TW202022024A - Light-shielding composition, cured film, light-shielding film, and solid-state imaging element - Google Patents

Abstract

Provided is a light-shielding composition which enables the formation of a cured film having excellent light-shielding properties, low reflectance, and light resistance. Also provided are a cured film, a light-shielding film, and a solid-state imaging element. This light-shielding composition contains a blacking material, a polymerizable compound, a photopolymerization initiator, and a resin. The resin contains a polymerizable group and a group represented by general formula (1). The number average molecular weight of the resin is 100 to 15000. The resin content is 2.0 to 15.0% by mass of the total solids content by mass of the light-shielding composition.

Description

Light-shielding composition, cured film, light-shielding film, solid-state imaging device

The present invention relates to a light-shielding composition, a hardened film, a light-shielding film and a solid-state imaging element.

Regarding the production of a cured film used as a light-shielding film suitable for solid-state imaging devices, etc., a method of curing the light-shielding composition layer after forming it on a substrate is common. At this time, the light-shielding composition layer is typically irradiated with light through a predetermined mask pattern, and then the development process is performed.

For example, Patent Document 1 discloses "a light-shielding coating film containing at least one component selected from (a) resin, (b) color material, (c) inorganic fine particles, (d) surfactant, and oil, This light-shielding coating film is characterized in that the concentration of at least one component selected from (d) surfactants and oils in the surface layer of the coating film is higher than that in the lower layer (Patent Scope 1)". As an example of the above oil, dimethyl Base silicone oil. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2011-141493 A

In recent years, there have been various requirements for cured films that are also used as light-shielding films in addition to good light-shielding properties. For example, with the miniaturization, thinning, and higher sensitivity of solid-state imaging devices, further reduction in reflection of the cured film is required. In addition, it is also required to maintain excellent low reflectivity even when the cured film is irradiated with light for a long period of time (hereinafter, these characteristics are also referred to as "the cured film (or light-shielding film) has excellent light resistance").

Therefore, the subject of the present invention is to provide a light-shielding composition capable of forming a cured film having excellent light-shielding properties, low reflectivity, and light resistance. In addition, the subject is to provide a cured film, a light-shielding film, and a solid-state imaging element.

As a result of intensive research, the inventors found that the above-mentioned problems can be solved by the following configuration.

[1] A light-shielding composition containing a black coloring material, a polymerizable compound, a photopolymerization initiator, and a resin, the resin containing a polymerizable group and a group represented by the general formula (1), and the number of the resin is average The molecular weight is 100 to 15000, the content of the resin is 2.0 to 15.0% by mass relative to the total mass of the solid content of the light-shielding composition, *-(SiR ¹ R ² -O) _na -* (1) General formula (1) In ), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. na represents an integer of 1 to 200. * Indicates the bonding position. [2] The light-shielding composition according to [1], wherein the resin is a compound represented by the general formula (2), R ³ -(SiR ¹ R ² -O) _nb -SiR ¹ R ² -R ³ ( 2) In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, R ³ represents a group containing an ethylenically unsaturated group, and nb represents 3 to 200 Integer. [3] The light-shielding composition according to [2], wherein at least one of the aforementioned R ³ has an acid group. [4] The light-shielding composition according to [2] or [3], wherein at least one of the aforementioned R ³ is selected from the group consisting of an ether bond, an ester bond, a urethane bond, and a thioether bond At least one of them. [5] The light-shielding composition according to any one of [1] to [4], wherein the black coloring material is one or more selected from the group consisting of metal nitrides and metal oxynitrides. [6] A cured film obtained using the light-shielding composition described in any one of [1] to [5]. [7] The cured film according to [6], wherein the cured film includes a black layer and a coating layer disposed on the surface of the black layer, the thickness of the coating layer is 20 to 200 nm, and the coating layer includes The cured product of this resin. [8] The cured film according to [6] or [7], which is a light-shielding film. [9] A solid-state imaging device comprising the cured film described in any one of [6] to [8]. [Invention Effect]

According to the present invention, it is possible to provide a light-shielding composition capable of forming a cured film excellent in light-shielding, low reflectivity, and light resistance. Moreover, it is also possible to provide a cured film, a light shielding film, and a solid-state imaging element.

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

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

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

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

In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene conversion values based on the GPC (Gel Permeation Chromatography) method. In this specification, the GPC method is based on the following method, that is, HLC-8020GPC (manufactured by TOSOH CORPORATION), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID×15cm) as the column THF (tetrahydrofuran) was used as the extract.

[Light-shielding composition] The light-shielding composition of the present invention (hereinafter, also simply referred to as "composition") contains a black coloring material, a polymerizable compound, a photopolymerization initiator, and a resin. The above-mentioned resin system contains a polymerizable group and a resin having a number average molecular weight of 100 to 15,000 (hereinafter, this resin is also referred to as "specific resin") of the group represented by the general formula (1) described later. The content of the specific resin is 2.0 to 15.0% by mass with respect to the total mass of the solid content of the light-shielding composition.

The mechanism by which the problem of the present invention can be solved by using the composition having the above-mentioned structure is not clear, but the present inventors speculate as follows. The (poly)siloxane group represented by the general formula (1) contained in the specific resin exhibits low surface free energy. In addition, the molecular weight is 100 to 15,000, so it can move relatively freely in the composition. Therefore, for example, in a composition layer formed by applying a composition on a substrate, a specific resin tends to be concentrated and present near the surface of the composition layer on the side opposite to the substrate. As a result, as shown in FIG. 1, the cured film 10 obtained from the cured composition layer on the substrate 16 has a black layer (lower layer) 12 containing a black coloring material and a coating layer (upper side) of a cured product containing a specific resin Layer) 14 two-layer structure. If these two-layer structures are formed, the light reflected on the surface of the cladding layer and the light reflected at the interface between the cladding layer and the black layer are eliminated due to interference, thereby achieving low reflectivity. In addition, the specific resin contains a polymerizable group, so even if the development process is performed in the process of forming the cured film, the coating layer is not removed from the cured film, and excellent low reflectivity can be achieved. Furthermore, it is estimated that since the structure of the (poly)siloxyalkyl group contained in the specific resin is rigid, it is unlikely to change even if it is irradiated with light, and therefore the light resistance is also improved.

First, the components of the composition of the present invention will be described.

〔Black coloring material〕 The light-shielding composition contains a black coloring material. The content of the black coloring material in the composition is preferably 10 to 90% by mass with respect to the total mass of the solid content of the composition, more preferably 30 to 80% by mass, and still more preferably 50 to 70% by mass. In addition, the "shielding" in which the cured film formed of the composition of the present invention is used as a light-shielding film also includes the concept of light attenuation that passes through the cured film (light-shielding film) while attenuating light. When using a cured film (light-shielding film) as a light attenuating film having such a function, the content of the black coloring material in the composition is preferably less than the above-mentioned appropriate range. A black coloring material may be used individually by 1 type, and may use 2 or more types. In addition, in this specification, when the composition contains a solvent (organic solvent, water, etc.), the solid content of the composition means all the components except the solvent. If it is a component other than the solvent, even the liquid component is regarded as solid. ingredient.

As a black coloring material, 1 or more types chosen from the group which consists of black pigments and black dyes are mentioned. In addition, it is possible to combine plural kinds of coloring agents that cannot be used alone as a black coloring material, and adjust so that the whole becomes black as a black coloring material. For example, in addition to using a pigment that expresses black alone as a black pigment, it is also possible to combine a plurality of pigments that have a color other than black when they are singly used as a black pigment. In the same way, in addition to using a dye that expresses black alone as a black dye, it is also possible to use a combination of a plurality of dyes that have colors other than black when alone. In addition, by using a coloring agent that cannot be used as a black coloring material alone, it is easy to adjust the light-shielding properties of the cured film. For example, when a cured film is used as a light attenuation film, it is easy to evenly attenuate each wavelength for light containing broad-wavelength components. In addition, the black coloring material means a coloring material that has absorption in all the wavelength ranges of 400 to 700 nm. More specifically, for example, a black coloring material that meets the evaluation criteria Z described below is preferable. First, a composition containing a color material, a transparent resin matrix (acrylic resin, etc.), and a solvent is prepared, and the content of the color material relative to the total solid content is 60% by mass. The obtained composition was applied on a glass substrate until the film thickness of the dried coating film became 1 μm, thereby forming a coating film. The light-shielding property of the coating film after drying was evaluated by a spectrophotometer (UV-3600 manufactured by Hitachi, Ltd., etc.). If the maximum value of the transmittance in the wavelength 400 to 700 nm of the dried coating film is less than 10%, it can be determined that the color material is a black color material that meets the evaluation criteria Z.

(Black paint) From the viewpoint of obtaining a cured film with more excellent low reflectivity, black pigments such as black coloring material-based metal nitrides and/or metal oxynitrides are preferred. As the black pigment, various well-known black pigments can be used. The black pigment can be an inorganic pigment or an organic pigment.

