrylate. In addition, the compounds described in paragraph 0027 of Japanese Patent Application Laid-Open No. 2010-097210 and paragraphs 0036 to 0037 of Japanese Patent Application Laid-Open No. 2015-068893 can also be used, the contents of which are incorporated herein by reference.

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

As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferable.

Examples of the curable group include the same curable groups that the above-mentioned polymer compound may contain, and the preferable range is also the same.

As the alkali-soluble resin containing a curable group, an alkali-soluble resin having a curable group in the side chain is preferable. Examples of the alkali-soluble resin containing a curable group include Dianal NR series (manufactured by Mitsubishi Rayon), Photomer6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscot R-264, and KS Resist 106 (all by Yuki Osaka). Kagaku Kogyo Co., Ltd.), Cyclomer P series (e.g., ACA230AA), Flaxel CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (produced by Daicel Allnex Co., Ltd.), and Acricure RD-F8 (Nippon Shokubai Co., Ltd.) j), etc.

Examples of alkali-soluble resins include Japanese Patent Publication No. 59-044615, Japanese Patent Publication No. 54-034327, Japanese Patent Publication No. 58-012577, Japanese Patent Publication No. 54-025957, and Japanese Patent Publication No. 54-025957. radical polymers containing a carboxylic acid group in the side chain described in Japanese Patent Application Publication No. 54-092723, Japanese Patent Application Publication No. 59-053836, and Japanese Patent Application Publication No. 59-071048; Acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group described in European Patent Publication No. 993966, European Patent Publication No. 1204000, and Japanese Patent Publication No. 2001-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon, and polyether, which is a reaction product of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, etc.; and the polyimide resin described in International Publication No. 2008/123097, etc. can be used.

As the alkali-soluble resin, for example, compounds described in paragraphs 0225 to 0245 of Japanese Patent Application Laid-Open No. 2016-075845 can also be used, the contents of which are incorporated herein by reference.

As an alkali-soluble resin, a polyimide precursor can also be used. A polyimide precursor means a resin obtained by carrying out an addition polymerization reaction of a compound containing an acid anhydride group and a diamine compound at 40 to 100°C.

Examples of polyimide precursors include resins containing a repeating unit represented by formula (1). As a polyimide precursor, for example, an amic acid structure represented by the following formula (2), a following formula (3) in which the amic acid structure is partially imide ring-closed, and a following formula (4) in which all of the amic acid structures are imide ring-closed. and polyimide precursors containing the imide structures shown.

In addition, in this specification, a polyimide precursor having an amic acid structure may be referred to as polyamic acid.

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

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

Specific examples of the polyimide precursor include, for example, the compounds described in paragraphs 0011 to 0031 of JP2008-106250, the compounds described in paragraphs 0022 to 0039 of JP2016-122101, and the compounds described in JP2016-106250A. The compounds described in paragraphs 0061 to 0092 of No. 068401, etc. can be mentioned, and the contents of the above are incorporated herein by reference.

The alkali-soluble resin also preferably contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor because the pattern shape of the patterned black layer obtained using the composition is superior.

The polyimide resin containing an alkali-soluble group is not particularly limited, and any known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include the resin described in paragraph 0050 of JP2014-137523A, the resin described in paragraph 0058 of JP2015-187676A, and the resins described in paragraphs 0012 to 0013 of JP2014-106326A. The resins described in and the like can be mentioned, and the above content is incorporated herein by reference.

As an alkali-soluble resin, a polybenzoxazole precursor can also be used.

Polybenzoxazole precursor is a resin synthesized from hydroxyl-containing diamine and dicarboxylic acid derivatives.

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

Examples of dicarboxylic acid derivatives include dicarboxylic acid derivatives such as dicarboxylic acid chloride and dicarboxylic acid ester, and aromatic dicarboxylic acid derivatives are preferable. Specific examples of dicarboxylic acid derivatives include isophthalic acid dichloride and terephthalic acid dichloride.

Specific examples of polybenzoxazole precursors include polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide.

Specific examples of polybenzoxazole precursors include, for example, the compounds described in paragraphs 0049 to 0062 of Japanese Patent Application Laid-Open No. 2003-121997, the compounds described in paragraphs 0050 to 0057 of International Publication No. 2017/057281, and International Publication No. 2016/ The compounds described in paragraphs 0015 to 0043 of No. 043203, etc. can be mentioned, the contents of which are incorporated herein by reference.

The copolymer of the polyimide precursor and the polybenzoxazole precursor is a copolymer having a polyamic acid ester structural unit and a hydroxypolyamide structural unit, for example, a polyamic acid ester structural unit and a hydroxypolyamide structural unit. Examples include copolymers having an alternating copolymer structure.

As the alkali-soluble resin, at least one selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and copolymers thereof is preferable, and polyimide resin is more preferable because the light resistance and heat resistance of the light shielding film are more excellent.

In addition, as the alkali-soluble resin, [benzyl (meth)acrylate/(meth)acrylic acid/other addition polymerizable vinyl monomer as needed] copolymer, and [allyl (meth)acrylate/(meth)acrylic acid/as needed] Accordingly, other addition-polymerizable vinyl monomer] copolymers are suitable because they have an excellent balance of film strength, sensitivity, and developability.

The other addition polymerizable vinyl monomers mentioned above may be used alone or in combination of two or more.

Since the moisture resistance of the black layer is more excellent, the copolymer preferably has a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth)acryloyl group.

For example, a curable group may be introduced into the copolymer by using a monomer having a curable group as the addition polymerizable vinyl monomer mentioned above. In addition, at least one, part or all 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 contain a curable group (preferably a (meth)acryloyl group). ethylenically unsaturated groups, etc.) may be introduced.

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

Examples of the ether dimer include compounds represented by the following general formula (ED1) and compounds represented by the following general formula (ED2).

[Formula 14]

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

[Formula 15]

In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of general formula (ED2), the description in Japanese Patent Application Publication No. 2010-168539 can be referred to.

As a specific example of the ether dimer, for example, paragraph 0317 of Japanese Patent Application Publication No. 2013-029760 can be referred to, and this content is incorporated herein by reference. The number of ether dimers may be one, or two or more types may be used.

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

<Polymerizable compound>

The light-shielding composition contains a polymerizable compound.

In this specification, a polymerizable compound means a compound that polymerizes under the action of a polymerization initiator described later, and means a component different from the dispersion resin and alkali-soluble resin described above.

The content of the polymerizable compound in the composition is not particularly limited, but is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass, based on the total solid content of the composition. . The polymerizable compound may be used individually or in combination of two or more types. When two or more types of polymerizable compounds are used together, it is preferable that the total content is within the above range.

The molecular weight (or weight average molecular weight) of the polymerizable compound is not particularly limited, but is preferably 2000 or less.

As the polymerizable compound, a compound containing an ethylenically unsaturated group is preferable.

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

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

As the polymerizable compound, for example, compounds described in paragraph 0050 of Japanese Patent Application Laid-Open No. 2008-260927 and paragraph 0040 of Japanese Patent Application Laid-Open No. 2015-068893 can be used, the contents of which are incorporated herein by reference.

The polymerizable compound may be in any chemical form, such as monomers, prepolymers, oligomers, mixtures thereof, and multimers thereof.

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

The polymerizable compound is also preferably a compound that contains one or more ethylenically unsaturated groups and has a boiling point of 100°C or higher under normal pressure. For example, reference can be made to the compounds described in paragraph 0227 of Japanese Patent Application Laid-Open No. 2013-029760 and paragraphs 0254 to 0257 of Japanese Patent Application Publication No. 2008-292970, the contents of which are incorporated herein by reference.

Polymerizable compounds include 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.), and Pentaerythritol 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 Shinnakamura Kogyo Chemical Co., Ltd.), and structures in which their (meth)acryloyl group is sandwiched between an ethylene glycol residue or a propylene glycol residue (for example, commercially available from Sartomer). SR454, SR499) are preferred. These oligomeric types can also be used. Additionally, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shinnakamura Chemical Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (all Product names (manufactured by Nippon Kayaku Co., Ltd.), etc. may be used.

The preferred embodiments of the polymerizable compound are shown below.

It is preferable that the light-shielding composition contains at least two types of polymerizable compounds.

Among them, since the heat resistance and moisture resistance of the light shielding film are more excellent, the compound containing two or more types of polymerizable compounds having similar structures and different numbers of ethylenically unsaturated groups, and having a smaller number of ethylenically unsaturated groups is at least preferred. It is preferable that it is a compound containing at least one hydroxyl group. It is not clear why the heat resistance and moisture resistance of the light shielding film are improved by using two or more types of polymerizable compounds, but by using a polymerizable compound having a hydroxyl group, compatibility with alkali-soluble resin is improved, and polymerizability is improved. It is presumed that this is because the compound is distributed uniformly in the black layer and the entire black layer is cured uniformly.

As a mixture of two or more compounds having similar structures and different numbers of ethylenically unsaturated groups, for example, they are represented by the formula (Z-1), formula (Z-4), or formula (Z-5) described later. , a mixture of compounds having different numbers of ethylenically unsaturated groups (preferably (meth)acryloyl groups) at the terminals, wherein the compound having a smaller number of ethylenically unsaturated groups is a compound containing at least one hydroxyl group. I can hear it.

The polymerizable compound may have acid groups 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 polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a polymerizable compound in which an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group is more preferred. Preferred, and in this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol is more preferable. Commercially available products include, for example, Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Corporation.

The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH/g, and more preferably 5 to 30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

The polymerizable compound is also a compound containing a caprolactone structure.

The compound containing the caprolactone structure is not particularly limited as long as it contains the caprolactone structure in the molecule, and examples include trimethylol ethane, ditrimethylol ethane, trimethylolpropane, ditrimethylolpropane, Modified ε-caprolactone obtained by esterifying (meth)acrylic acid and ε-caprolactone with a polyhydric alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine. and polyfunctional (meth)acrylate. Among them, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferable.

[Formula 16]

In the formula (Z-1), all 6 R are groups represented by the formula (Z-2) below, or 1 to 5 of the 6 R are groups represented by the formula (Z-2) below, and the remainder is represented by the formula (Z-2) below. It is a group represented by the formula (Z-3).

[Formula 17]

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

[Formula 18]

In formula (Z-3), R ¹ 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 (m = 1 in the above formulas (Z-1) to (Z-3), Number of groups represented by formula (Z-2) = 2, compound where R ¹ is all hydrogen atom), DPCA-30 (same formula, m = 1, number of groups represented by formula (Z-2) = 3, R Compound where ¹ is all a hydrogen atom), DPCA-60 (same formula, m=1, number of groups represented by formula (Z-2)=6, compound where R ¹ is all a hydrogen atom), and DPCA-120 (same formula In the formula, m = 2, the number of groups represented by the formula (Z-2) = 6, and compounds in which all R ¹ are hydrogen atoms), etc. can be mentioned. Additionally, commercially available polymerizable compounds containing a caprolactone structure include M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.

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

[Formula 19]

In formulas (Z-4) and (Z-5), E represents -((CH ₂ ) _y CH ₂ O)-, or ((CH ₂ ) _y CH(CH ₃ )O)-, and y is , 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 of (meth)acryloyl groups is 3 or 4, m represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.

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

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

Moreover, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.

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

Moreover, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.

In addition, -((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)- in formula (Z-4) or formula (Z-5) is the terminal on the oxygen atom side. This form of binding to X is preferred.

The compounds represented by formula (Z-4) or formula (Z-5) may be used individually, or two or more types may be used in combination. In particular, in formula (Z-5), a form in which all 6 A preferred embodiment is a mixture with a compound in which each is a hydrogen atom. With such a structure, the heat resistance and moisture resistance of the light shielding film can be further improved, and developability can be further improved.

Moreover, 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 preferable.

Additionally, the polymerizable compound may contain a cardo skeleton.

As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.

The polymerizable compound containing a cardo skeleton is not limited, but examples include Oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).