As the black pigment, a pigment that expresses black alone is preferable. As the black pigment, various well-known black pigments can be used. The black pigment can be an inorganic pigment or an organic pigment. As the black inorganic pigment, for example, one or more selected from the group consisting of metal nitrides, metal oxynitrides, and metal oxides are preferred, and are selected from the group consisting of metal nitrides and metal oxynitrides. One or more of them is more preferable. Examples of metal nitrides, metal oxynitrides, and metal oxides include, more specifically, metal elements selected from Group 4 including titanium (Ti) and zirconium (Zr), vanadium (V), and niobium. (Nb) and other Group 5 metal elements, cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn) One or two or more metal elements in the group of silver (Ag), such as metal nitrides, metal oxynitrides, and metal oxides. Surface modification treatment can be applied to inorganic pigments. For example, inorganic particles that have been surface-modified with a surface treatment agent having both a silicon group and an alkyl group are used, and examples include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., LTD.). In addition, metal nitrides, metal oxynitrides, and metal oxides can also be used as particles further mixed with other atoms. For example, it can also be used as metal nitrides, metal oxynitrides, and metal oxides that further contain atoms (preferably sulfur atoms) selected from elements of groups 13 to 17 of the periodic table. As a black pigment, carbon black can also be mentioned. As carbon black, carbon black whose surface is coated with resin can be used. As black pigments, commercially available organic pigments such as C.I. Pigment Black 1 and Irgaphor Black S 0100 CF, and inorganic pigments such as C.I. Pigment Black 7.

In addition, in this specification, titanium nitride means TiN, and may contain oxygen atoms that are unavoidable in production (for example, the surface of TiN particles is oxidized unexpectedly, etc.). In this specification, titanium nitride refers to a compound derived from the refraction angle 2θ of the peak of the (200) plane when CuKα rays are used as an X-ray source and is 42.5° to 42.8°. In addition, in this specification, titanium oxynitride means a compound whose refraction angle 2θ derived from the peak of the (200) plane when CuKα rays are used as an X-ray source is greater than 42.8°. The upper limit of the refraction angle 2θ of titanium oxynitride is not particularly limited, but 43.5° or less is preferred. As the titanium oxynitride, for example, titanium black can be mentioned. More specifically, for example, it can be exemplified by containing low-valent titanium dioxide represented by TiO ₂ and Ti _n O _2n-1 (1≤n≤20) and/or TiN _x O _y (0<x<2.0, 0.1<y<2.0) represents the form of titanium oxynitride. In the following description, titanium nitride (the above-mentioned refraction angle 2θ is 42.5° to 42.8°) and titanium oxynitride (the above-mentioned refraction angle 2θ greater than 42.8°) are collectively referred to as titanium nitrides, and their morphology will be explained. In addition, titanium nitride can be used as a particle further mixed with other atoms. For example, titanium nitride can be used as titanium-containing nitride particles further containing atoms (preferably sulfur atoms) selected from the elements of groups 13 to 17 of the periodic table. In addition, similarly to other metal nitrides, metal nitrides, which are collectively called metal nitrides and oxynitride metals, can be used as particles further mixed with other atoms. For example, metal nitrides can also be used as metal nitrides that further contain atoms (preferably sulfur atoms) selected from elements of groups 13 to 17 of the periodic table.

When CuKα rays are used as the X-ray source to measure the X-ray refraction spectrum of titanium nitrides, as the strongest peak, TiN is observed at 2θ=42.5° near the peak derived from the (200) plane, while TiO is at 2θ=43.4° A peak from the (200) plane was observed nearby. On the other hand, although it is not the strongest peak, anatase type TiO _{2 has} a peak originating from the (200) plane around 2θ=48.1°, while rutile type TiO ₂ is observed around 2θ=39.2° At the peak from (200) face. Therefore, as the titanium oxynitride contains more oxygen atoms, the peak position shifts to the higher angle side with respect to 42.5°.

When titanium nitride contains titanium oxide TiO ₂ , as the strongest peak, a peak derived from anatase TiO ₂ (101) can be observed near 2θ=25.3°, and a peak derived from anatase type TiO ₂ (101) is observed near 2θ=27.4° The peak of rutile TiO ₂ (110). However, TiO ₂ is white, which will reduce the light-shielding properties of the cured film obtained from the cured composition, so it is better to reduce it to such an extent that it is not observed as a peak.

The size of the crystallite constituting the titanium nitride is obtained from the half-width of the peak obtained by the measurement of the above-mentioned X-ray refraction spectrum. The calculation of the crystallite size can be performed using Scherrer's formula.

The crystallite size constituting the titanium nitride is preferably 50 nm or less, and preferably 20 nm or more. If the crystallite size is 20-50 nm, the ultraviolet (especially i-ray (wavelength: 365 nm)) transmittance of the cured film formed from the composition is likely to be higher, and a composition with higher sensitivity can be obtained.

The specific surface area of the titanium nitride is not particularly limited, and it can be determined by the BET (Brunauer, Emmett, Teller) method. The specific surface area of titanium nitride is 5 ~ 100m ² / g is preferred, 10 ~ 60m ² / g is more preferred.

The manufacturing method of the black pigment is not particularly limited, and a known manufacturing method can be used. For example, a gas phase reaction method can be mentioned. Examples of the gas phase reaction method include an electric furnace method and a thermoplasma method. However, the thermoplasma method is preferred from the viewpoints that the mixing of impurities is small, the particle size is easily uniform, and the productivity is high. In the thermoplasma method, there are no particular restrictions on the method of generating thermoplasma. Examples include direct current arc discharge, multilayer arc discharge, high frequency (RF) plasma, and hybrid plasma. Frequency plasma is better. There is no particular limitation on the specific production method of the black pigment based on the thermoplasmic method. For example, as the method of producing titanium nitride, a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Application Publication No. 2 -022110 Bulletin); a method of evaporating titanium powder using high-frequency thermoplasma, introducing nitrogen as a carrier gas, and nitriding it during cooling to synthesize it (Japanese Patent Laid-Open No. 61-011140); and A method of blowing ammonia gas into the periphery of the plasma (Japanese Patent Laid-Open No. 63-085007), etc. However, the manufacturing method of the black pigment is not limited to the above, and the manufacturing method is not limited as long as the black pigment having the required physical properties can be obtained.

The black pigment may have a layer of silicon-containing compound (hereinafter referred to as "silicon-containing compound") on its surface. That is, the (oxy)nitride of the metal atom can be coated with a silicon-containing compound as a black pigment. The method for coating the (oxy)nitride of the metal atom is not particularly limited, and a known method can be used. For example, the method described on page 2 bottom right to page 4 top right of JP 53-033228 A can be mentioned. (Using metal atom (oxy)nitride instead of titanium oxide), the method described in paragraphs 0015 to 0043 of JP 2008-069193 A (using metal atom (oxy)nitride instead of particulate titanium dioxide), The method described in paragraph 0020 and paragraphs 0124 to 0138 of JP 2016-074870 A (using metal atom (oxy)nitride instead of metal oxide fine particles) is incorporated into this specification.

Furthermore, when the light-shielding composition contains titanium black, it is also preferable to contain titanium black as a dispersed body containing titanium black and Si atoms. In this form, titanium black is contained in the composition as a dispersion, and the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersion is preferably 0.05 or more in terms of mass, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable. Here, the above-mentioned dispersed body includes both those in the state of titanium black-based primary particles and those in the state of aggregates (secondary particles). In order to change the Si/Ti of the dispersion (for example, 0.05 or more), the following method can be used. First, by using a dispersing machine to disperse titanium oxide and silicon dioxide particles to obtain a dispersion, the dispersion is reduced at a high temperature (for example, 850 ~ 1000 ℃), whereby the titanium black particles can be obtained as The main component and contains Si and Ti to be dispersed. The above reduction treatment can also be performed in an atmosphere of reducing gas such as ammonium. As titanium oxide, TTO-51N (trade name: manufactured by ISHIHARA SANGYO KAISHA, LTD.) and the like can be mentioned. Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade name: manufactured by EVONIK). A dispersant can be used to disperse titanium oxide and silicon dioxide particles. Examples of the dispersant include those described below as a dispersant. The above dispersion can be performed in a solvent. Examples of solvents include water and organic solvents. Examples include those described below in the column of organic solvents. For example, titanium black with Si/Ti adjusted to 0.05 or more can be produced by the method described in paragraph 0005 and paragraphs 0016 to 0021 of JP 2008-266045 A, for example.

By adjusting the content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersion containing titanium black and Si atoms to a preferable range (for example, 0.05 or more), the composition containing the dispersion is used to When the cured film is formed, residues derived from the composition outside the area where the cured film is formed are reduced. In addition, the residue contains components derived from compositions such as titanium black particles and resin components. The reason for the decrease in residue is not clear, but it is presumed as follows: the dispersed body as described above tends to have a small particle size (for example, the particle size is 30 nm or less), and further, the Si atom-containing component of the dispersed body increases, and This lowers the adsorptivity to the base of the entire film, which contributes to the improvement of the development and removability of the uncured composition (especially titanium black) during the formation of the cured film. In addition, titanium black has excellent light-shielding properties against light in a wide range of wavelengths from ultraviolet light to infrared light. Therefore, a dispersion containing the above-mentioned titanium black and Si atoms (preferably Si/Ti in terms of mass is used) 0.05 or more) The formed cured film exhibits excellent light-shielding properties. In addition, the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersion can be, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP 2013-249417 A To determine. Also, regarding the dispersion contained in the cured film obtained by curing the composition, the method (2) described in paragraph 0035 of JP 2013-249417 A was used to determine the Si atoms and Ti atoms in the dispersion Is the content ratio (Si/Ti) above 0.05?

Among the dispersions containing titanium black and Si atoms, the above-mentioned titanium black can be used. Hereinafter, the material used when introducing Si atoms into the dispersion is described. When introducing Si atoms into the dispersion, a Si-containing substance such as silicon dioxide may be used. As the silica that can be used, precipitated silica, vapor-phase silica, colloidal silica, synthetic silica, and the like can be cited, and these can be appropriately selected and used. Furthermore, if the particle size of the silicon dioxide particles is smaller than the film thickness when the cured film is formed, the light-shielding properties will be more excellent. Therefore, it is preferable to use fine-particle type silicon dioxide as the silicon dioxide particles. In addition, as an example of the fine particle type silicon dioxide, for example, the silicon dioxide described in paragraph 0039 of JP 2013-249417 A, and these contents are incorporated in this specification. It is also preferable to use zirconium nitride or zirconium oxynitride. Zirconium nitride and zirconium oxynitride are preferably coated with an inorganic compound. By coating with an inorganic compound, the photocatalytic activity of the light-shielding pigment is suppressed without impairing the light-shielding property of the light-shielding pigment due to the surface coating, and it is easy to prevent the deterioration of the light-shielding composition. Specific examples of the inorganic compound include titanium dioxide, zirconium oxide, silicon dioxide, aluminum oxide, etc., preferably silicon dioxide and aluminum oxide. For example, titanium black and zirconium nitride, titanium black and zirconium oxynitride, titanium black and silicon dioxide coated zirconium nitride, titanium black and aluminum oxide coated zirconium nitride are the same, and it is better to use them in combination.

Furthermore, as described above, it is also possible to use a combination of a plurality of pigments having colors other than black when used alone as a black pigment. In this way, the pigment having a color other than black may be an inorganic pigment or an organic pigment. As a pigment having a color other than black when alone, for example, color pigments (color pigments) such as R (red), G (green), and B (blue) can also be used.

There are no particular restrictions on the inorganic pigment having a color other than black when alone, and known inorganic pigments can be used. As the above-mentioned inorganic pigments, for example, titanium oxide, chromium oxide, iron oxide, red lead, iron oxide red, yellow lead, zinc yellow (zinc potassium chromate), tetrabasic zinc chromate (zinc tetroxy chromate), ultramarin blue, Prussian blue (potassium ferrocyanide), zircon grey, Praseodymium yellow, chrome titanium yellow, chrome green, malachite green, Victoria Green (victoria green), iron blue (iron blue) (not related to Prussian blue), vanadium zirconium blue (vanadium zirconium blue), chrome tin pink (chrome tin pink), manganese red (manganese pink) and orange red (salmon pink), etc. . The above-mentioned inorganic pigment may be subjected to surface modification treatment. For example, inorganic particles that have been surface-modified with a surface treatment agent having both a silicon group and an alkyl group are used, and examples include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., LTD.).

系、有機群青、藍紅）等； C.I.顏料綠7、10、36、37、58、59等； C.I.顏料紫1、19、23、27、32、37、42等； C.I.顏料藍1、2、15、15：1、15：2、15：3、15:4、15:6、16、22、29、60、64、66、79、80、87（單偶氮系）、88（次甲基/聚次甲基系）等；。As an organic pigment having a color other than black when alone, for example, it is selected from the following organic pigments. Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc., CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 etc. CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294 (𠮿

Series, organic ultramarine blue, blue-red) etc.; CI pigment green 7, 10, 36, 37, 58, 59 etc.; CI pigment violet 1, 19, 23, 27, 32, 37, 42 etc.; CI pigment blue 1, 2 , 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo series), 88 (times Methyl/polymethine series) etc.;

The pigment can be used in combination with the dye described later. In order to adjust the color tone and increase the light-shielding in the desired wavelength range, for example, red, green, yellow, orange, purple, and blue can be mixed with a pigment that expresses black alone and/or a pigment that has a color other than black when alone. Pigment or dye mentioned later. Moreover, it is preferable to mix a red pigment or dye, or a purple pigment or dye to a pigment that absorbs infrared rays and express black alone, and it is more preferable to mix a red pigment. Furthermore, you may add an infrared absorber mentioned later.

In addition, as a pigment that has a color other than black and absorbs infrared rays when it is alone, tungsten compounds, metal borides, and the like can also be used. Among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding properties of wavelengths in the infrared region. The tungsten compound has excellent light transmittance in the light absorption wavelength region and visible light region of the oxime-based polymerization initiator related to the curing efficiency by exposure.

In consideration of handling properties, the average primary particle size of the black pigment is preferably 0.01 to 0.1 μm, and more preferably 0.01 to 0.05 μm. When the black pigment includes a combination of plural kinds of pigments, one or more of the pigments constituting the black pigment are preferably within the above range, and it is more preferable that all of the pigments constituting the black pigment are within the above range.

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

(Black dye) As the black dye, a dye that independently expresses black can be used. Furthermore, as described above, it is also possible to use a combination of a plurality of dyes having colors other than black when they are singly used as a black dye. As such coloring dyes, for example, in addition to color dyes (color dyes) such as R (red), G (green), and B (blue), the ones described in paragraphs 0027 to 0200 of JP 2014-042375 can also be used. Colorant.

In addition, as the dye, for example, Japanese Patent Application Publication No. 64-90403, Japanese Patent Application Publication No. 64-91102, Japanese Patent Application Publication No. 1-94301, Japanese Patent Application Publication No. 6-11614, Japanese Patent Application Publication No. 2592207 Number, U.S. Patent No. 4808501 Specification, U.S. Patent No. 5667920 Specification, U.S. Patent No. 505950 Specification, Japanese Patent Application Publication No. 5-333207, Japanese Patent Application Publication No. 6-35183, Japanese Patent Application Publication No. 6-51115 and The pigment disclosed in Japanese Patent Laid-Open No. 6-194828, etc. If distinguished as a chemical structure, pyrazole azo compounds, pyrrole methylene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazole compounds can be used Azolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds or pyrrolopyrazole azomethine compounds, etc. In addition, as the dye, a dye multimer can be used. Examples of the dye multimer include the compounds described in Japanese Patent Application Publication No. 2011-213925 and Japanese Patent Application Publication No. 2013-041097. In addition, polymerizable dyes having polymerizability in the molecule can also be used. As a commercially available product, for example, RDW series manufactured by Wako Pure Chemical Industries, Ltd. can be cited.

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

As a coloring agent having the aforementioned spectroscopic properties, the compounds disclosed in paragraphs 0004 to 0016 of JP-A-H07-164729 and/or the compounds disclosed in paragraphs 0027 to 0062 of JP-A 2002-146254 can also be used. The compound, disclosed in paragraphs 0034 to 0067 of JP 2011-164583 A, includes near-infrared absorbing particles containing Cu and/or P oxide crystallites and having a number average aggregated particle size of 5 to 200 nm.

As a compound having a maximum absorption in the wavelength region of 675 to 900 nm, at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, aromatic acid cyanine compounds, phthalocyanine compounds, and naphthalocyanine compounds is more preferred. good. In addition, the infrared absorber is preferably a compound that dissolves 1% by mass or more in water at 25°C, and more preferably a compound that dissolves 10% by mass or more in water at 25°C. By using these compounds, solvent resistance is improved. For the pyrrolopyrrole compound, reference can be made to 0049 to 0062 of JP 2010-222557 A, and this content is incorporated in this specification. The cyanine compounds and aromatic acid cyanine compounds can refer to paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of Japanese Patent Application Publication No. 2014-59550, Paragraphs 0013 to 0091 of International Publication No. 2012/169447, Paragraphs 0019 to 0033 of JP 2015-176046, Paragraphs 0053 to 0099 of JP 2014-63144, and JP 2014-52431 Paragraphs 0085 to 0150, paragraphs 0076 to 0124 of JP 2014-44301, paragraphs 0045 to 0078 of JP 2012-8532, paragraphs 0027 to 067 of JP 2015-172102, JP Paragraphs 0029～0067 of 2015-172004, Paragraphs 0029～0085 of JP 2015-040895, Paragraphs 0022～0036 of JP 2014-126642, Paragraph 0011 of JP 2014-148567 ～0017, paragraphs 0010 to 0025 of JP 2015-157893, paragraphs 0013 to 0026 of JP 2014-095007, paragraphs 0013 to 0047 of JP 2014-080487, and JP 2013- Paragraphs 0007 to 0028, etc. of 227403 Bulletin are incorporated into this specification.

〔Resin (specific resin)〕 The resin of the present invention contains a specific resin. The content of the specific resin in the composition is 2.0 to 15.0% by mass relative to the total solid content of the composition. From the viewpoint that the light shielding and low reflectivity of the cured film formed are excellent in a better balance, 2.0 to 10.0% by mass For better. Moreover, when the composition contains the main chain type specific resin mentioned later as a specific resin, it is more preferable that the content of the main chain type specific resin is 2.0-6.0 mass% with respect to the total solid content of the composition. When the composition contains the side chain type specific resin described later as the specific resin, the content of the side chain type specific resin relative to the total solid content of the composition is more preferably greater than 3.0 and 10 or less. When two or more specific resins are used, the total content is preferably within the above-mentioned range. The mass ratio of the content of the specific resin in the composition to the black colorant is preferably 0.02 to 0.9, more preferably 0.02 to 0.3, more preferably 0.02 to 0.2, particularly preferably 0.02 to 0.1. In addition, the mass ratio of the content indicates (content of specific resin)/(content of black colorant) in the composition.