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

The content of ethylenically unsaturated groups in the polymerizable compound (meaning the number of ethylenically unsaturated groups in the polymerizable compound divided by the molecular weight (g/mol) of the polymerizable compound) is preferably 5.0 mmol/g or more. The upper limit is not particularly limited, but is generally 20.0 mmol/g or less.

<Polymerization initiator>

The light-shielding composition preferably contains a polymerization initiator.

The polymerization initiator is not particularly limited, and known polymerization initiators can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, with the photopolymerization initiator being preferable. Moreover, as a polymerization initiator, a so-called radical polymerization initiator is preferable.

The content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and still more preferably 1.5 to 8% by mass, based on the total solid content of the composition. A polymerization initiator may be used individually by 1 type, or may use 2 or more types together. When using two or more types of polymerization initiators together, it is preferable that the total content is within the above range.

(Thermal polymerization initiator)

As a thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalononitrile and dimethyl-(2,2')-azobis. Azo compounds such as (2-methylpropionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate are included.

Specific examples of the thermal polymerization initiator include the polymerization initiators described on pages 65 to 148 of "Ultraviolet Curing System" by Kiyomi Kato (published by Sogo Kijutsu Center Co., Ltd.: 1st year of Heisei).

(Photopolymerization initiator)

The composition preferably contains a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and any known photopolymerization initiator can be used. As a photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from the ultraviolet region to the visible light region is preferable. Additionally, it may be an activator that generates active radicals by producing a certain effect with the photoexcited sensitizer, or it may be an initiator that initiates cationic polymerization depending on the type of polymerizable compound.

Moreover, the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 within the range of 300 to 800 nm (330 to 500 nm is more preferable).

The content of the photopolymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and still more preferably 1.5 to 8% by mass, relative to the total solid content of the composition. The photopolymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more types. When using two or more types of photopolymerization initiators together, it is preferable that the total content is within the above range.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaaryl. Oxime compounds such as biimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.

As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-029760 can be referred to, and this content is incorporated herein by reference.

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

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

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

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

·Oxime compound

As a photopolymerization initiator, an oxime ester polymerization initiator (oxime compound) is more preferable. In particular, oxime compounds are preferable because they are highly sensitive, have high polymerization efficiency, and make it easy to design a high content of the colorant in the composition.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, or compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

Examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-3-. one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

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

Commercially available products include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF). In addition, TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Ackles NCI-831, Adeka Ackles NCI-930 (made by ADEKA), Alternatively, N-1919 (a photoinitiator containing a carbazole/oxime ester skeleton (manufactured by ADEKA) 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 carbazole N; Compounds described in US Patent No. 7626957 in which a hetero substituent is introduced at the benzophenone moiety; Compounds described in Japanese Patent Application Publication No. 2010-015025 and U.S. Patent Application Publication No. 2009-292039, in which a nitro group is introduced into the pigment portion; Ketoxime compounds described in International Publication No. 2009-131189; and compounds described in U.S. Patent Publication No. 7556910, which contain a triazine skeleton and an oxime skeleton in the same molecule; Compounds such as those described in Japanese Patent Application Laid-Open No. 2009-221114, which have a maximum absorption at 405 nm and good sensitivity to g-ray light sources, may be used.

For example, paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-029760 may be referred to, the contents of which are incorporated herein by reference.

Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. Additionally, 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.

[Formula 20]

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

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

Examples of the monovalent non-metallic atomic group include alkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic group, alkylthiocarbonyl group, and arylthiocarbonyl group. Additionally, these groups may have one or more substituents. In addition, the above-mentioned substituent may be further substituted with another substituent.

Substituents include halogen atoms, aryloxy groups, alkoxycarbonyl or aryloxycarbonyl groups, acyloxy groups, acyl groups, alkyl groups, and aryl groups.

In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group, and an aryl group or a heterocyclic group is more preferable. These groups may have one or more substituents. Examples of the substituent include the substituents described above.

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

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 Application Laid-Open No. 2010-262028; Compounds 24, 36-40 described in Japanese Patent Publication No. 2014-500852; and compound (C-3) described in Japanese Patent Application Laid-Open No. 2013-164471. This content is incorporated herein by reference.

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

[Formula 21]

[Formula 22]

In formula (1), R ¹ and R ² are each independently an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 4 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an aryl group with 7 to 30 carbon atoms. When it represents an alkyl group and R ¹ and R ² are phenyl groups, the phenyl groups may combine to form a fluorene group, and R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, and 6 to 30 carbon atoms. represents an aryl group, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 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 meaning as R ¹ , R ² , R ³ , and R ⁴ in formula (1), and R ⁵ is - R ⁶ , -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, a halogen atom, or a hydroxyl group, and R ⁶ represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 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), R ¹ represents an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 4 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an arylalkyl group with 7 to 30 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 4 to 20 carbon atoms, and Or it represents a carbonyl group.

In formula (4), R ¹ , R ³ , and R ⁴ have the same meaning as R ¹ , R ³ , and R ⁴ in formula (3), and R ⁵ is -R ⁶ , -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen represents an atom or a hydroxyl group, R ⁶ represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 4 to 20 carbon atoms, and Or represents a carbonyl group, and a represents an integer of 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group, or phenyl group. R ³ is preferably a methyl group, ethyl group, phenyl group, tolyl group, or xylyl group. R ⁴ is preferably an alkyl group or phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably a methyl group, ethyl group, phenyl group, tolyl group, or naphthyl group. X is preferably directly bonded.

Moreover, in the above formulas (3) and (4), R ¹ is preferably a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group, or phenyl group. R ³ is preferably a methyl group, ethyl group, phenyl group, tolyl group, or xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ⁵ is preferably a methyl group, ethyl group, phenyl group, tolyl group, or naphthyl group. X is preferably directly bonded.

Specific examples of the compounds represented by formula (1) and formula (2) include the compounds described in paragraphs 0076 to 0079 of Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated herein by reference.

Specific examples of oxime compounds preferably used in the composition are shown below. Among the oxime compounds shown below, the oxime compound represented by formula (C-13) is more preferable.

In addition, as the oxime compound, the compounds described in Table 1 of International Publication No. 2015-036910 can also be used, the contents of which are incorporated herein by reference.

[Formula 23]

[Formula 24]

The oxime compound preferably has a maximum absorption in the wavelength range of 350 to 500 nm, more preferably has a maximum absorption in the wavelength range of 360 to 480 nm, and has a high absorbance in the wavelengths of 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and still more preferably 5,000 to 200,000.

The molar extinction coefficient of a compound can be measured by a known method, but is preferably measured at a concentration of 0.01 g/L using ethyl acetate, for example, with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian). do.

The photopolymerization initiator may be used in combination of two or more types as needed.

In addition, as a photopolymerization initiator, compounds described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2008-260927, paragraphs 0033 to 0037 of Japanese Patent Application Laid-Open No. 2010-097210, and paragraph 0044 of Japanese Patent Application Laid-Open No. 2015-068893 can also be used. , the above contents are incorporated in this specification.

<Polymerization inhibitor>

The composition may contain a polymerization inhibitor.

The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used. Examples of polymerization inhibitors 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-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc. ); Hydroquinone-based polymerization inhibitors (e.g., hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); Quinone-based polymerization inhibitors (for example, benzoquinone, etc.); Free radical polymerization inhibitors (e.g., 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- oxyl free radical, etc.); Nitrobenzene-based polymerization inhibitors (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors (for example, phenothiazine, 2-methoxyphenothiazine, etc.).

Among them, a phenol-based polymerization inhibitor or a free radical-based polymerization inhibitor is preferable because the composition has a more excellent effect.

The effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group.

The content of the polymerization inhibitor in the composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, more preferably 0.001 to 0.2% by mass, and still more preferably 0.008 to 0.05% by mass, based on the total solid content of the composition. . The polymerization inhibitor may be used individually as one type, or may be used in combination of two or more types. When using two or more types of polymerization inhibitors together, it is preferable that the total content is within the above range.

Moreover, 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, and more preferably 0.0006 to 0.02. , 0.0006 to 0.005 is more preferable.

<UV absorbent>

The composition may contain an ultraviolet absorber. As a result, the shape of the pattern of the black layer can be made more excellent (fine).

As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As these specific examples, the compounds of paragraphs 0137 to 0142 of Japanese Patent Application Laid-Open No. 2012-068418 (corresponding paragraphs 0251 to 0254 of US2012/0068292) can be used, the content of which can be used, and is included in this specification.

In addition, diethylamino-phenylsulfonyl-based ultraviolet absorbers (manufactured by Daito Chemical Co., Ltd., brand name, UV-503) are also suitably used.

Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of Japanese Patent Application Laid-Open No. 2012-032556.

The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass, based on the total solid content of the composition.

<Silane coupling agent (adhesive agent)>

The composition may contain a silane coupling agent. The silane coupling agent functions as an adhesive that improves the adhesion between the substrate and the black layer when forming the black layer on the substrate.

A silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. Additionally, hydrolyzable groups such as alkoxy groups are bonded to silicon atoms.

A hydrolyzable group refers to a substituent that is directly connected to a silicon atom and can generate a siloxane bond through a hydrolysis reaction and/or condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, and alkenyloxy groups. When the hydrolyzable group contains carbon atoms, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group with 4 or less carbon atoms or an alkenyloxy group with 4 or less carbon atoms is preferable.

In addition, when forming a black layer on a substrate, the silane coupling agent improves the adhesion between the substrate and the black layer, so it does not contain fluorine atoms and silicon atoms (except silicon atoms to which hydrolyzable groups are bonded). It is preferable that it does not contain a fluorine atom, a silicon atom (however, excluding the silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a straight-chain alkyl group with 8 or more carbon atoms, and a branched alkyl group with 3 or more carbon atoms. desirable.

The silane coupling agent may contain an ethylenically unsaturated group such as a (meth)acryloyl group. When it contains 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 (for example, compounds containing a hydrolyzable group and an ethylenically unsaturated group and having a molecular weight of 2000 or less) do not correspond to the polymerizable compounds described above.

The content of the silane coupling agent in the composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 1.0 to 6% by mass, based on the total solid content in the composition.

The composition may contain one type of silane coupling agent, or may contain two or more types of silane coupling agent. When the composition contains two or more types of silane coupling agents, the total may be within the above range.

Silane coupling agents include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. Doxypropylmethyl diethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane are included.

<Surfactant>

The composition may contain a surfactant. Surfactants contribute to improving the applicability of the composition.

When the composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and more preferably 0.01 to 0.1% by mass, based on the total solid content of the composition. desirable.

Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more types of surfactants are used together, it is preferable that the total amount is within the above range.

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

For example, when the composition contains a fluorine-based surfactant, the liquid properties (particularly fluidity) of the composition are further improved. That is, in the case of forming a film using a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and the applicability to the surface to be coated is improved. . For this reason, even when a thin film of the order of several μm is formed with a small amount of liquid, it is effective in that a film of uniform thickness with small thickness unevenness can be formed more suitably.

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

Examples of fluorine-based surfactants include Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, and F482. , F554, and F780 (manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (manufactured by Sumitomo 3M Corporation); Surfron S-382, East SC-101, East SC-103, East SC-104, East SC-105, East SC-1068, East SC-381, East SC-383, East S-393, and East KH- 40 (above, manufactured by Asahi Glass Co., Ltd.); and PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA).

Block polymers can also be used as fluorine-based surfactants, and specific examples include compounds described in Japanese Patent Application Laid-Open No. 2011-089090.

<Solvent>

The composition preferably contains a solvent.

The solvent is not particularly limited and any known solvent can be used.

The content of the solvent in the composition is not particularly limited, but the solid content of the composition is preferably 10 to 90% by mass, more preferably 10 to 40% by mass, and 15 to 35% by mass. This is more preferable.

One type of solvent may be used individually, or two or more types may be used together. When using two or more types of solvents together, it is preferable to adjust the total solid content of the composition so that it falls within the above range.

Examples of solvents include water and organic solvents.