The specific resin contains a polymerizable group. Examples of polymerizable groups include ethylenically unsaturated groups (groups with ethylenically unsaturated bonds, for example, (meth)acrylic groups, vinyl groups, allyl groups, and styryl groups) and cyclic ethers. Group (for example, epoxy group, oxetanyl group, etc.) etc., but not limited thereto. Among them, from the viewpoint of enabling polymerization control in a radical reaction, as the polymerizable group, an ethylenically unsaturated group is preferred, and a (meth)acrylic acid group is more preferred.

The number average molecular weight of the specific resin is 100 to 15,000. Among them, 200 to 15000 are preferred. The weight average molecular weight of the specific resin is preferably 500 to 40,000.

The specific resin contains a group represented by the general formula (1). *-(SiR ¹ R ² -O) _na -* (1)

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. The presence of a plurality of R ^1, there are a plurality of R ¹ each may be the same, also be different. When plural R ² present, presence of a plurality of R ² may be the same, also be different. As the above-mentioned alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable, and examples thereof include methyl, ethyl, propyl, n-butyl, secondary butyl, hexyl, and octyl. Among them, methyl is preferred. The above-mentioned cycloalkyl group may be monocyclic or polycyclic. As the monocyclic ring, a cycloalkyl group having 3 to 8 carbon atoms is preferred, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. As the polycyclic ring, a cycloalkyl group having 6 to 20 carbon atoms is preferred, for example, adamantyl group, norbornyl group, isobornyl group, camphenyl group, dicyclopentyl group, α-pinenyl group (pinel group) , Tricyclodecyl, tetracyclododecyl and androstanyl group, etc. The aryl group is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

In the general formula (1), na represents an integer of 1 to 200, preferably 5 to 100, and more preferably 5 to 70. * Indicates the bonding position.

The existence form of the group represented by the general formula (1) in the specific resin is not limited. The group represented by the general formula (1) can exist as the main chain in the specific resin. The group represented by the general formula (1) Groups can also exist as side chains in specific resins. In addition, the longest chain in the specific resin is used as the main chain, and the chain bonded to the main chain is used as the side chain.

<Specific resin in which the group represented by the general formula (1) exists as the main chain (main chain type specific resin)> In the specific resin in which the group represented by the general formula (1) exists as the main chain (hereinafter, also referred to as "main-chain type specific resin"), the group represented by the general formula (1) may exist only one , There can be more than two. In the main chain type specific resin, when there are plural groups represented by the general formula (1), for example, between the plural groups represented by the general formula (1), except for the groups represented by the general formula (1) Groups other than the indicated groups exist as linking groups. The number of groups represented by the general formula (1) contained in the main-chain type specific resin is preferably 1-10, more preferably 1-5, and even more preferably 1. The main chain type specific resin may be branched or linear, and linear is preferred. Moreover, it is preferable that the main chain type specific resin contains the group containing a polymerizable group (preferably an ethylenic unsaturated group) at the terminal of at least 1 (preferably 2 or more). Among them, it is preferable that the main chain type specific resin is linear and contains a group containing a polymerizable group (preferably an ethylenically unsaturated group) at both ends thereof. In addition, one or more of the groups at the terminal of the main chain type specific resin may contain acid groups such as carboxylic acid groups, sulfonic acid groups, and/or phosphonic acid groups. One or more of the groups at the terminal of the main chain type specific resin may contain both an acid group and a polymerizable group (preferably an ethylenically unsaturated group). The weight average molecular weight of the main chain type specific resin is preferably 500 to 20,000, more preferably 500 to 10,000, and even more preferably 600 to 10,000. The number average molecular weight of the main chain type specific resin is preferably 200 to 10,000, more preferably 300 to 7,500, and more preferably 350 to 7,500. The dispersion degree (weight average molecular weight/number average molecular weight) of the main chain type specific resin is preferably 8 or less, and more preferably 4 or less. Generally, the lower limit of the degree of dispersion is 1 or more.

The main chain type specific resin is preferably a compound represented by the general formula (2), for example. R ³ -(SiR ¹ R ² -O) _nb -SiR ¹ R ² -R ³ (2)

In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Are the same as the general formula R (2) is ¹ and R ² in the general formula (1) R ¹ and R ^2.

In the general formula (2), R ³ represents a group containing an ethylenically unsaturated group. A plurality of R ³ may be the same or different. R ³ may contain an ethylenic unsaturated group in a part, and R ³ may be an ethylenic unsaturated group itself. As an ethylenically unsaturated group, (meth)acryloyl group, a vinyl group, an allyl group, and a styryl group are mentioned, for example, (meth)acryloyl group is preferable. The structure of R ³ is not particularly limited as long as it contains an ethylenically unsaturated group. The carbon number of R ³ is preferably 40 or less, and more preferably 30 or less. Generally, the lower limit of the carbon number of R ³ is 2 or more. The number of ethylenically unsaturated groups possessed by R ³ is preferably 1 to 5, and more preferably 1 to 2. At least one R ³ may contain a hetero atom (oxygen atom, sulfur atom and/or nitrogen atom, etc.). For example, a (meth)acryloyl group can form a (meth)acryloyloxy group together with an oxygen atom. In addition, it is preferable that at least one R ³ contains at least one of an ether bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, a urea bond, and a thioether bond, and it contains an ether bond and an ester bond , At least one of the urethane bond and the thioether bond is more preferred. In addition, at least one R ³ may further contain an acid group such as a carboxylic acid group, a sulfonic acid group and/or a phosphonic acid group, and preferably a carboxylic acid group. When the main chain type specific resin has an acid value, the acid value is preferably 100 mgKOH/g or less, and more preferably 10-50 mgKOH/g. If it is in this range, the main chain type specific resin which is not immobilized during exposure will be easily removed from the cured film during development. In addition, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample, and in this specification, the unit is described as mgKOH/g. In addition, in the main chain type specific resin, the ethylenically unsaturated group content is preferably 0.001 to 10.0 mmol/g, and more preferably 0.1 to 6.0 mmol/g with respect to the total mass of the resin.

In the general formula (2), nb represents an integer of 5 to 200, preferably 5 to 100, and more preferably 5 to 70.

<Specific resin in which the group represented by the general formula (1) exists as a side chain (side chain type specific resin)> The weight average molecular weight of the specific resin in which the group represented by the general formula (1) exists as a side chain (hereinafter also referred to as "side chain specific resin") is preferably 500 to 40,000, more preferably 500 to 20,000 , 500～10000 is further preferred. The number average molecular weight of the side chain type specific resin is preferably 500 to 15,000, and more preferably 500 to 8,000. The degree of dispersion (weight average molecular weight/number average molecular weight) of the side chain type specific resin is preferably 8 or less, and more preferably 4 or less. Generally, the lower limit of the degree of dispersion is 1 or more.

The side chain type specific resin preferably contains a group represented by the general formula (3), for example. *-(SiR ¹ R ² -O) _nc -SiR ¹ R ² -R ⁴ (3)

In the general formula (3), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Are the same as the general formula R (3) is ¹ and R ² in the general formula (1) R ¹ and R ^2.

In the general formula (3), R ⁴ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. When R ⁴ is an organic group, it may contain a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). Among them, R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the general formula (3), nc represents an integer of 1 to 200, preferably 2 to 100.

The side chain type specific resin preferably further contains a side chain containing an acid group such as an alkali-soluble group. Thereby, the side chain type specific resin that is not hardened during exposure becomes easy to be removed during development. In addition, the side chain type specific resin may contain a side chain containing two or more kinds of acid groups.

The acid group contained in the side chain type specific resin is not particularly limited, but a carboxylic acid group, a phenolic hydroxyl group, a sulfonic acid group, and the like are preferable.

The acid value of the side chain type specific resin is preferably 100 mgKOH/g or less, and more preferably 10-50 mgKOH/g. If it is this range, the side chain type specific resin which is not immobilized at the time of exposure will become easy to remove from a cured film at the time of development.

The side chain containing the acid group can be directly formed by polymerization reaction, or can be formed by chemical conversion after polymerization reaction.

The side chain type specific resin can be synthesized, for example, by reacting a copolymer with a compound containing a functional group capable of bonding to a reactive group and a polymerizable group (preferably an ethylenically unsaturated group). The copolymer can be By making a monomer containing a group represented by the general formula (1) (preferably a group represented by the general formula (3)), a monomer containing a reactive group, a monomer containing an acid group as required, and / Or copolymerized with other monomers.

The monomers represented by the general formula (4) containing the group represented by the general formula (1) used in the synthesis of the side chain type specific resin are preferred. CH ₂ =CR ^s -COO-Z- (SiR ¹ R ² -O) _nc -SiR ¹ R ² -R ⁴ (4)

In the general formula (4), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ⁴ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. ^{1, 1,} the same general formula R (4) R ² in general formula and R ⁴ are R (3) in R ² and R ^4. In the general formula (4), R ^s represents a hydrogen atom or a methyl group. In the general formula (4), Z represents a single bond or a divalent organic group having 1 to 6 carbon atoms. Z is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, and examples include -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH _2- , -C (CH ₃ ) ₂ -, -CH (CH ₂ CH ₃ ) -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH (CH ₂ CH ₂ CH ₃ ) -, -CH ₂ (CH2) ₃ CH ₂ -and -CH (CH ₂ CH (CH ₃ ) ₂ ) -.

The reactive group-containing monomer is not particularly limited. For example, monomers containing hydroxyl groups, acid anhydrides containing ethylenic double bonds, monomers containing carboxylic acid groups, and monomers containing epoxy groups can be used. Two or more kinds. In addition, it is preferable that the monomer containing a reactive group does not contain the group represented by the general formula (1).