(organic solvent)

Organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol. Lycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, Ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, 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-methoxypropylacetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate. etc., but are not limited to these.

(water)

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

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

<Other optional ingredients>

The composition may further contain other optional components other than the components mentioned above. Examples include sensitizers, co-sensitizers, cross-linking agents, curing accelerators, thermal curing accelerators, fillers, plasticizers, diluents, and sensing agents, as well as adhesion accelerators to the substrate surface and other accelerators. Known additives such as auxiliaries (e.g., conductive particles, fillers, anti-foaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc.) may be added as needed.

These ingredients are, for example, paragraphs 0183 to 0228 of Japanese Patent Application Publication No. 2012-003225 (paragraphs 0237 to 0309 of corresponding US Patent Application Publication No. 2013/0034812), and paragraphs 0101 to 0102 of Japanese Patent Application Publication No. 2008-250074. , paragraphs 0103 to 0104, paragraphs 0107 to 0109, and paragraphs 0159 to 0184 of Japanese Patent Application Publication No. 2013-195480, etc., can be referred to, and these contents are incorporated in this specification.

<Method for producing light-shielding composition>

It is preferable to first prepare a colorant composition containing a black colorant, and then further mix the obtained colorant composition with other components to form a composition.

The colorant composition is preferably prepared by mixing a black colorant, a resin (preferably a dispersion resin), and a solvent. Moreover, it is also preferable to contain a polymerization inhibitor in the color material composition.

The colorant composition can be prepared by mixing each of the above components using a known mixing method (e.g., a mixing method using a stirrer, homogenizer, high-pressure emulsifier, wet grinder, or wet disperser). You can.

In preparing the light-shielding composition, each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then blended sequentially. Additionally, the order of addition and working conditions during mixing are not particularly limited.

The light-shielding composition is preferably filtered with a filter for purposes such as removal of foreign substances and reduction of defects. As a filter, any filter that has been conventionally used for filtration purposes, etc. can be used without particular restrictions. For example, filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide-based resins such as nylon, and polyolefin-based resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high molecular weight). can be mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The hole diameter of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, more preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. Within this range, it is possible to reliably remove fine foreign substances such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment (including black pigment).

When using filters, you can combine different filters. In that case, filtering using the first filter may be performed only once, or may be performed twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the hole diameter of the second filtering is the same or larger than the hole diameter of the first filtering. Additionally, first filters with different hole diameters within the above-mentioned range may be combined. The hole diameter here can refer to the filter manufacturer's nominal value. As commercially available filters, one can select from various filters provided by, for example, Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlis Co., Ltd.), and Kits Micro Filter Co., Ltd.

The second filter may be a filter formed of the same material as the first filter described above. The hole diameter of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and still more preferably 0.3 to 6.0 μm.

The composition preferably does not contain impurities such as metals, metal salts containing halogens, acids, or alkalis. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 1 ppb by mass or less, more preferably 100 ppt by mass or less, especially preferably 10 ppt by mass or less, and does not contain substantially any impurities. Most preferably (below the detection limit of the measuring device).

Additionally, the impurities can be measured using an inductively coupled plasma mass spectrometer (Yokogawa Analytical Systems, Agilent 7500cs type).

[Formation of black layer]

The method of forming the black layer is not particularly limited, and a black layer (including a patterned black layer) is formed by applying the light-shielding composition of the present invention on a support and curing the obtained coating film.

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

·Coat film formation process

·Curing process

·Development process

Hereinafter, each process will be described.

<Coat film formation process>

In the coating film formation step, prior to curing (exposure), a light-shielding composition is applied onto the support to form a coating film (composition layer). As a support, for example, a substrate for a solid-state imaging device in which an imaging device (light-receiving device) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate) can be used. there is. Additionally, if necessary, an undercoating layer may be provided on the support to improve adhesion to the upper layer, prevent diffusion of substances, and flatten the substrate surface.

As a method of applying the composition to the support, various application methods such as slit coating, inkjet, rotational coating, flexible coating, roll coating, and screen printing can be applied. As a film thickness of a coating film, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, and 0.2-3 micrometers is still more preferable. Drying (prebake) of the coating film applied on the support can be performed, for example, on a hot plate, oven, etc. at a temperature of 50 to 140°C for 10 to 300 seconds.

<Curing process>

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

The method of light irradiation is not particularly limited, but it is preferable to irradiate light through a photomask having openings in a pattern.

Exposure is preferably performed by irradiation with radiation. As radiation that can be used in exposure, ultraviolet rays such as g-rays, h-rays, and i-rays are particularly preferred, and as the light source, a high-pressure mercury lamp is preferred. The irradiation intensity is preferably 5 to 1500 mJ/cm ² and more preferably 10 to 1000 mJ/cm ² .

Additionally, when the composition contains a thermal polymerization initiator, the coating film may be heated in the curing step. The heating temperature is not particularly limited, but is preferably 80 to 250°C. Moreover, the heating time is not particularly limited, but is preferably 30 to 300 seconds.

In addition, in the curing process, when heating the coating film, the post-bake described later may also be performed. In other words, when the coating film is heated in the curing process, the method for producing the black layer does not need to include a post-bake process.

<Development process>

The development process is a process of developing the coating film after exposure. Through this process, the coating film of the unirradiated portion in the curing step is eluted, only the photocured portion remains, and a patterned black layer is obtained.

The type of developer used in the development process is not particularly limited, but an alkaline developer that does not cause damage to the underlying imaging element and circuit, etc. is preferable.

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

Development time is, for example, 20 to 90 seconds. In order to better remove residue, in some cases it is recently carried out for 120 to 180 seconds. Furthermore, in order to further improve residue removal, the process of shaking off the developer every 60 seconds and supplying new developer may be repeated several more 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 preferable.

Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. , tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene, etc. (Among these, organic alkali is preferable).

In addition, when used as an alkaline developer, washing treatment with water is generally performed after development.

<Post-bake>

After the curing process, it is preferable to perform post-heating treatment (post-baking). Post-baking is a heat treatment after development to ensure complete hardening. The heating temperature is preferably 240°C or lower, and more preferably 220°C or lower. There is no particular lower limit, but considering efficient and effective treatment, 50°C or higher is preferable, and 100°C or higher is more preferable.

Post-baking can be performed continuously or in a batch manner using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater.

The above post-baking is preferably performed in an atmosphere with low oxygen concentration. The oxygen concentration is preferably 19 volume% or less, more preferably 15 volume% or less, more preferably 10 volume% or less, particularly preferably 7 volume% or less, and most preferably 3 volume% or less. There is no particular lower limit, but 10 volume ppm or more is practical.

In addition, the curing may be completed by changing to the above-mentioned post-baking method by heating and irradiating UV (ultraviolet rays).

In this case, it is preferable that the above-mentioned composition further contains a UV curing agent. The UV curing agent is preferably one that can cure at a shorter wavelength than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process using normal i-line exposure. Examples of UV curing agents include Ciba Irgacure 2959 (brand name). In the case of UV irradiation, it is preferable that the coating film is a material that hardens at a wavelength of 340 nm or less. There is no particular lower limit for the wavelength, but 220 nm or more is common. Moreover, the exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and still more preferably 800 to 3500 mJ. This UV curing process is preferably performed after the curing process in order to perform low-temperature curing more effectively. It is desirable to use an ozoneless mercury lamp as the exposure light source.

〔Physical properties of black layer〕

Since the black layer has excellent light blocking properties, the optical density (OD: Optical Density) per 1.0 μm of thickness in the wavelength range of 400 to 1200 nm is preferably 1.7 or more, more preferably 2.0 or more, and 2.1 or more. This is more preferable. Additionally, the upper limit is not particularly limited, but is generally preferably 10 or less.

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

In addition, the optical density of the black layer (light-shielding film) is first formed on a glass substrate and measured using an integrating sphere-type light receiving unit of a spectrophotometer U-4100 (trade name, manufactured by Hitachi High Technologies). , it can be measured by measuring the thickness of the measurement point and calculating the optical density per predetermined thickness.

For example, the thickness of the black layer is preferably 0.1 to 4.0 μm, and more preferably 1.0 to 2.5 μm. Additionally, the black layer may be thinner or thicker than this range depending on the intended use.

Additionally, when using the black layer as a light attenuation film, the light-shielding property may be adjusted by making the black layer thinner than the above range (for example, 0.1 to 0.5 μm). In this case, 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 blocking layer]

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

Examples of the oxygen barrier layer include layers with an oxygen permeability in the thickness direction (hereinafter simply referred to as "oxygen permeability") of 50 ml/(m ² ·day·atm) or less, and an oxygen permeability of 10 ml/(m ² ·day). ·atm) or less is preferable, a layer of 1.5 ml/(m ² ·day·atm) or less is more preferable, and a layer of 1.0 ml/(m ² ·day·atm) or less is more preferable. The lower limit of oxygen permeability is preferably 0.001ml/(m ² ·day·atm).

Oxygen permeability can be measured, for example, using an oxygen permeation measuring device (Model8001, manufactured by Illinois Corporation).

The oxygen blocking layer is a single layer made of an inorganic material.

In this specification, “single layer” means a layer in which the composition of the material constituting the layer is uniform along the thickness direction and the in-plane direction. Therefore, for example, in a laminate of layer A made of inorganic material a and layer B made of inorganic material b whose composition is different from that of inorganic material a, even if both layers A and layer B have the function of blocking oxygen, It is not included in the oxygen barrier layer defined in this specification.

Additionally, “consisting of an inorganic material” 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. The content of the carbon atoms is preferably 2.5% by mass or less relative to the total mass of the oxygen blocking layer. Additionally, the lower limit of the carbon atom content is not particularly limited and may be below the detection limit.

The content of carbon atoms in the material constituting the oxygen barrier layer is determined by forming a smooth surface on the oxygen barrier layer by polishing or cutting, and then measuring the formed smooth surface with an electron beam microanalyzer (EPMA: Electron Probe Micro Analyzer) (e.g. For example, it is measured by analysis using "JXA-8530F" (brand name) manufactured by Nippon Electronics Co., Ltd.

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

When the thickness of the oxygen blocking layer is within the above range, a light-shielding film with a better balance of light resistance and moisture resistance can be manufactured. More specifically, if the thickness of the oxygen blocking layer is 10 nm or more, the effect of suppressing fluctuations in the film thickness of the light-shielding film and fluctuations in optical properties (transmittance and reflectance) after the light resistance test is improved, and the thickness of the oxygen blocking layer is 500 nm. If it is below, the effect of suppressing peeling of the black layer from the substrate after the moisture resistance test is improved.

It is not clear why moisture resistance improves when the thickness of the oxygen barrier layer is 500 nm or less, but when the thickness of the oxygen barrier layer exceeds 500 nm, the difference in shrinkage rate between the black layer including the oxygen barrier layer and the substrate after the moisture resistance test is unclear. It is presumed that this is because the stress generated becomes stronger and causes peeling of the black layer from the substrate.

In addition, when the thickness of the oxygen blocking layer is 500 nm or less, when a light shielding film composed of a black layer and an oxygen blocking layer is provided on the device, interference between light reflected from the surface of the black layer and light reflected from the surface of the oxygen blocking layer is reduced, Deterioration of device performance can be prevented.

The thickness of the oxygen blocking layer is preferably more than 50 nm and less than 250 nm, and more preferably 70 to 200 nm, because the moisture resistance and heat resistance of the light shielding film are more excellent.

Additionally, the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer (thickness of the black layer/thickness of the oxygen blocking layer) may be 2 to 100, and since the moisture resistance and heat resistance of the light shielding film are superior, it may be 7 to 30. is preferable, and 10 to 25 is more preferable.

The inorganic material constituting the oxygen blocking layer is not particularly limited and includes metal oxides, metal nitrides, and metal oxynitrides.

Metals contained in the inorganic material include silicon, titanium, aluminum, indium, tin, niobium, zirconium, cerium, tantalum, and zinc. Silicon, titanium, or aluminum is preferred, and silicon is more preferred.

Specific examples of the inorganic material constituting the oxygen blocking layer include silicon oxide, silicon nitride, indium oxide, tin oxide, niobium oxide, titanium oxide, zirconium oxide, cerium oxide, tantalum oxide, aluminum oxide, and zinc oxide. , silicon oxide and silicon nitride are preferable, and silicon oxide is more preferable because the light resistance and moisture resistance of the light shielding film are more excellent.

Additionally, the oxygen blocking layer of the present invention is a single layer made of an inorganic material and does not contain substantially any organic components.

When the oxygen blocking layer contains an organic component, light irradiation to the oxygen blocking layer decomposes the organic component contained therein, thereby lowering the oxygen blocking ability. In contrast, the oxygen blocking layer of the present invention, which is a single layer made of an inorganic material, can prevent such a decrease in oxygen blocking ability.

In addition, in this specification, the oxygen barrier layer "does not contain substantially any organic components" 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. do. The content of carbon atoms in the material constituting the oxygen blocking layer is measured using an electron beam microanalyzer according to the method described above.

The oxygen blocking layer preferably contains substantially no particles because it has better heat resistance. When the oxygen barrier layer contains particles, the composition of the material constituting the layer becomes non-uniform, resulting in regions with different heat shrinkage properties, which may cause the oxygen barrier layer to be greatly distorted in a high-temperature environment and reduce heat resistance. Because there is.

Additionally, the oxygen blocking layer preferably contains substantially no particles because the surface becomes smoother and the in-plane uniformity of reflectance is improved.

In addition, the above "particles" refer to particles of a material whose composition is different from the inorganic material constituting the oxygen barrier layer, and whose particle size is 10 nm or more.

The content of particles in the oxygen barrier layer can be measured by the following method using an electron beam microanalyzer (EPMA) (e.g., "JXA-8530F" (trade name) manufactured by Nippon Electronics Co., Ltd.). First, the oxygen blocking layer is polished or cut to form a smooth surface. After that, the distribution of the elemental composition on the formed smooth surface is measured using an electron beam microanalyzer, and a mapping image of the elemental composition is obtained. In the obtained mapping image, the area where particles exist is specified based on the difference in elemental composition from the continuous phase. Next, the area ratio occupied by the particles in the observation surface is obtained by dividing the total area of the particle areas by the observation area. Next, the area ratio is converted to a volume ratio (3/2 of the area ratio) and further converted to a mass ratio based on the elemental composition to obtain the particle content relative to the total amount of the oxygen barrier layer.

For example, when silicon oxide particles are present in an oxygen blocking layer made of silicon oxide (SiO ₂ ), the outline of the silicon oxide particles is displayed in the mapping image due to the silanol group (SiOH) present on the surface of the silicon oxide particles. Therefore, the presence of particles can be confirmed. In this way, according to the above method, the content of particles can be measured based on the difference in composition between the continuous phase and the particles in the oxygen barrier layer.

In addition, in this specification, the oxygen barrier layer "substantially does not contain particles" means that the content of particles in the oxygen barrier layer measured by the above method is 5% by mass or less with respect to the total mass of the oxygen barrier layer. , or below the detection limit.

[Formation of oxygen blocking layer]

The method of forming the oxygen blocking layer is not particularly limited, and known film forming methods of inorganic materials can be used.

Film formation methods include deposition methods such as sputtering, vacuum deposition, ion beam assisted deposition, ion plate method, and plasma CVD (chemical vapor deposition) method, as well as spin coating, dip coating, cast, slit coating, and spray methods. Wet methods such as these can be mentioned.

Among them, it is preferable to form the oxygen blocking layer by vapor deposition because it is easier to form a thin film, and because it is easier to control the thickness and has better adhesion with the black layer as the target, it is preferable to form the oxygen blocking layer by the sputtering method. It is more preferable to form an oxygen blocking layer.

The sputtering method is not particularly limited and may be known methods such as pulse sputtering method, AC sputtering method, and digital sputtering method.

For example, when forming an oxygen blocking layer by the sputtering method, a substrate with a black layer formed on the surface is placed in a chamber in a mixed gas atmosphere of an inert gas and a reactive gas (e.g., oxygen or nitrogen, etc.), and the desired A target is selected so that the composition is suitable and an oxygen blocking layer is deposited.

Additionally, the type of inert gas is not particularly limited, and inert gases such as argon or helium can be used. Additionally, the reactive gas may be selected depending on the composition of the oxygen blocking layer to be formed.

The pressure in the chamber due to the mixed gas of the inert gas and the reactive gas is not particularly limited, and may be 1.0 Pa or less, and is preferably 0.5 Pa or less. The lower limit of the pressure in the chamber due to the mixed gas of the inert gas and the reactive gas is not particularly limited, but is preferably 0.1 Pa or more, for example.

Additionally, when forming the oxygen blocking layer by the sputtering method, the thickness of the oxygen blocking layer can be adjusted by adjusting the discharge power or film formation time.

[Manufacture of light-shielding film]

The manufacturing method of the light-shielding film of the present invention is not particularly limited.

The light-shielding film of the present invention includes the steps of applying a light-shielding composition containing a black colorant, a resin, a polymerizable compound, and a polymerization initiator onto a support, curing the obtained coating film to form a black layer, and forming a black layer on the black layer. It can be manufactured by a manufacturing method including a step of forming an oxygen blocking layer.

As the "process of forming a black layer", the method described in "Formation of a black layer" may be applied, and as the "process of forming an oxygen blocking layer", the method described in "Formation of an oxygen blocking layer" may be applied. Just apply it.

[Properties and uses of light blocking film]

For example, the thickness of the light-shielding film is preferably 0.1 to 6.0 μm, and more preferably 1.0 to 3.5 μm. Additionally, the light-shielding film may be thinner or thicker than this range depending on the intended use.

The reflectance of the light shielding film is preferably less than 5%, more preferably less than 3%, and still more preferably less than 2%.

In addition, the light shielding film is used in portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printers, multi-function printers, and scanners; Industrial devices such as surveillance cameras, barcode readers, automated teller machines (ATMs), high-speed cameras, and devices with identity authentication functions using facial image authentication or biometric authentication; In-vehicle camera devices; Medical camera devices such as endoscopes, capsule endoscopes, and catheters; and optical filters used in space devices such as biometric sensors, biosensors, military reconnaissance cameras, three-dimensional map cameras, weather and marine observation cameras, land resource exploration cameras, and exploration cameras for astronomical and deep space targets in space, etc.; It is suitable for light-shielding members and light-shielding films of modules, as well as anti-reflection members and anti-reflection films.

The light shielding film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The light-shielding film is suitable for members that provide a light-shielding function or anti-reflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.

Examples of micro LED and micro OLED include those described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.

The light-shielding film is also suitable as an optical filter and optical film used in quantum dot sensors and quantum dot solid-state imaging devices. Additionally, it is suitable as a member that provides a light-shielding function and an anti-reflection function. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in US Patent Application Publication No. 2012/0037789 and International Publication No. 2008/131313.

[Optical elements, solid-state imaging elements, and solid-state imaging devices]

The light-shielding film of the present invention is also preferably used in a solid-state imaging device.

As described above, the light-shielding film of the present invention is excellent in light resistance and moisture resistance. Additionally, the light-shielding film of the present invention has excellent heat resistance.

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

Among them, the optical element is preferably a solid-state imaging element mounted on, for example, a camera.

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

There are no particular restrictions on the form in which the solid-state imaging device contains the light-shielding film, for example, a plurality of photodiodes and polysilicon constituting the light-receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate. A form having a light-receiving element formed of a light-receiving element and having a light-shielding film on the side of the light-receiving element forming surface of the support (for example, parts other than the light-receiving part and/or color adjustment pixels, etc.) or on the opposite side of the forming surface can be mentioned.

Additionally, when the light shielding film is used as a light attenuation film, for example, the dynamic range of the solid-state imaging device can be improved by arranging the light attenuation film so that some light passes through the light attenuation film and then enters the light receiving element.

A solid-state imaging device includes the solid-state imaging element.

Configuration examples of a solid-state imaging device and a solid-state imaging element will be described with reference to FIGS. 1 and 2. In addition, in Figures 1 and 2, in order to make each part clear, the ratio of thickness and/or width to each other is ignored and some parts are exaggerated.

1 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device containing the solid-state imaging device of the present invention.

As shown in FIG. 1, the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass supported above the solid-state imaging element 101 and sealing the solid-state imaging element 101. (103) is provided. Additionally, on this cover glass 103, a lens layer 111 is provided overlapping with a spacer 104 interposed therebetween. The lens layer 111 is composed of a support body 113 and a lens material 112. The lens layer 111 may be formed by integrally molding the support 113 and the lens material 112. When stray light enters the peripheral edge area of the lens layer 111, the effect of condensing light in the lens material 112 is weakened due to diffusion of light, and the light reaching the imaging unit 102 is reduced. Additionally, noise due to stray light also occurs. Therefore, the peripheral edge area of this lens layer 111 is shielded from light by providing a light-shielding film 114. The light-shielding film of the present invention can be used as the light-shielding film 114.

The solid-state imaging device 101 photoelectrically converts the optical image formed by the imaging unit 102, which serves as the light-receiving surface, and outputs it as an image signal. This solid-state imaging device 101 is provided with a laminated substrate 105 in which two substrates are stacked. The laminated board 105 is made of a rectangular chip board 106 and a circuit board 107 of the same size, and the circuit board 107 is laminated on the back side of the chip board 106.

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

An imaging unit 102 is provided in the central portion of the surface of the chip substrate 106. Additionally, a light-shielding film 115 is provided at the peripheral edge area of the imaging unit 102. The light shielding film 115 blocks stray light incident on this peripheral edge area, thereby preventing the generation of dark current (noise) from the circuit in this peripheral edge 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 surface edge of the chip substrate 106. The electrode pad 108 is electrically connected to the imaging unit 102 through a signal line (possibly a bonding wire), not shown, provided on the surface of the chip substrate 106.

On the back of the circuit board 107, external connection terminals 109 are provided at positions approximately below each electrode pad 108. Each external connection terminal 109 is connected to each electrode pad 108 through a through electrode 110 that vertically penetrates the laminated substrate 105. In addition, each external connection terminal 109 includes a control circuit that controls the driving of the solid-state imaging device 101 through wiring not shown, and a circuit that performs image processing on the imaging signal output from the solid-state imaging device 101. It is connected to an image processing circuit, etc.

Figure 2 shows a schematic cross-sectional view of the imaging unit 102. As shown in FIG. 2, the imaging unit 102 is composed of various parts provided on the substrate 204, such as a light receiving element 201, a color filter 202, and a micro lens 203. 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 may be used as a black matrix (205bm).

As the material for the substrate 204, the same material as the chip substrate 106 described above can be used. A p-well layer 206 is formed on the surface layer of the substrate 204. Within this p-well layer 206, light-receiving elements 201 made of 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 made of an n-type layer is formed via a read gate portion 207 on the surface of the p-well layer 206. Additionally, on the other side of the light receiving element 201, a vertical transmission path 208 belonging to an adjacent pixel is formed via an element isolation region 209 made of a p-type layer. The read gate portion 207 is a channel area for reading the signal charge accumulated in the light receiving element 201 to the vertical transmission path 208.

A gate insulating film 210 made of an Oxide-Nitride-Oxide (ONO) film is formed on the surface of the substrate 204. On this gate insulating film 210, a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed so as to cover approximately immediately above the vertical transfer path 208, the read gate portion 207, and the device isolation region 209. This is formed. The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to transfer charge, and a read electrode that drives the read gate portion 207 to read signal charge. The signal charge is sequentially transferred from the vertical transmission path 208 to the horizontal transmission path (not shown) and the output unit (floating diffusion amplifier), and is then output as a voltage signal.

A light-shielding film 212 is formed on the vertical transfer electrode 211 to cover its surface. The light-shielding film 212 has an opening at a position immediately above the light-receiving element 201 and blocks light from other areas. The light-shielding film of the present invention may be used as the light-shielding film 212 .