Examples of monomers containing a hydroxyl group include hydroxyethyl 2-(meth)acrylate, hydroxypropyl 2-(meth)acrylate, hydroxypropyl 3-(meth)acrylate, and 4-(methyl) Hydroxybutyl acrylate, hydroxypentyl 5-(meth)acrylate, hydroxyhexyl 6-(meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate , 3-chloro-2-(meth)hydroxypropyl acrylate, glycerol (meth)acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2- Hydroxyethyl allyl ether, N-hydroxymethyl(meth)acrylamide and N,N-bis(hydroxymethyl)(meth)acrylamide.

Furthermore, the monomer containing a hydroxyl group may contain a polyoxyalkylene group whose terminal is a hydroxyl group. Examples of such hydroxyl-containing monomers include CH ₂ =CHOCH ₂ C ₆ H ₁₀ CH ₂ O (CH ₂ CH ₂ O) _k H, CH ₂ =CHOC ₄ H ₈ O (CH ₂ CH ₂ O) _k H, CH ₂ = CHCOOCH ₂ CH ₂ O (CH ₂ CH ₂ O) _k H, CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ O (CH ₂ CH ₂ O) _k H, CH ₂ = CHCOOCH ₂ CH ₂ O (CH ₂ CH ₂ O) m (C ₃ H ₆ O) _j H, CH ₂ =C (CH ₃ ) COOC ₂ H ₄ O (CH ₂ CH ₂ O) _m (C ₃ H ₆ O) _j H (K is an integer from 1 to 100, m is an integer from 0 to 100, j is an integer from 1 to 100, m+j is from 1 to 100.) and the like. In addition, the above-mentioned C ₆ H ₁₀ is cyclohexylene, C ₄ H ₈ is n-butylene, and C ₃ H ₆ is 2-propylene.

Examples of acid anhydrides containing ethylenic double bonds include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5 ,6-Tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl succinic anhydride, etc.

Examples of monomers containing carboxylic acid groups include acrylic acid, methacrylic acid, ethylene acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. .

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate and 3,4-epoxycyclohexyl methacrylate.

As the monomer containing an acid group, for example, a monomer containing a carboxylic acid group, a monomer containing a phenolic hydroxyl group, a monomer containing a sulfonic acid group, and the like can be used. In addition, when a monomer containing a carboxylic acid group is used as a monomer containing an acid group, and a monomer containing a carboxylic acid group is also used as a monomer containing a reactive group, the ethylenic double bond will not be introduced at the end, and it will be used as the carboxylic acid group. The remaining ones are regarded as monomers containing acid groups.

As monomers containing phenolic hydroxyl groups, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and one or more hydrogen atoms of these benzene rings are substituted by methyl, ethyl, or n-butyl. Alkoxy groups such as alkyl groups, methoxy groups, ethoxy groups, n-butoxy groups, halogen atoms, haloalkyl groups containing more than one halogen atom, nitro groups, cyano groups and/or amide groups, etc. Compound etc.

Examples of monomers containing sulfonic acid groups include vinyl sulfonic acid, styrene sulfonic acid, (meth)allyl sulfonic acid, and 2-hydroxy-3-(methyl)allyloxy propane sulfonic acid. , 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, 2-hydroxy-3-(meth)propenoxypropanesulfonic acid and 2-(meth)propylene Amide-2-methylpropane sulfonic acid and the like.

Examples of other monomers include hydrocarbon-based olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth)acrylates, ( Meth)acrylamides, aromatic vinyl compounds, chloroolefins, and conjugated dienes, etc. If the heat resistance of the cured film is considered, (meth)acrylates or (meth)acrylamides For better. In addition, these compounds may contain functional groups such as carbonyl groups and alkoxy groups.

The ratio of the mass of the monomer containing the group represented by the general formula (1) to the total mass of the monomers to be copolymerized is preferably 20 to 80% by mass, more preferably 30 to 60% by mass. If it is within the above-mentioned mass range, the low reflectivity of the cured film and the adhesion between the cured film and the substrate are well balanced.

The ratio of the mass of the reactive group-containing monomer to the total mass of the monomers to be copolymerized is preferably 20 to 70% by mass, more preferably 30 to 50% by mass. If it is this range, the immobilization and developability of a side chain type specific resin will become favorable.

The ratio of the mass of the acid group-containing monomer to the total mass of the monomer to be copolymerized is preferably 2-20%, more preferably 4-12%. If it is this range, the developability of the side chain type specific resin which is not hardened at the time of exposure will become favorable.

From the viewpoint of excellent developability, the ratio of the mass of other monomers to the total mass of the monomers to be copolymerized is preferably 70% by mass or less, and more preferably 50% by mass or less.

A copolymer containing a side chain containing a group represented by the general formula (1) and a side chain containing a reactive group, as required, can be synthesized as follows: a copolymer containing a side chain represented by the general formula (1) Group monomers, monomers containing reactive groups, monomers containing acid groups and/or other monomers as needed are dissolved in a solvent and heated, and a polymerization initiator is added to copolymerize them. In addition, during copolymerization, it is preferable to add a chain transfer agent as necessary. In addition, monomers, polymerization initiators, solvents, and chain transfer agents may be continuously added.

As the polymerization initiator, solvent, and chain transfer agent, those described in paragraphs 0053 to 0056 of International Publication No. 2007/69703 can be used.

As a combination of a reactive group and a compound containing a functional group capable of bonding to the reactive group and a polymerizable group (preferably an ethylenically unsaturated group), for example, the following combinations can be mentioned. (1) Anhydrides containing ethylenically unsaturated groups relative to hydroxyl groups, (2) Compounds containing isocyanate groups and ethylenically unsaturated groups relative to hydroxyl groups, (3) Compounds containing chlorinated acyl groups and ethylenically unsaturated groups relative to hydroxyl groups, (4) Compared with acid anhydrides, compounds containing hydroxyl and ethylenically unsaturated groups, (5) Compounds containing epoxy groups and ethylenically unsaturated groups relative to carboxylic acid groups, (6) A compound containing a carboxylic acid group and an ethylenically unsaturated group relative to an epoxy group.

Examples of compounds containing isocyanate groups and ethylenically unsaturated groups include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl)ethyl Group isocyanate and so on. Among them, from the viewpoint that side-chain type specific resins containing side chains with two or more ethylenically unsaturated groups are easily immobilized near the upper surface of the cured film, 1,1-bis((meth)acryloyloxy) Methyl)ethyl isocyanate is preferred. As a compound containing a chlorinated acyl group and an ethylenically unsaturated group, (meth)acrylic acid chloride etc. are mentioned, for example. As an ethylenically unsaturated group-containing acid anhydride, for example, the compounds exemplified in the aforementioned reactive group-containing monomers can be used. As the compound containing a hydroxyl group and an ethylenically unsaturated group, for example, the compounds exemplified in the aforementioned hydroxyl group-containing monomer can be used. As the compound containing an epoxy group and an ethylenically unsaturated group, for example, the compounds exemplified in the aforementioned epoxy group-containing monomer can be used. As the compound containing a carboxylic acid group and an ethylenically unsaturated group, for example, the compounds exemplified in the aforementioned carboxylic acid group-containing monomer can be used.

In addition, a copolymer containing a side chain containing a group represented by the general formula (1) and a side chain containing a reactive group, and if necessary, a side chain containing an acid group, and a copolymer containing a side chain capable of bonding to the reactive group When the compound of the functional group and the polymerizable group (preferably ethylenically unsaturated group) reacts, from the viewpoint of the excellent balance between the appearance of the cured film and the low reflectivity, the functional group of the compound is relative to the copolymer The equivalent ratio of the reactive groups is preferably 0.5 to 2.0, and more preferably 0.8 to 1.5.

The side chain type specific resin can be synthesized as follows: a copolymer containing a side chain containing a group represented by the general formula (1), a side chain containing a reactive group, and a side chain containing an acid group as required, and a copolymer containing The functional group to which the reactive group is bonded and the compound of the ethylenically unsaturated group are dissolved in a solvent to react.

In addition, as described above, the acid group-containing side chain in the side chain type specific resin can also be formed by chemical conversion after the polymerization reaction. For example, a copolymer containing a side chain containing a group represented by the general formula (1) and a side chain containing a reactive group and a copolymer containing a functional group capable of bonding to the reactive group and an ethylenically unsaturated group can also be used. After the compound reacts, an acid group is formed. Specifically, when the combination of (6) above is used, the hydroxyl group generated in the reaction with the epoxy group and the carboxylic acid group can be reacted with a polybasic acid anhydride (maleic anhydride, etc.) to introduce the carboxylic acid group into the side Chain type specific resin.

The content of the polymerizable group (preferably ethylenically unsaturated group) relative to the total resin mass of the side chain type specific resin is not limited. Among them, in the side chain type specific resin, the content of the ethylenically unsaturated group relative to the total mass of the resin is preferably 0.001 to 10.0 mmol/g, and more preferably 0.1 to 2 mmol/g.

In this specification, the ethylenically unsaturated group content may be referred to as "C=C valence". In this specification, the ethylenic unsaturated group content (C=C valence) means the value measured by the following method. In addition, when synthesizing a resin containing an ethylenically unsaturated group, calculation can be made from the amount of raw materials used instead of measurement. Moreover, when the composition contains a plurality of resins and the C=C valence of each resin is clear, the C=C valence as the total mass of the resin contained in the composition can be calculated from the blending ratio of each resin.