On the light shielding film 212, a transparent intermediate layer is provided including an insulating film 213 made of BPSG (borophospho silicate glass), an insulating film (passivation film) 214 made of P-SiN, and a planarization film 215 made of transparent resin, etc. . The color filter 202 is formed on the intermediate layer.

[Image display device]

The image display device of the present invention includes the light-shielding film of the present invention.

As an example of an image display device having a light-shielding film, a color filter containing a light-shielding film as a black matrix is used in the image display device.

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

[Black Matrix]

The light-shielding film of the present invention is also preferably used as a black matrix. Black matrices may be contained in image display devices such as color filters, solid-state imaging devices, and liquid crystal display devices.

As the black matrix, those already described above; A black frame provided on the peripheral edge of an image display device such as a liquid crystal display device; Black portions in grids and/or stripes between red, blue, and green pixels; Dot-shaped and/or line-shaped black patterns for TFT (thin film transistor) light blocking can be used. For the definition of this black matrix, see, for example, Taihei Kanno, "Liquid Crystal Display Manufacturing Device Terminology Dictionary", 2nd edition, Nikkan Kogyo Shinbunsha, 1996, p. There is a description in 64.

The black matrix has high light blocking properties (optical density OD of 3) to improve display contrast and, in the case of liquid crystal display devices using an active matrix drive method using thin film transistors (TFT), to prevent image quality degradation due to current leakage of light. or more) is desirable.

The manufacturing method of the black matrix is not particularly limited, but can be manufactured by the same method as the manufacturing method of the above-described light-shielding film. Specifically, the black matrix can be manufactured by applying the composition to a substrate, forming a coating film, exposing and developing to form a patterned black layer, and then forming an oxygen blocking layer on the black layer. Additionally, the film thickness of the light-shielding film used as the black matrix is preferably 0.1 to 4.0 μm.

The material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more to visible light (wavelength 400 to 800 nm). Specific examples of such materials include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; Plastics, such as polyester resin and polyolefin resin, are mentioned, and alkali-free glass or quartz glass is preferable from the viewpoint of chemical resistance and heat resistance.

<Color Filter>

It is also preferable that the light-shielding film of the present invention is contained in a color filter.

The form in which the color filter contains the light-shielding film is not particularly limited, and includes a color filter provided with a substrate and the black matrix. That is, an example may be a color filter having red, green, and blue colored pixels formed in an opening of the black matrix formed on a substrate.

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

First, a coating film of a composition containing a pigment corresponding to each colored pixel of the color filter is formed in the opening of the patterned black matrix formed on the substrate. In addition, the composition for coloring is not particularly limited, and known compositions can be used. However, in the composition described in this specification, it is preferable to use a composition in which the black colorant is replaced with a colorant corresponding to each pixel.

Next, the coating film is exposed through a photomask having a pattern corresponding to the openings of the black matrix. Next, after removing the unexposed portion by developing treatment, the colored pixel can be formed in the opening of the black matrix by baking. By performing a series of operations using, for example, a coloring composition containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be produced.

<Liquid crystal display device>

It is also preferable that the light-shielding film of the present invention is contained in a liquid crystal display device. There are no particular restrictions on the form in which the liquid crystal display device contains the light-shielding film, but examples include forms in which the liquid crystal display device contains a color filter containing the black matrix already described.

The liquid crystal display device according to the present embodiment includes, for example, a pair of substrates arranged opposite each other and a liquid crystal compound encapsulated between the substrates. The substrate is the same as what has already been described as a black matrix substrate.

Specific forms of the liquid crystal display device include, for example, from the user side: 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. A laminate containing in this order can be mentioned.

In addition, the liquid crystal display device is not limited to the above, and examples include "Electronic Display Device (written by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)" and "Display Device (written by Ibuki Sumiaki, Sangyo Tosho Co., Ltd., published in 1990)" A liquid crystal display device described in "Published", etc. can be mentioned. Also, for example, there is a liquid crystal display device described in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd., 1994)."

[Infrared sensor]

The light-shielding film of the present invention is also preferably contained in an infrared sensor.

The infrared sensor according to the above embodiment will be explained using FIG. 3. Fig. 3 is a schematic cross-sectional view showing a configuration example of an infrared sensor provided with a light-shielding film of the present invention. The infrared sensor 300 shown in FIG. 3 includes a solid-state imaging element 310.

The imaging area provided on the solid-state imaging device 310 is configured by combining an infrared absorption filter 311 and a color filter 312 according to an embodiment of the present invention.

The infrared absorption filter 311 transmits light in the visible region (for example, light with a wavelength of 400 to 700 nm) and transmits light in the infrared region (for example, light with a wavelength of 800 to 1,300 nm, preferably light with a wavelength of 900 to 900 nm). It is a film that shields light of 1200 nm, more preferably light of a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorber (as already described in the form of an infrared absorber) as a colorant can be used.

The color filter 312 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible light region, for example, color filters formed with pixels of red (R), green (G), and blue (B). A filter or the like is used, and its form is the same as that already described.

Between the infrared transmission filter 313 and the solid-state imaging device 310, a resin film 314 (for example, a transparent resin film, etc.) capable of transmitting light of the wavelength that passed through the infrared transmission filter 313 is disposed. there is.

The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and is a colorant (for example, a perylene compound and/or a benzofuranone compound, etc.) that absorbs light in the visible light region. In addition, the light-shielding film of the present invention containing an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethane compound) can be used. The infrared transmission filter 313 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm, for example.

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

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

In addition, in the form shown in FIG. 3, the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thicknesses of both may be different.

In addition, in the form shown in FIG. 3, the color filter 312 is provided on the side of the incident light (hν) rather than the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 is changed, The infrared absorption filter 311 may be provided on the side of the incident light hν rather than the color filter 312.

In addition, in the form shown in FIG. 3, the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other, but the two filters do not necessarily have to be adjacent, and another layer may be provided between them. The light-shielding film of the present invention can be used as a light-shielding film for the ends and/or sides of the surface of the infrared absorption filter 311, and when used on the inner wall of the device of an infrared sensor, internal reflection and/or unintentional damage to the light receiving part is prevented. By preventing light from entering, sensitivity can be improved.

According to this infrared sensor, since image information can be read simultaneously, motion sensing that recognizes an object whose movement is detected is possible. Additionally, since distance information can be acquired using this infrared sensor, it is also possible to capture images including 3D information. Additionally, this infrared sensor can also be used as a biometric authentication sensor.

Next, a solid-state imaging device using the infrared sensor will be described.

The solid-state imaging device contains a lens optical system, a solid-state imaging element, an infrared light-emitting diode, and the like. In addition, regarding each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of Japanese Patent Application Laid-Open No. 2011-233983 can be referred to, and this content is incorporated in this specification.

[Headlight unit]

The light-shielding film of the present invention is also preferably contained in a headlight unit of a vehicle lamp such as an automobile. The light-shielding film of the present invention contained in a headlight unit is preferably formed in a pattern so as to block at least part of the light emitted from the light source.

The headlight unit according to the above embodiment will be explained using FIGS. 4 and 5.

FIG. 4 is a schematic diagram showing an example of the configuration of a headlight unit, and FIG. 5 is a schematic perspective view showing an example of the configuration of a light blocking portion of the headlight unit.

As shown in FIG. 4, the headlight unit 10 has a light source 12, a light blocking portion 14, and a lens 16. The light source 12, the light blocking portion 14, and the lens 16 ) are arranged in the order of.

The light-shielding portion 14 has a base 20 and a light-shielding film 22, as shown in FIG. 5 .

The light shielding film 22 is formed with pattern-shaped openings 23 for irradiating light emitted from the light source 12 in a specific shape. The light distribution pattern emitted from the lens 16 is determined by the shape of the opening 23 of the light shielding film 22. The lens 16 projects the light L from the light source 12 that has passed through the light blocking portion 14. If a specific light distribution pattern can be irradiated from the light source 12, the lens 16 is not necessarily necessary. The lens 16 is appropriately determined depending on the irradiation distance and irradiation range of the light L.

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

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

Additionally, the light source 12 is not limited to one, and may be arranged in a row or a matrix, for example. When providing a plurality of light sources, for example, one light-shielding portion 14 may be provided for one light source 12. In this case, each light-shielding film 22 of the plurality of light-shielding portions 14 may have the same pattern, or may have different patterns.

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

FIG. 6 is a schematic diagram showing an example of a light distribution pattern by a headlight unit, and FIG. 7 is a schematic diagram showing another example of a light distribution pattern by 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 areas where light is irradiated. In addition, the area 31 shown in FIG. 6 and the area 31 shown in FIG. 7 both represent irradiation areas irradiated from the light source 12 (see FIG. 4) when the light shielding film 22 is not provided.

Due to the pattern of the light shielding film 22, the intensity of light rapidly decreases at the edge 30a, for example, as in the light distribution pattern 30 shown in FIG. 6. The light distribution pattern 30 shown in FIG. 6 is a pattern that does not illuminate oncoming vehicles when driving on the left, for example.

Additionally, like the light distribution pattern 32 shown in FIG. 7, a part of the light distribution pattern 30 shown in FIG. 6 can be cut out. In this case as well, as in the light distribution pattern 30 shown in FIG. 6, the intensity of light rapidly decreases at the edge 32a, resulting in a pattern that does not illuminate the oncoming vehicle when driving on the left, for example. . Additionally, the intensity of light is rapidly decreasing in the notch 33 as well. For this reason, a mark indicating a state such as a curved road, an uphill slope, or a downhill slope, for example, can be displayed in the area corresponding to the notch 33. As a result, safety during night driving can be improved.

In addition, the light blocking portion 14 is not limited to being fixedly disposed between the light source 12 and the lens 16, and is positioned between the light source 12 and the lens 16 by a driving mechanism (not shown). Alternatively, it can be configured to obtain a specific light distribution pattern by entering it as needed.

Additionally, the light blocking portion 14 and a shade member capable of blocking light from the light source 12 may be formed.

In this case, a drive mechanism (not shown) can be used to enter between the light source 12 and the lens 16 as needed to obtain a specific light distribution pattern.

Example

The present invention will be described in more detail below based on examples. Materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the examples shown below.

[Preparation of color material composition]

A colorant composition containing the following black colorant was prepared and used to prepare 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 Daica Co., Ltd.) with an average particle diameter of 15 nm, 25 g of silicon oxide particles AEROSIL (registered trademark) 300/30 (manufactured by Evonik Corporation) with a BET surface area of 300 m ² /g, and dispersant Disperbyk190 ( 100 g of (brand name, manufactured by Big Chemistry) was weighed and mixed. To the obtained mixture, 71 g of ion electrically exchanged water was added. The obtained mixture was treated for 20 minutes at an revolution speed of 1360 rpm and a rotation speed of 1047 rpm using a MAZERUSTAR KK-400W manufactured by KURABO to obtain a uniform dispersion. This dispersion liquid was filled in a quartz container and heated to 920°C in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). After that, the atmosphere was replaced with nitrogen, and nitriding reduction treatment was performed by flowing ammonia gas at 100 mL/min for 5 hours at the same temperature. After completion of the nitriding reduction treatment, the recovered powder was pulverized in a mortar to obtain powdery titanium black (color material a-1) with a specific surface area of 73 m ² /g.

To the colorant a-1 (20 parts by mass) obtained above, dispersion resin Propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) was further added.

[Formula 25]

In the above formula (X-1), the number attached to each repeating unit means the molar ratio of each repeating unit. Additionally, the weight average molecular weight of the dispersion resin X-1 was 32000.

The obtained dispersion was sufficiently stirred using a stirrer and premixed. The obtained dispersion was subjected to dispersion treatment under the following conditions using a disperser NPM Pilot (trade name, manufactured by Shinmaru Enterprises Co., Ltd.) to obtain colorant composition A-1, which is a dispersion containing the colorant a-1.