As a method for measuring the ethylenic unsaturated group content of the resin, when the ethylenic unsaturated group is a (meth)acrylic acid group, it is measured by the following method. First, the solid components (black pigments, etc.) in the composition are precipitated by centrifugal separation and the remaining liquid components are separated. Furthermore, by the GPC method, a component having a weight average molecular weight within a predetermined range is fractionated from the obtained liquid component, and this is used as the resin to be measured. Next, 0.25 mg of the resin to be measured was dissolved in 50 mL of THF (tetrahydrofuran), and 15 mL of methanol was added to prepare a solution. 10 mL of 4N sodium hydroxide aqueous solution was added to the prepared solution to obtain a mixed solution. Next, the above-mentioned mixed liquid was stirred at a liquid temperature of 40°C for 2 hours. Furthermore, 10.2 mL of 4N methanesulfonic acid aqueous solution was added to the mixed liquid, and it stirred. Furthermore, 5 mL of desalinated water was added to the mixed solution, and 2 mL of methanol was continuously added to prepare a measurement solution. Measure the content of (meth)acrylic acid in the solution by HPLC (high performance liquid chromatography) method (absolute calibration curve method), and calculate the ethylenic unsaturated group content. HPLC determination condition column: Synergi 4μ Polar-RP 80A (4.6mm×250mm) manufactured by Phenomenex Column temperature: 40℃ Flow rate: 1.0mL/min Detector wavelength: 210nm Eluent: THF (tetrahydrofuran, for HPLC) 55/buffer water 45 Buffer water: 0.2%-phosphoric acid, 0.2%-triethylamine aqueous solution Injection volume: 5μL

As a method for measuring the content of ethylenic unsaturated groups in resins, ethylenic unsaturated groups are groups other than (meth)acrylic groups or a combination of (meth)acrylic groups and other than (meth)acrylic groups In the case of the group, the method for measuring bromination of the resin to be measured separated by the above method can be mentioned. The bromine value is measured in accordance with JIS K2605:1996. In addition, the content of ethylenically unsaturated groups is converted from the number of grams of bromine (Br ₂ ) added to 100 g of the resin to be measured (gBr ₂ /100 g) obtained at the above bromine value to bromine added per 1 g of resin (Br ₂ ) The value of the number of moles.

[Polymerizable compound] The composition of the present invention preferably contains a polymerizable compound. In this specification, the polymerizable compound means a compound that is polymerized by the action of a polymerization initiator described below, and means a component different from the dispersant and alkali-soluble resin described below. In addition, the polymerizable compound means a component different from the epoxy group-containing compound described later.

The content of the polymerizable compound in the composition is not particularly limited. It is preferably 1 to 35% by mass relative to the total solid content of the composition, more preferably 4 to 25% by mass, and more preferably 10 to 20% by mass. Better. A polymerizable compound may be used individually by 1 type, and may use 2 or more types. When two or more types of polymerizable compounds are used, the total content is preferably within the above range. The content of the specific resin in the composition relative to the mass ratio of the polymerizable compound is preferably 0.1-50, more preferably 0.1-20, more preferably 0.1-2, particularly preferably 0.2-2, and most preferably 0.2-1 good. The mass ratio of the content indicates (content of specific resin)/(content of polymerizable compound) in the composition. The polymerizable compound is preferably a low-molecular compound. The low-molecular compound mentioned here is preferably a compound having a molecular weight of 2000 or less. The polymerizable compound preferably does not contain the repeating unit represented by the general formula (1), and more preferably does not contain the (poly)siloxane structure.

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

As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP 2008-260927 A and paragraph 0040 of JP 2015-68893 A can be used, and the above-mentioned contents are incorporated in this specification.

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

The polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100°C or higher under normal pressure. For example, the compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, and this content is incorporated in this specification.

The polymerizable compound is dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku CO., LTD.), and dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku CO. , LTD.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku CO., LTD.), dipentaerythritol hexa(meth)acrylate (as a commercial product) , KAYARAD DPHA; manufactured by Nippon Kayaku CO., LTD., A-DPH-12E; manufactured by Shin-Nakamura Chemical CO., LTD) and these (meth)acrylic groups mediate ethylene glycol residues or propylene glycol residues The structure (for example, SR454 and SR499 commercially available from Sartomer company Inc.) is preferable. These oligomer types can also be used. In addition, NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Co., LTD.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, KAYARAD DPEA-12 ( Nippon Kayaku Co., Ltd.) and VISCOAT #802 (OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), etc. The aspect of the preferable polymerizable compound is shown below.

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

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

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

[Chemical Formula 1]

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

[Chemical Formula 2]

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

[Chemical formula 3]

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

Polymeric compounds containing a caprolactone structure are commercially available as KAYARAD DPCA series from Nippon Kayaku CO., LTD., for example, DPCA-20 (in the above formulas (Z-1) to (Z-3), m=1, The number of groups represented by the formula (Z-2) = 2, and R ¹ is a compound with all hydrogen atoms), DPCA-30 (in the above formulas (Z-1) to (Z-3), m=1, according to the formula The number of groups represented by (Z-2) = 3, and R ¹ is a compound with all hydrogen atoms), DPCA-60 (in the above formulas (Z-1) to (Z-3), m=1, according to the formula ( The number of groups represented by Z-2) = 6, and R ¹ is a compound with all hydrogen atoms), DPCA-120 (in the above formulas (Z-1) to (Z-3), m=2, according to formula (Z -2) The number of represented groups=6, and R ¹ is a compound with all hydrogen atoms) etc.

The polymerizable compound can also be a compound represented by the following formula (Z-6).

[Chemical formula 4]

In formula (Z-6), E each independently represents -((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)-, y independently represents 0～10 Integer of, X each independently represents a (meth)acryloyl group, a hydrogen atom or a carboxylic acid group. In formula (Z-6), p independently represents an integer of 0-10, and q represents an integer of 0-3. In formula (Z-6), the total number of (meth)acrylic groups is preferably (3+2t) or (4+2t). In formula (Z-6), the total of each p is preferably 0 to (40+20t). It is preferable that p is an integer of 0-6, and an integer of 0-4 is more preferable. The total of each p is preferably 0 to (16+8t), and more preferably 0 to (12+6t).

In addition, -((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)- in formula (Z-6) is bonded to X at the end on the oxygen atom side: Better.

The compound represented by formula (Z-6) may be used singly, or two or more kinds may be used. In particular, in the case of t=1, a mixture of a compound in which all of the six Xs are acryloyl groups and a compound in which at least one of the six Xs is a hydrogen atom is preferred. With such a structure, the developability can be further improved. Furthermore, it is also preferable to use a mixture of compounds represented by formula (Z-6) having different values of t. As such a mixture, the content of each of the compound with t=1, the compound with t=2, and the compound with t=3 is preferably 5 to 35% by mass, 30 to 75% by mass, and 3 to 35% by mass, respectively.

In addition, as the total content of the compound represented by the formula (Z-6) in the polymerizable compound, 20% by mass or more is preferable, and 50% by mass or more is more preferable. Among the compounds represented by the formula (Z-6), neopentylerythritol derivatives, dineopentylerythritol derivatives, trineopentylerythritol derivatives and/or tetraneopentylerythritol derivatives are more preferable.

In addition, the polymerizable compound may contain a Cardo skeleton. As the polymerizable compound containing a cardo skeleton, a polymerizable compound having a 9,9-diarylfluorene skeleton is preferred. The polymerizable compound containing a cardo skeleton is not limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD) and Ogsol (manufactured by Osaka Gas Chemicals Co., LTD.). The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. As an example of such a polymerizable compound, NK Ester A-9300 (manufactured by Shin Nakamura Chemical Co., LTD.) is mentioned, for example. The content of the ethylenically unsaturated group of the polymerizable compound (representing the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g/mol) of the polymerizable compound) is preferably 5.0 mmol/g or more. The upper limit is not particularly limited, but is usually 20.0 mmol/g or less. In addition, when the composition contains multiple types of polymerizable compounds and the double bond equivalents of each are not the same, the mass ratio of each polymerizable compound in the fully polymerizable compound and the product of the double bond equivalent of each polymerizable compound are added up. The value is preferably within the above range.

〔Photopolymerization initiator〕 The above composition contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can initiate the polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from an ultraviolet region to a visible light region is preferable. In addition, the polymerization initiator may be an active agent that has some effect with the photosensitizer excited by light and generates active free radicals, or it may be an initiator that initiates cationic polymerization according to the type of polymerizable compound. Regarding the photopolymerization initiator, from the viewpoint of obtaining a cured film with more excellent low reflectivity, the optical path length of a solution of 0.001% by mass of the photopolymerization initiator dissolved in acetonitrile is 0.45 or more at a wavelength of 340nm. Better. In addition, in this specification, the absorbance of the solution of the said photopolymerization initiator is measured with the ultraviolet-visible-near-infrared spectrophotometer U-4100 (made by Hitachi High-Technologies Corporation.).

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

As the photopolymerization initiator, for example, halogenated hydrocarbon derivatives (for example, triazine skeleton-containing compounds, oxadiazole skeleton-containing compounds, etc.), acylphosphine compounds such as phosphine oxide, hexaaryl bis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, hydroxyacetophenone, etc. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP 2013-29760 A can be referred to, and this content is incorporated into this specification.