(dispersion condition)

·Beads diameter: ø0.05mm

·Beads filling rate: 65% by volume

·Wheat speed: 10m/sec

·Separator peripheral speed: 11m/s

·Amount of mixed liquid to be dispersed: 15.0g

·Circulation flow rate (pump supply volume): 60kg/hour

·Treatment liquid temperature: 20~25℃

Coolant: Tap water (5℃)

·Bead mill circular passage internal volume: 2.2L

·Number of passes: 84 passes

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

Organic pigment containing a benzofuranone compound as colorant a-2 (trade name "Irgaphor Black S0100CF", manufactured by BASF) (150 parts by mass), dispersion resin (manufactured by Brizol, Inc.) (25 parts by mass), and 3-methoxybutylacetate (MBA) (750 parts by mass) were mixed. Dispersion resin

The obtained mixture was stirred for 20 minutes with a homomixer (manufactured by Primix) to obtain a preliminary dispersion. Furthermore, the obtained preliminary dispersion was subjected to dispersion treatment for 3 hours under the following dispersion conditions using an Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator to obtain a dispersion composition. After dispersion was completed, the beads and the dispersion were separated through a filter, and colorant composition A-2, which was a dispersion containing the colorant a-2, was obtained. The solid concentration of the obtained dispersion was 25% by mass, and the ratio of colorant a-2/resin component (sum 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 that has a tertiary amine as a pigment adsorbent.

(dispersion condition)

Beads used: zirconia beads of ϕ0.30 mm (YTZ ball, manufactured by Nethlen)

·Beads filling rate: 75% by volume

·Wheat speed: 8m/sec

·Amount of mixed liquid to be dispersed: 1000g

·Circulation flow rate (pump supply volume): 13kg/hour

·Treatment liquid temperature: 25~30℃

Coolant: Tap water (5℃)

·Bead mill circular passage inner volume: 0.15L

·Number of passes: 90 passes

<Preparation of organic pigment dispersion (color composition A-3)>

Instead of colorant a-2, an organic pigment containing a perylene compound (trade name "PALIOGEN Black S0084", manufactured by BASF) was used as colorant a-3, and the colorant was prepared according to the manufacturing method of colorant composition A-2 above. Color material composition A-3, which is a dispersion containing a-3, was obtained.

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

Carbon black was produced using a normal oil furnace method. However, as the raw material oil, ethylene bottom oil with low Na content, Ca content, and S content was used, and combustion was performed using gas fuel. Additionally, as reaction stop water, pure water treated with an ion exchange resin was used.

Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14,500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. This slurry was transferred to a container equipped with a screw-type stirrer, and while mixing at about 1,000 rpm, toluene (600 g) in which epoxy resin "Epicoat 828" (made by Japan Epoxy Resin Co., Ltd.) (60 g) was dissolved was added in small amounts into the container. In about 15 minutes, all of the carbon black dispersed in water was transferred to toluene, forming particles with a particle size of about 1 mm.

Next, after dehydration was performed using a 60-mesh wire mesh, the separated particles were placed in a vacuum dryer, dried at 70°C for 7 hours, toluene and water were removed, and resin-coated carbon black (color material a-4) was obtained. The resin coating amount of the obtained resin-coated carbon black was 10% by mass based on the total amount of carbon black and resin.

The colorant a-4 (20 parts by mass) obtained above, the dispersion resin PGMEA was added so that it became 35% by mass. Dispersion resin X-1 is the same as that used in preparing the colorant composition A-1 above.

The obtained dispersion was sufficiently stirred using a stirrer and premixed. The obtained dispersion was subjected to dispersion treatment under the following conditions using Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. to obtain a dispersion composition. After dispersion was completed, the beads and the dispersion liquid were separated using a filter to obtain colorant composition A-4, which is a dispersion liquid containing the colorant a-4.

(dispersion condition)

·Bead diameter: ø0.05mm

·Beads filling rate: 75% by volume

·Wheat speed: 8m/sec

·Amount of mixed liquid to be dispersed: 500g

·Circulation flow rate (pump supply volume): 13kg/hour

·Treatment liquid temperature: 25~30℃

Coolant: Tap water (5℃)

·Bead mill circular passage internal volume: 0.15L

·Number of passes: 90 passes

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

Instead of dispersion resin X-1, dispersion resin Colorant composition A-5, a dispersion, was obtained.

[Formula 26]

In the above formula (X-2), the number attached to each repeating unit means the molar ratio of each repeating unit. Additionally, the weight average molecular weight of the dispersion resin X-2 was 33000.

[Alkali-soluble resin]

<Synthesis of alkali-soluble resin B-1>

Under a stream of dry nitrogen, 30.03 g 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.082 mole), 1.24 g 1,3-bis(3-aminopropyl)tetramethyl. Disiloxane (0.005 mol) and 2.73 g of 3-aminophenol (0.025 mol) as an end 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 further stirred at 180°C for 4 hours while removing water. After completion of the reaction, the reaction solution was added to 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 alkali-soluble resin B-1 (polyimide resin).

<Alkali soluble resin B-2>

Additionally, as alkali-soluble resin B-2, a resin having a structure represented by the following formula (B-2) was used.

[Formula 27]

<Synthesis of alkali-soluble resin B-3>

0.16 mole of a mixture of dicarboxylic acid derivatives obtained by reacting 41.3 g of diphenyl ether-4,4'-dicarboxylic acid and 43.2 g of 1-hydroxy-1,2,3-benzotriazole under a nitrogen stream and 2,2 -73.3 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 560 g of NMP, and then reacted at 75°C for 12 hours. Next, 13.1 g of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added and stirred for an additional 12 hours. After filtering the reaction mixture, it was added dropwise to a solution of water/methanol = 3/1 (volume ratio) to obtain a white precipitate. After washing the precipitate with water three times, it was dried in a vacuum dryer at 80°C for 24 hours to obtain alkali-soluble resin B-3 (resin consisting of a polybenzoxazole precursor).

[Polymerization initiator]

The following polymerization initiators were used to prepare the light-shielding composition.

·Polymerization initiator C-1: Compound represented by the following formula (C-1)

・Polymerization initiator C-2: IRGACURE OXE-02 (brand name, manufactured by BASF)

・Polymerization initiator C-3: IRGACURE 369 (brand name, manufactured by BASF)

The above polymerization initiators are all photopolymerization initiators, and among the above polymerization initiators, polymerization initiators C-1 and C-2 are oxime ester-based polymerization initiators.

[Formula 28]

[Polymerizable compound]

Polymerizable compound D-1 represented by the following formula (D-1) and polymerizable compound D-2 represented by the following formula (D-2) were used to prepare the composition.

Polymerizable compound D-1 is a mixture of a 5-functional polymerizable compound and a 6-functional polymerizable compound, and the mixing ratio is 5-functional polymerizable compound/6-functional polymerizable compound = 30/70 (mass ratio). .

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

[Formula 29]

[Formula 30]

[Surfactants]

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

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

[Formula 31]

[Polymerization inhibitor]

As a polymerization inhibitor, p-methoxyphenol was used to prepare the light-shielding composition.

[solvent]

As a solvent, cyclohexanone was used to prepare the light-shielding composition.

[Example 1]

<Preparation of light-shielding composition 1>

Light-shielding composition 1 of Example 1 was prepared by mixing the following components with a stirrer.

·63 parts by mass of colorant composition A-1 prepared above

・Alkali soluble resin B-1 3.5 parts by mass

・1.8 parts by mass of polymerization initiator C-1

6.1 parts by mass of polymerizable compound D-1

·Surfactant 0.02 parts by mass

·Polymerization inhibitor 0.003 parts by mass

· Solvent 25.5 parts by mass

<Production of the black layer>

The light-shielding composition 1 obtained above was applied on a glass substrate by spin coating to form a coating film with a thickness of 1.7 μm. The substrate with the coating film was prebaked at 100°C for 120 seconds. Next, using a UX-1000SM-EH04 (product name, Ushio Denki Co., Ltd.) through a mask with an L/S (line and space) pattern with an aperture line width of 50 μm, a high-pressure mercury lamp (lamp power: 50 mW/cm ² ) was used. Exposure by the proximity method was performed on the substrate containing the coating film. Next, using AD-1200 (manufactured by Mikasa Co., Ltd.), puddle development was carried out for 15 seconds with developer "CD-2060" (brand name, manufactured by Fujifilm Electronic Materials, Inc.). Next, it was washed with pure water using a shower nozzle for 30 seconds to remove the uncured portion, thereby forming a black layer on the substrate.

<Formation of oxygen blocking layer E-1>

Produced as above by introducing a mixed gas of argon and oxygen (oxygen: 40% by volume) into the vacuum chamber of a sputtering device (manufactured by Shinko Seiki, product name "SRV-4300"), and performing sputtering using a silicon target. On the surface of the black layer, an oxygen blocking layer E-1 (thickness: 100 nm) made of silicon oxide (SiO ₂ ) was formed.

As a result, the light-shielding film of Example 1 was obtained, in which the black layer and the oxygen blocking layer E-1 were formed in this order on the substrate.

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

In accordance with the method described in Example 1, except that each component used was replaced or the amount of colorant composition A-1 added was adjusted so that the composition of the light-shielding composition was the composition shown in Tables 1 and 2. The light-shielding compositions of the examples were prepared respectively.

Examples 2 to 6, 8, 9 and 14, in which a black layer and an oxygen blocking layer are formed in this order on a substrate according to the method described in Example 1 except that each light-shielding composition obtained above is used. 17 light shields were produced respectively.

[Example 7]

In the sputtering process, a mixed gas of argon and nitrogen (nitrogen: 50% by volume) is introduced into a vacuum chamber and sputtering is performed to form an oxygen blocking layer E- made of silicon nitride (Si ₃ N ₄ ) on the surface of the black layer. 2 (thickness: 100 nm), the light-shielding film of Example 7 was produced in which the black layer and the oxygen blocking layer E-2 were formed in this order on the substrate according to the method described in Example 1. .

[Examples 10 to 13]

In the sputtering process, the discharge power and film formation time were adjusted, and the oxygen blocking layers E-3 to E-6 made of silicon oxide (SiO ₂ ) having the thickness shown in Table 2 were formed in Example 1, respectively. According to the described method, light-shielding films of Examples 10 to 13 were produced, respectively, in which a black layer and an oxygen blocking layer were formed in this order on a substrate.

[Comparative Example 1]

<Preparation of composition for forming oxygen barrier layer>

The following components were mixed to prepare comparative composition 1.

· Polyvinyl alcohol (PVA): 32.2 parts by mass (Product name: PVA205, Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550)

・Polyvinylpyrrolidone (PVP): 14.9 parts by mass (Product name: K-30, manufactured by ISP Japan Co., Ltd.)

Distilled water: 524 parts by mass

Methanol: 429 parts by mass

<Formation of comparative oxygen barrier layer CE-1>

According to the black layer production method described in Example 1, a black layer was formed on the substrate.

Composition 1 was applied to the surface of the produced black layer using a spin coater. The application amount of Composition 1 was adjusted so that the thickness of the layer after drying was 1000 nm. After that, using a hot plate, the coating film of resin composition 1 was dried at 100°C for 120 seconds to form an oxygen barrier layer CE-1 (thickness: 1000 nm) for comparison.

As a result, the light-shielding film of Comparative Example 1 was obtained, in which the black layer and the oxygen blocking layer CE-1 were formed in this order on the substrate.

[Comparative Example 2]

In the process of forming the oxygen blocking layer, a black layer and an oxygen blocking layer CE-2 were formed on the substrate according to the method described in Comparative Example 1, except that the application amount of Composition 1 was adjusted so that the thickness of the layer after drying was 500 nm. The light-shielding film of Comparative Example 2, which was formed in this order, was produced.

[Comparative Example 3]

In the preparation process of the light-shielding composition, a black layer and an oxygen blocking layer CE- were formed on the substrate according to the method described in Comparative Example 1, except that alkali-soluble resin B-2 was used instead of alkali-soluble resin B-1. The light-shielding film of Comparative Example 3, in which 1 was formed in this order, was produced.

[Comparative Examples 4-6]

In the sputtering process, a black layer and an oxygen blocking layer CE- were formed on the substrate according to the method described in Example 1, except that the discharge power and film formation time were adjusted and the layers having the thicknesses shown in Table 3 were formed, respectively. Light-shielding films of Comparative Examples 4 to 6, in which 3 to CE-5 were formed in this order, were produced, respectively.

[Comparative 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 Application Publication No. 2013-253145, tetramethoxysilane (TMOS) and trifluoropropyltrimethoxysilane (TFPTMS) were hydrated. Composition 2 for comparison was prepared by mixing the decomposition product and the silica sol in which the beads-shaped colloidal silica particles were dispersed.

<Formation of comparative oxygen barrier layer CE-6>

Comparative Example 1, except that in the process of forming the oxygen barrier layer, Comparative Composition 2 prepared above was used instead of Composition 1, and the application amount of Comparative Composition 2 was adjusted so that the thickness of the layer after drying was 190 nm. According to the method described in , a light-shielding film of Comparative Example 7 was produced in which a black layer and an oxygen blocking layer CE-6 were formed in this order on a substrate.

Additionally, the surface of the oxygen barrier layer CE-6 was polished to form a smooth surface, and the formed smooth surface was then analyzed using an electron beam microanalyzer (“JXA-8530F” (trade name) manufactured by Nippon Electronics Co., Ltd.). As a result, the content of carbon atoms in the material constituting the oxygen barrier layer CE-6 was 27% by mass with respect to the total mass of the oxygen barrier layer.

[Comparative Examples 8 to 10]

Light-shielding films of Comparative Examples 8 to 10 in which only the black layer was formed on the substrate were produced according to the method described in Examples 1, 6, and 5, except that the oxygen blocking layer E-1 was not formed.

〔evaluation〕

Each oxygen blocking layer or each light-shielding film obtained above was subjected to the following tests and evaluations.

[Measurement of oxygen permeability]

Examples 1, 7 and 10 to 13, and Comparative Examples 1, 2 and 4 to 7, except that instead of the black layer-containing substrate, a peeling layer-containing substrate was used and each oxygen blocking layer was formed on the peeling layer. According to the described method, laminates in which a release layer and an oxygen blocking layer were formed in this order on a substrate were produced, respectively. Next, the oxygen barrier layer was peeled from the obtained laminate to produce an oxygen barrier layer for evaluating oxygen permeability.

The oxygen permeability (ml/(m ² ·day·atm)) of the oxygen barrier layer for evaluation produced above was measured using an oxygen permeation measuring device (Model8001, manufactured by Illinois Corporation).

[Evaluation of lightfastness]

<Investigation Test>

The light-shielding film obtained above was tested for 500 hours using a ^light resistance tester (Super conducted an investigative test.

<Change in film thickness before and after irradiation test>

The film thickness of the light-shielding film before and after the irradiation test was measured using a contact-type film thickness meter. The rate of change in the film thickness of the light-shielding film before and after the irradiation test was calculated using the following equation, and evaluated from the following viewpoint.

In addition, the “film thickness of the light-shielding film” means the sum of the thickness of the black layer and the thickness of the oxygen blocking layer, and does not include the thickness of the substrate.

Rate of change in film thickness (%) = ((Thickness of the light-shielding film before the irradiation test - Film thickness of the light-shielding film after the irradiation test)/(Thickness of the light-shielding film before the irradiation test) × 100)

A: The rate of change in film thickness is less than 2%.

B: The rate of change in film thickness is 2% or more and less than 5%

C: Rate of change in film thickness is 5% or more and less than 10%

D: The rate of change in film thickness is 10% or more.

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

Using a spectrometer V7200 (brand name, manufactured by Nippon Bunko Co., Ltd.), light was incident at an incident angle of 5° onto the light shielding film before and after the irradiation test, and among the obtained transmission and reflection spectra, the maximum transmittance at a wavelength of 350 to 1200 nm (hereinafter referred to as , described as transmittance) and reflectance at a wavelength of 550 nm were measured.

The rate of change in the transmittance and reflectance of the light-shielding film before and after the irradiation test, calculated from the following equation, was evaluated from the following viewpoints.

Rate of change in transmittance (%) = ((Transmittance before irradiation test - Transmittance after irradiation test)/Transmittance before irradiation test × 100)

Rate of change in reflectance (%) = ((Reflectance before irradiation test - Reflectance after irradiation test) / Reflectance before irradiation test × 100)

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

B: Among the rate of change of transmittance and reflectance, one is 2% or more and the other is less than 2%

C: The rate of change of transmittance and the rate of change of reflectance are both 2% or more.

[Evaluation of heat resistance]

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

The film thickness of the light-shielding film before and after the heat resistance test was measured using a contact-type film thickness meter. The rate of change in the film thickness of the light-shielding film before and after the heat resistance test was calculated using the following equation, and evaluated from the following viewpoint.

Rate of change in film thickness (%) = ((film thickness before heat resistance test - film thickness after heat resistance test) / (film thickness of light-shielding film before heat resistance test - thickness of substrate) × 100)

A: The rate of change in film thickness is less than 2%.

B: The rate of change in film thickness is 2% or more and less than 4%

C: The rate of change in film thickness is 4% or more and less than 6%

D: Rate of change in film thickness is 6% or more

[Evaluation of moisture resistance]

The light-shielding film obtained above was placed in a constant temperature and humidity chamber, and a moisture resistance test was conducted for 500 hours under conditions of 85°C and 85%RH. For the substrate after the moisture resistance test, a cross section of a line pattern with an aperture line width of 50 μm was observed using a scanning electron microscope (SEM) S-4800 (brand name, manufactured by Nippon Electronics Co., Ltd.). From the SEM image of the obtained cross-section, the presence or absence of pattern peeling was evaluated from the following viewpoints.

A: No peeling is visible throughout the pattern.

B: Peeling is observed in less than 20% of the entire pattern.

C: Peeling is observed in 20% or more but less than 50% of the entire pattern.

D: Peeling is observed 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 each test on the light-shielding films produced using these light-shielding compositions.

In Tables 1 to 3, "color material content" means 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" of the "oxygen barrier layer" means that the oxygen barrier layer is a layer composed of the following materials.

A: Sputtered layer of silicon oxide (SiO ₂ )

B: Sputtered layer of silicon nitride (Si ₃ N ₄ )

C: Organic layer consisting of PVA and PVP

D: Organic layer made of polyorganosiloxane containing silicon oxide particles

In Tables 1 to 3, the "thickness" column of "oxygen blocking layer" means the thickness (nm) of each oxygen blocking layer measured using a contact film thickness meter.

In addition, in Tables 1 to 3, "thickness of black layer/thickness of oxygen blocking layer" means the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer, measured using a contact film thickness meter.

[Table 1]

[Table 2]

[Table 3]

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

It was confirmed that the content of the black colorant is preferably 70% by mass or less and more preferably 65% by mass or less because the moisture resistance of the light shielding film is more excellent (comparison of Example 1, Examples 15 and 17).

It was confirmed that the content of the black colorant is preferably 30% by mass or more and more preferably 50% by mass or more because the heat resistance of the light shielding film is more excellent (comparison of Example 1, Examples 14 and 16).

It was confirmed that the black colorant preferably contains titanium oxynitride, a benzofuranone compound, or a perylene compound because the moisture resistance of the light shielding film is more excellent (comparison of Examples 1, 3, 4, and 5).

In addition, it was confirmed that the black colorant preferably contains titanium oxynitride or carbon black because the light resistance of the light shielding film is more excellent (comparison of Examples 1, 3, 4, and 5).

In addition, from Examples 18 to 20 described later, the black color material containing vanadium nitride, niobium nitride, or zirconium nitride is the same as the black color material containing titanium oxynitride in that it has better moisture resistance and light resistance of the light shielding film. It has been confirmed that it is desirable.

It was confirmed that the dispersion resin preferably contains an ethylenically unsaturated group because the light resistance, heat resistance, and moisture resistance of the light shielding film are more excellent (comparison of Example 1 and Example 9).

It was confirmed that polyimide resin is preferable as the alkali-soluble resin because it has superior light resistance and heat resistance of the light shielding film (comparison of Example 1 and Example 6). In addition, from Example 21 described later, it was confirmed that a resin made of a polybenzoxazole precursor is preferable as an alkali-soluble resin, as is a polyimide resin, because the light resistance and moisture resistance of the light shielding film are more excellent.

It was confirmed that polymerization initiator C-1 is preferable because the light resistance and heat resistance of the light shielding film are more excellent (comparison of Example 1 and Example 8).

It was confirmed that the polymerizable compound D-1 is preferable because it has better heat resistance and moisture resistance of the light shielding film (comparison of Example 1 and Example 2).

It was confirmed that the oxygen blocking layer preferably contains silicon oxide because the light resistance and moisture resistance of the light shielding film are more excellent (comparison of Example 1 and Example 7).

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

It was confirmed that the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is preferably 7 to 30 because the moisture resistance and heat resistance of the light shielding film are more excellent (comparison of Example 1 with Examples 10 and 11).

[Examples 18-20]

Color material compositions A-6 to A-8 were prepared according to the preparation method of color material composition A-1 above, except that the following color materials a-5 to a-7 were used instead of titanium black (color material a-1). Each was prepared.

Color material a-5: Vanadium nitride (brand name “VN-O”, manufactured by Nippon Shinkinzoku Co., Ltd.)

Color material a-6: Niobium nitride (brand name “NbN-O”, manufactured by Nippon Shinkinzoku Co., Ltd.)

Colorant a-7: Zirconium nitride (prepared by the method of Example 1 of Japanese Patent Publication No. 2017-222559)

The light-shielding properties of Examples 18-20 were obtained according to the preparation method of the light-shielding composition 1 of Example 1, except that each of the coloring compositions A-6 to A-8 prepared above was used instead of coloring composition A-1. Each composition was prepared. Examples 18 to 20, in which a black layer and an oxygen blocking layer are formed in this order on a substrate according to the method described in Example 1, except that each of the obtained light-shielding compositions is used instead of light-shielding composition 1. A light shield was produced for each. All evaluation results of the light-shielding films of Examples 18 to 20 were equivalent to those of Example 1.

Except that colorant a-8 was used instead of titanium black (colorant a-1), a colorant composition was prepared according to the preparation method of colorant composition A-1 above, and the same evaluation as in Example 1 was performed.

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

The evaluation results were the same as Example 1.

Instead of titanium black (colorant a-1), the weight ratio of colorant a-1 and colorant a-7 is a-1:a-7=1:9, 3:7, 5:5, 7:3, 9, respectively. A colorant composition was prepared according to the preparation method of colorant composition A-1 above, except that a mixture of 1 was used, and the same evaluation as in Example 1 was performed.

The evaluation results were the same as Example 1.

Also, instead of titanium black (colorant a-1), the weight ratio of colorant a-1 and colorant a-8 is a-1:a-8=1:9, 3:7, 5:5, 7:3, respectively. , A color material composition was prepared according to the preparation method of color material composition A-1 described above, and the same evaluation as in Example 1 was performed, except that a mixture of 9:1 was used.

The evaluation results were the same as 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 alkali-soluble resin B-3 was used instead of alkali-soluble resin B-1.

A light-shielding film of Example 21 was produced in which a black layer and an oxygen blocking layer were formed in this order on a substrate according to the method described in Example 1, except that the obtained light-shielding composition was used instead of light-shielding composition 1. did. All evaluation results of the light-shielding film of Example 21 were equivalent to those of Example 1.

[Example 22]

The light-shielding composition of Example 22 was prepared according to the preparation method of light-shielding composition 1 of Example 1, except that polymerization initiator C-3 was used instead of polymerization initiator C-2. A light-shielding film of Example 22 was produced in which a black layer and an oxygen blocking layer were formed in this order on a substrate according to the method described in Example 1, except that the obtained light-shielding composition was used instead of the light-shielding composition 1. did. The evaluation results of the light-shielding film of Example 22 were equivalent to those of Example 8 except that the heat resistance was C.