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

(Oxime compound) As the photopolymerization initiator, an oxime ester-based polymerization initiator (oxime compound) is more preferable. In particular, the oxime compound has high sensitivity and high polymerization efficiency, and it is easy to set the content of the black colorant in the composition high, so it is preferable. As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-080068 A, or the compound described in JP 2006-342166 A can be used. As the oxime compound, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-acetoxyimino Butan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyloxy Imino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy) iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-benzene Propane-1-one and so on. In addition, JCSPerkin II (1979) pp.1653-1660, JCSPerkin 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, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2004-534797, and Japanese Patent Application Publication No. 2006-342166 Recorded compounds, etc. Among the commercially available products, IRGACURE-OXE01 (made by BASF), IRGACURE-OXE02 (made by BASF), IRGACURE-OXE03 (made by BASF), or IRGACURE-OXE04 (made by BASF) are also preferred. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arkls NCI-831, Adeka Arkls NCI-930 (manufactured by ADEKA CORPORATION) or N-1919 (containing carbazole•oxime ester skeleton light Starter (manufactured by ADEKA CORPORATION).

In addition, as oxime compounds other than those described above, compounds described in Japanese Patent Application Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole can be used; those with hetero substituents introduced at the benzophenone site The compound described in U.S. Patent No. 7626957; the compound described in Japanese Patent Laid-Open No. 2010-015025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into the pigment site; and the compound described in International Publication No. 2009-131189 Ketone oxime compounds; and compounds described in U.S. Patent No. 7556910 containing triazine skeletons and oxime skeletons in the same molecule; Japanese Patent Application Publication No. 2009-221114, which has great absorption at 405nm and good sensitivity to g-ray light sources Compounds recorded in the bulletin; etc. For example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, and this content is incorporated into this specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. In addition, the N-O bond of the oxime compound may be an oxime compound in the (E) form, or an oxime compound in the (Z) form, or a mixture of the (E) form and the (Z) form.

[Chemical formula 5]

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

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

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

[Chemical formula 6]

[Chemical formula 7]

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

In the formula ^{(2), R 1, 1, R 2} , the same as R ^2, R ³ and R ⁴ meaning as in formula R (1) in R ³ and R ^4, R ⁵ represents -R ^6, -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom Or hydroxyl, R ⁶ represents an alkyl group with 1 to 20 carbons, an aryl group with 6 to 30 carbons, an aralkyl group with 7 to 30 carbons, or a heterocyclic group with 4 to 20 carbons, and X represents a direct bond or In the carbonyl group, a represents an integer of 0-4.

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

In the formula (4), R ^{1, 1,} the same meaning as R ³ and R ⁴ R ³ and R ⁴ of the formula R (3) in, R ⁵ represents ^{-R 6, -OR 6, -SR 6} , - COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or hydroxyl, R ⁶ represents An alkyl group having 1 to 20 carbons, an aryl group having 6 to 30 carbons, an aralkyl group having 7 to 30 carbons, or a heterocyclic group having 4 to 20 carbons. X represents a direct bond or a carbonyl group, and a represents 0 to An integer of 4.

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

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

[化學式9]

[Chemical formula 8]

[Chemical formula 9]

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

In addition, as the photopolymerization initiator, for example, paragraph 0052 of Japanese Patent Application Publication No. 2008-260927, paragraphs 0033 to 0037 of Japanese Patent Application Publication No. 2010-097210, and Japanese Patent Application Publication No. 2015-68893 may also be used. For the compound described in paragraph 0044 of, the above content is incorporated into this specification.

〔Other resins〕 The composition of the present invention may contain other resins other than the above-mentioned specific resin. It is preferable that other resins do not contain the repeating unit represented by the general formula (1), and it is more preferable that they do not contain a (poly)siloxane structure. Examples of other resins include dispersants and alkali-soluble resins. The content of other resins in the composition is not particularly limited. With respect to the total solid content of the composition, 3-60% by mass is preferable, 10-40% by mass is more preferable, and 15-35% by mass is further more. good. The other resins may be used singly or in two or more types. For example, as other resins, a dispersant described later and an alkali-soluble resin described later can be used. When two or more other resins are used, the total content is preferably within the above-mentioned range. Other resins are preferably dissolved in the composition and have a molecular weight greater than 2000. In addition, when the molecular weight of other resins is polydisperse, the weight average molecular weight is preferably greater than 2,000.

＜Dispersant＞ The composition preferably contains a dispersant. In addition, in this specification, a dispersant means a compound different from the alkali-soluble resin mentioned later. The content of the dispersant in the composition is not particularly limited. With respect to the total solid content of the composition, 3-40% by mass is preferable, 5-35% by mass is more preferable, and 10-30% by mass is more preferable. good. A dispersant may be used individually by 1 type, and may use 2 or more types. When two or more dispersants are used, the total content is preferably within the above range. In addition, the mass ratio of the content of the dispersant (preferably grafted polymer) to the content of the pigment (dispersant content/pigment content) in the composition is preferably 0.05 to 1.00, and 0.05 to 0.35 is More preferably, 0.20 to 0.35 is even more preferable.

As the dispersant, for example, a known dispersant can be appropriately selected and used. Among them, polymer compounds are preferred. As the dispersant, a polymer dispersant (for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, Modified poly(meth)acrylate, (meth)acrylic acid copolymer, formalin naphthalenesulfonate condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine and pigment derivatives. Polymer compounds can be further classified into linear polymers, terminal modified polymers, grafted polymers, and block polymers based on their structures.

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

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

The resin (other resin) having a curable group preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and/or a polyether structure. As described later, when the resin contains a structural unit containing a graft chain, the polymer chain may contain a polyester structure and/or a polyether structure. As the resin, it is more preferable that the polymer chain contains a polyester structure.

The polymer compound preferably contains a structural unit containing a graft chain. In addition, in this specification, "structural unit" and "repeating unit" have the same meaning. The polymer compound containing the structural unit containing the graft chain has affinity with the solvent due to the graft chain, so the dispersibility of the pigment and the like and the dispersion stability over time (stability over time) are excellent. In addition, by the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has affinity with the polymerizable compound or other resins (specific resins etc.) that can be used in combination. As a result, residues are less likely to be generated during alkali development. If the graft chain becomes longer, the steric repulsion effect is improved and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorption force to the pigment or the like will decrease, and the dispersibility of the pigment or the like will tend to decrease. Therefore, in the graft chain, the number of atoms other than hydrogen atoms is preferably from 40 to 10,000, the number of atoms other than hydrogen atoms is more preferably from 50 to 2000, and the number of atoms other than hydrogen atoms is from 60 to 500. Better. Wherein, the graft chain means the root of the main chain of the copolymer (atoms bonded to the main chain from the group branched from the main chain) to the end of the group branched from the main chain.

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

As a macromonomer containing such a graft chain (a monomer that has a polymer structure and is bonded to the main chain of the copolymer to form the graft chain), there is no particular limitation, and a reactive double bond can be preferably used. The giant monomer of the sex group.

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

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

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

[Chemical formula 10]

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. As X ¹ , X ² , X ³ , X ⁴ and X ⁵ , from the viewpoint of synthesis constraints, each independently is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (carbon atoms), respectively It is more preferable to independently be a hydrogen atom or a methyl group, and a methyl group is even more preferable.

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

[Chemical formula 11]

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

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

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

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

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

[Chemical formula 12]

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

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

[Chemical formula 13]

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

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

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

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

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

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

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

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

[Chemical formula 14]

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The polymer compound may have one or more structural units containing acid groups. The polymer compound may or may not contain the structural unit containing an acid group, but when it contains, the content of the structural unit containing the acid group is calculated in terms of mass, and is preferably 5 to 80% by mass relative to the total mass of the polymer compound. From the viewpoint of suppressing damage to the image strength due to alkali development, 10 to 60% by mass is more preferable.

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

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

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

[Chemical formula 15]

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

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

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

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

In formulas (iv) to (vi), Z _{1 in} addition to the graft chain also represents a functional group that can interact with pigments, etc., preferably a carboxylic acid group or a tertiary amine group, and more preferably a carboxylic acid group .

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

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

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

From the viewpoints of interaction with pigments, etc., stability over time, and permeability to developing solutions, the content of structural units containing functional groups capable of interacting with pigments, etc., relative to the total mass of the polymer compound is 0.05 to 90% by mass is preferable, 1.0 to 80% by mass is more preferable, and 10 to 70% by mass is still more preferable.

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

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

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

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

Specific examples of polymer compounds include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., "Disperbyk-101 (polyamide phosphate) manufactured by BYKChemie, 107 (carboxylate), 110 (containing acid Base copolymer), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 167, 170, 190 (polymer copolymer)", "BYK-P104 , P105 (high molecular weight unsaturated polycarboxylic acid), "EFKA4047, 4050-4010-4165 (polyurethane series), EFKA 4330-4340 (block copolymer), 4400-4402 (modified) manufactured by EFKA Polyacrylate), 5010 (polyamide ester), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", Ajinomoto Fine -Techno Co., Inc. "AJISPER PB821, PB822, PB880, PB881", KYOEISHA CHEMICAL Co., LTD. "FLOREN TG-710 (urethane oligomer)", "Polyflow No.50E, No. 300 (Acrylic Copolymer)", "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50 manufactured by Kusumoto Chemicals, Ltd. , DA-705, DA-725", Kao Corporation "DEMOL RN, N (formalin naphthalenesulfonate condensation polymer), MS, C, SN-B (aromatic sulfonate formalin condensation polymer)", "HOMOGENOL L -18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)", "ACETAMIN 86 (stearyl amine acetate)", "SOLSPERSE manufactured by The Lubrinzol corporation" 5000 (phthalocyanine derivatives), 22000 (azo pigment derivatives), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymers with functional parts at the end), 24000, 28000, 32000 , 38500 (graft copolymer), "Nikkor T106 (polyoxyethylene sorbitol monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikkol Chemicals CO., LTD., Kawaken Fine Chemic HINOAKUTO T-8000E manufactured by als CO., LTD., polyorganosiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., LTD., "W001: cationic surfactant" manufactured by Yusho Co Ltd, Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene Nonionic surfactants such as diol distearate and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, and W017", "EFKA-46, EFKA" manufactured by MORISHITA & CO., LTD. -47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" manufactured by SAN NOPCO LIMITED, etc. Polymer dispersant, "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION and "Ionet (trade name) S-20" manufactured by Sanyo Chemical Industries, Ltd., etc. In addition, Acrybase FFS-6752 and Acrybase FFS-187 can also be used.