[Example 23]

In the preparation of light-shielding composition 1, instead of 6.1 parts by mass of polymerizable compound D-1, a mixture of polymerizable compound D-1 and polymerizable compound D-2 at a mass ratio of 1:1 was used, except that 6.1 parts by mass were used. According to the method of Example 1, the light-shielding composition of Example 23 was prepared. A light-shielding film of Example 23 was produced in which a black layer and an oxygen blocking layer were formed in this order on a substrate according to the method described in Example 1, except that the obtained light-shielding composition was used instead of light-shielding composition 1. did. The evaluation results of the light-shielding film of Example 23 were equivalent to those of Example 1 except that the moisture resistance was B.

[Examples 24-25]

In the sputtering process, the discharge power and film formation time were adjusted, and the oxygen blocking layers E-7 and E-8 made of silicon oxide (SiO ₂ ) with a thickness of 70 nm and 200 nm were formed, respectively, in Example 1. According to the described method, light-shielding films of Examples 24 and 25 were produced, respectively, in which a black layer and an oxygen blocking layer were formed in this order on a substrate. All evaluation results of the light-shielding films of Examples 24 and 25 were equivalent to those of Example 1.

[Examples 26-27]

The light-shielding composition of Example 26 was prepared according to the preparation method of light-shielding composition 1 of Example 1, except that no polymerization inhibitor was used. Additionally, the light-shielding composition of Example 27 was prepared according to the preparation method of light-shielding composition 1 of Example 1, except that no surfactant was used. Light-shielding films of Examples 26 and 27, in which a black layer and an oxygen blocking layer are formed in this order on a substrate according to the method described in Example 1, except that each of the obtained light-shielding compositions is used instead of light-shielding composition 1. were produced respectively. All evaluation results of the light-shielding films of Examples 26 and 27 were equivalent to those of Example 1.

[Example 28]

<Production of a color filter having a black matrix>

Light-shielding composition 1 of Example 1 was applied to a glass wafer by spin coating to form a composition layer. Next, the glass wafer was placed on a hot plate, and prebaking was performed at 120°C for 2 minutes. Next, using an i-line stepper, the composition layer was exposed at an exposure dose of 500 mJ/cm ² through a photomask with an island pattern of 0.1 mm.

Next, the composition layer after exposure was puddle developed at 23°C for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide to obtain a cured film. The obtained cured film was rinsed using a spin shower and further washed with pure water to form a patterned black layer.

Next, according to the method for forming the oxygen barrier layer E-1 in Example 1, an oxygen barrier layer made of silicon oxide is formed on the surface of the black layer produced above, thereby forming a black layer and an oxygen barrier layer on the glass wafer. A light shielding film (black matrix) formed in this order was produced. As a result of manufacturing a color filter using the black matrix, it had good performance.

[Example 29]

<Manufacturing of a solid-state imaging device having a light-shielding film>

Curable composition for lenses (a composition obtained by adding 1% by mass of an arylsulfonium salt derivative (manufactured by ADEKA, brand name "SP-172") to an alicyclic epoxy resin (manufactured by Daicel Chemical Company, brand name "EHPE-3150")) (2 mL) was applied on a 5 x 5 cm glass substrate (thickness 1 mm, manufactured by Schott, brand name "BK7"), and the coating film was cured by heating at 200°C for 1 minute to form a lens film that can evaluate residues on the lens.

Light-shielding composition 1 of Example 1 was applied onto the glass wafer on which the lens film was formed, to form a composition layer. Next, the glass wafer was placed on a hot plate, and prebaking was performed at 120°C for 120 seconds. The thickness of the composition layer after heating was 2.0 μm.

Next, the composition layer was exposed at an exposure dose of 500 mJ/cm ² using a high-pressure mercury lamp through a photomask with a 10 mm hole pattern. Next, the exposed composition layer was subjected to puddle development for 60 seconds at a temperature of 23°C using a 0.3% aqueous solution of tetramethylammonium hydroxide to obtain a cured film. The obtained cured film was rinsed using a spin shower and further washed with pure water to form a patterned black layer.

Next, according to the method for forming the oxygen barrier layer E-1 in Example 1, an oxygen barrier layer made of silicon oxide is formed on the surface of the black layer produced above, thereby forming a black layer and an oxygen barrier layer on the glass wafer. A light-shielding film formed in this order was produced.

On the glass wafer on which the light-shielding film prepared above was formed, a curable composition for lenses (alicyclic epoxy resin (manufactured by Daicel Chemical Company, brand name "EHPE-3150")) and an arylsulfonium salt derivative (manufactured by ADEKA, brand name "SP-172") were added. A curable resin layer was formed using a composition to which 1% by mass of ") was added. Next, the shape was transferred to a quartz mold having a lens shape, and the curable resin layer was cured by exposure to a high-pressure mercury lamp at an exposure dose of 400 mJ/cm ² to produce a wafer-level lens array having a plurality of wafer-level lenses. .

The produced wafer-level lens array was cut, a lens module was produced using the obtained wafer-level lens, and then an imaging element and a sensor substrate were mounted to produce a solid-state imaging element provided with the light-shielding film of the present invention.

The obtained solid-state imaging device had good transmittance with no residue in the lens opening of the wafer level lens, and also had high light-shielding properties due to the high uniformity of the applied surface of the light-shielding film.

[Example 30]

<Production of a headlight unit with a light shield>

On a 10 cm square glass substrate, the light-shielding composition 1 of Example 1 obtained above was applied by spin coating to form a composition layer. The glass substrate was placed on a hot plate and prebaked at 120°C for 2 minutes.

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

Next, development was performed using a developing device (Act-8, manufactured by Tokyo Electron). As a developing solution, a 0.3% aqueous solution of tetramethylammonium hydroxide was used, and puddle development was performed at 23°C for 60 seconds. Thereafter, the obtained cured film was rinsed with a spin shower using pure water to obtain a black layer with a predetermined light distribution pattern.

Next, according to the method for forming the oxygen barrier layer E-1 in Example 1, an oxygen barrier layer made of silicon oxide is formed on the surface of the black layer produced above, thereby forming a black layer and an oxygen barrier layer on the glass substrate. A light-shielding film formed in this order was produced.

As a result of manufacturing a headlight unit using the obtained light shielding film, light source, and lens, it had good performance.

10… headlight unit
12… light source
14… shading part
16… lens
20… gas
22… sunshade
23… opening
30… light distribution pattern
30a… edge
31… area
32… light distribution pattern
32a… edge
33… notch
100… solid-state imaging device
101… solid-state imaging device
102… imaging department
103… cover glass
104… spacer
105… laminated board
106… chip board
107… circuit board
108… electrode pad
109… external connection terminal
110… penetrating electrode
111… lens layer
112… lens material
113… support
114, 115… sunshade
201… light receiving element
202… color filter
203… micro lens
204… Board
205b… blue pixel
205r… red pixel
205g… green pixel
205bm… black matrix
206… p-well layer
207… Read gate section
208… vertical transmission line
209… device isolation area
210… gate insulating film
211… vertical transmission electrode
212… sunshade
213, 214… insulating 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

Claims (19)

A black layer containing a black colorant,
A light shielding film having an oxygen blocking layer formed on the black layer,
The oxygen blocking layer is a single layer made of an inorganic material,
The thickness of the oxygen blocking layer is 10 to 500 nm,
The ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is 7 to 30,
The black layer contains two or more polymerizable compounds having different numbers of ethylenically unsaturated groups, and the compound having a smaller number of ethylenically unsaturated groups is a compound containing at least one hydroxyl group,
A light shielding film, wherein the two or more types of polymerizable compounds having different numbers of ethylenically unsaturated groups include a polymerizable compound having five ethylenically unsaturated groups and a polymerizable compound having six ethylenically unsaturated groups. A black layer containing a black colorant,
A light shielding film having an oxygen blocking layer formed on the black layer,
The oxygen blocking layer is a single layer made of an inorganic material,
The thickness of the oxygen blocking layer is 10 to 500 nm,
The black layer contains an alkali-soluble resin containing at least one selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and copolymers thereof,
The black layer contains two or more polymerizable compounds having different numbers of ethylenically unsaturated groups, and the compound having a smaller number of ethylenically unsaturated groups is a compound containing at least one hydroxyl group,
A light shielding film, wherein the two or more types of polymerizable compounds having different numbers of ethylenically unsaturated groups include a polymerizable compound having five ethylenically unsaturated groups and a polymerizable compound having six ethylenically unsaturated groups. In claim 1 or claim 2,
A light-shielding film in which the black color material contains an oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium, and niobium. In claim 1 or claim 2,
A light-shielding film in which the black colorant contains carbon black, a benzofuranone compound, or a perylene compound. In claim 1 or claim 2,
A light-shielding film wherein the content of the black colorant is 20 to 80% by mass with respect to the total mass of the black layer. In claim 1 or claim 2,
A light-shielding film in which the oxygen blocking layer contains silicon oxide. In claim 2,
A light-shielding film wherein the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is 2 to 100. In claim 1 or claim 2,
A light shielding film wherein the oxygen transmission rate of the oxygen blocking layer is 10 ml/(m ² ·day·atm) or less. In claim 1 or claim 2,
A light-shielding film, wherein the oxygen blocking layer contains substantially no particles. A step of applying a light-shielding composition containing a black colorant, a resin, a polymerizable compound, and a polymerization initiator onto a support, and curing the obtained coating film to form a black layer;
A process of forming an oxygen blocking layer on the black layer,
The oxygen blocking layer is a single layer made of an inorganic material,
The thickness of the oxygen blocking layer is 10 to 500 nm,
The ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is 7 to 30,
The black layer contains two or more polymerizable compounds having different numbers of ethylenically unsaturated groups, and the compound having a smaller number of ethylenically unsaturated groups is a compound containing at least one hydroxyl group,
A method for producing a light-shielding film, wherein the two or more types of polymerizable compounds having different numbers of ethylenically unsaturated groups include a polymerizable compound having five ethylenically unsaturated groups and a polymerizable compound having six ethylenically unsaturated groups. A step of applying a light-shielding composition containing a black colorant, a resin, a polymerizable compound, and a polymerization initiator onto a support, and curing the obtained coating film to form a black layer;
A process of forming an oxygen blocking layer on the black layer,
The oxygen blocking layer is a single layer made of an inorganic material,
The thickness of the oxygen blocking layer is 10 to 500 nm,
The resin contains an alkali-soluble resin containing at least one member selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and copolymers thereof,
The black layer contains two or more polymerizable compounds having different numbers of ethylenically unsaturated groups, and the compound having a smaller number of ethylenically unsaturated groups is a compound containing at least one hydroxyl group,
A method for producing a light-shielding film, wherein the two or more types of polymerizable compounds having different numbers of ethylenically unsaturated groups include a polymerizable compound having five ethylenically unsaturated groups and a polymerizable compound having six ethylenically unsaturated groups. In claim 10 or claim 11,
A method of manufacturing a light-shielding film, wherein the step of forming the oxygen blocking layer includes a step of depositing an inorganic material. In claim 10,
A method for producing a light-shielding film, wherein the resin contains an alkali-soluble resin containing at least one selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and copolymers thereof. delete In claim 10 or claim 11,
A method for producing a light-shielding film, wherein the polymerization initiator is a compound represented by the following formula (C-13).
[Formula 1]

In claim 10 or claim 11,
A method for producing a light-shielding film, wherein the resin contains a resin having an ethylenically unsaturated group. An optical element containing the light-shielding film according to claim 1 or 2. A solid-state imaging device containing the light-shielding film according to claim 1 or 2. As a headlight unit of a vehicle light,
light source,
It has a light-shielding portion that blocks at least a portion of the light emitted from the light source,
A headlight unit in which the light-shielding portion contains the light-shielding film according to claim 1 or 2.