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

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

In addition, as the dispersant, in addition to the above-mentioned polymer compound, a graft copolymer of paragraphs 0037 to 0115 of Japanese Patent Application Laid-Open No. 2010-106268 (corresponding to paragraphs 0075 to 0133 of US2011/0124824) can also be used. And other content, and introduced into this manual. Furthermore, in addition to the above, paragraphs 0028 to 084 of Japanese Patent Laid-Open No. 2011-153283 (corresponding to paragraphs 0075 to 0133 of US2011/0279759) including side chain structures containing acid groups bonded via linking groups can also be used. The polymer compounds of the constituent components can use these contents and be incorporated into this specification.

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

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

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

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

As a specific example of the alkali-soluble resin, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be given. The unsaturated carboxylic acid is not particularly limited. Examples include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinyl acetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid. Acid, or its anhydride; and mono(2-(meth)acryloyloxyethyl) phthalate and other polycarboxylic acid monoesters; etc.

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

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

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

As the alkali-soluble resin, for example, Japanese Patent Application Publication No. 59-044615, Japanese Patent Application Publication No. 54-034327, Japanese Patent Application Publication No. 58-012577, Japanese Patent Application Publication No. 54-025957, Japanese Patent Application Publication No. 54 -092723, Japanese Patent Application Publication No. 59-053836, and Japanese Patent Application Publication No. 59-071048 described in the free radical polymer containing a carboxylic acid group in the side chain; European Patent No. 993966, European Patent No. 1204000 Alkali-soluble group-containing acetal-modified polyvinyl alcohol-based binder resin; polypyrrolidone; polyvinyloxy; alcohol-soluble nylon and 2,2 described in various publications such as Japanese Patent Application Publication No. 2001-318463 -Bis-(4-hydroxyphenyl)-propane and epichlorohydrin reactant, namely polyether, etc.; and polyimide resin described in International Publication No. 2008/123097; etc.

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

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

[Chemical formula 16]

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

[Chemical formula 17]

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

As a specific example of the ether dimer, for example, paragraph 0317 of JP 2013-29760 A can be referred to, and this content is incorporated in this specification. There may be only one type of ether dimer, or two or more types.

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

[Chemical formula 18]

[Chemical formula 19]

[Chemical formula 20]

[Chemical formula 21]

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

As specific examples of the polyimide precursors, for example, the compounds described in paragraphs 0011 to 0031 of JP 2008-106250 A, and the compounds described in paragraphs 0022 to 0039 of JP 2016-122101 A can be cited. For the compound and the compound described in paragraphs 0061 to 0092 of JP 2016-68401 A, the above-mentioned contents are incorporated in this specification.

From the viewpoint that the pattern shape of the patterned cured film obtained using the composition is more excellent, it is also preferable that the alkali-soluble resin contains at least one selected from the group consisting of polyimide resin and polyimide precursor. The polyimide resin containing an alkali-soluble group is not particularly limited, and polyimide resins containing known alkali-soluble groups can be used. Examples of the polyimide resin include the resin described in paragraph 0050 of JP 2014-137523 A, the resin described in paragraph 0058 of JP 2015-187676 A, and JP 2014-106326 For the resins described in paragraphs 0012 to 0013 of the Bulletin, the above contents are incorporated into this specification.

(Resin containing ethylenic unsaturated group) From the viewpoint that the cross-sectional shape of the cured film obtained is more excellent in rectangularity, the composition of the present invention may contain other resins containing ethylenically unsaturated groups in addition to the specific resin. Other resins containing ethylenically unsaturated groups may be dispersants or alkali-soluble resins. Furthermore, it may be a resin other than a dispersant or an alkali-soluble resin. The lower limit of the content of other resins containing ethylenically unsaturated groups in the composition is preferably 30% by mass or more relative to the total mass of other resins contained in the composition, more preferably 50% by mass or more, and 65% by mass or more More preferably, 85% by mass or more is particularly preferable. The upper limit of the content of the other resin containing the ethylenically unsaturated group in the composition is preferably 100% by mass or less relative to the total mass of the other resin contained in the composition. The other resin containing ethylenic unsaturated group may be used individually by 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that the total content is in the said range. In addition, other resins containing ethylenically unsaturated groups mean other resins containing one or more ethylenically unsaturated groups in one molecule.

The content of other resins containing ethylenically unsaturated groups can be calculated from the amount of raw materials used.

In addition, the content of ethylenically unsaturated groups relative to the total mass of other resins is not particularly limited, but 0.001 to 5.00 mmol/g is preferable, 0.10 to 3.00 mmol/g is more preferable, and 0.26 to 2.50 mmol/g is Further better. When the ethylenically unsaturated group content is in the range of 0.10 to 3.00 mmol/g, the rectangularity of the cross-sectional shape of the cured film obtained using the composition is more excellent. In addition, the total mass of other resins mentioned above indicates the total mass of other resins contained in the composition. For example, when the composition includes other resins containing ethylenically unsaturated groups and other resins not containing ethylenically unsaturated groups, the total mass of the two It corresponds to the total mass of the other resins mentioned above. Therefore, the content of the above-mentioned ethylenic unsaturated group means the content of the ethylenic unsaturated group in the other resin resin containing the ethylenic unsaturated group relative to the total mass of the other resin resin.

In addition, the content of the ethylenically unsaturated group relative to the total mass of the resin in the composition containing both the specific resin and other resins is not particularly limited, but 0.001 to 5.00 mmol/g is preferred, and 0.10 to 4.00 mmol /g is better. In addition, the acid value of the entire resin in the composition containing both the specific resin and other resins is not particularly limited, but usually 30 to 500 mgKOH/g is preferable, and 50 to 200 mgKOH/g or less is more preferable.

As for the method for measuring the content of ethylenically unsaturated groups, similarly, the method for measuring the content of ethylenically unsaturated groups (C=C valence) described in the description of the specific resin can be cited.

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

The effect of polymerization inhibitors is remarkable when used together with resins containing curable groups. The content of the polymerization inhibitor in the light-shielding composition is not particularly limited. With respect to the total solid content of the composition, 0.0001 to 0.5% by mass is preferable, 0.001 to 0.2% by mass is more preferable, and 0.008 to 0.05% by mass It is further preferred. A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types. When two or more kinds of polymerization inhibitors are used, the total content is preferably within the above range. The mass ratio of the polymerization inhibitor to the content of the specific resin in the composition is preferably 0 to 0.006, more preferably 0.001 to 0.005, and still more preferably 0.002 to 0.005. The mass ratio of the above content represents (the content of the polymerization inhibitor)/(the content of the specific resin) in the composition.

[Compounds containing epoxy groups] The composition of the present invention can use epoxy-containing compounds. Examples of the epoxy group-containing compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups in one molecule are preferred. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit may be 10 or less, for example, or 5 or less. The lower limit is preferably 2 or more. In addition, the epoxy group-containing compound means a component different from the above-mentioned specific resin, dispersant, alkali-soluble resin, and polymerizable compound.

The epoxy equivalent of the epoxy-containing compound (= the molecular weight of the epoxy-containing compound/the number of epoxy groups) is preferably 500g/equivalent or less, 100-400g/equivalent is more preferably, 100-300g/equivalent is more Better.

The epoxy-containing compound may be a low-molecular compound (for example, a molecular weight less than 2000), or a macromolecule (for example, a molecular weight of 2000 or more, in the case of a polymer, the weight average molecular weight is 2000 or more). The weight average molecular weight of the epoxy-containing compound is preferably 200-100000, more preferably 500-50000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, more preferably 5,000 or less, and particularly preferably 3,000 or less.

Commercial products can be used for the epoxy group-containing compound. For example, EHPE3150 (manufactured by Daicel Corporation) and EPICLON N-695 (manufactured by DIC) can be mentioned. In addition, the epoxy group-containing compound can use paragraphs 0034 to 0036 of JP 2013-011869 A, paragraphs 0147 to 0156 of JP 2014-043556, and paragraph 0085 to JP 2014-089408 of The compound described in 0092. Incorporate such content into this manual.

The content of the epoxy group-containing compound in the composition is preferably 0.1-10% by mass relative to the total solid content of the composition, more preferably 0.5-8% by mass, and still more preferably 1.0-6% by mass . The epoxy group-containing compound may be used singly or in two or more types. When the above composition contains two or more epoxy group-containing compounds, the total content is preferably within the above range.

〔Ultraviolet absorber〕 The composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of the cured film can be made into a more excellent (fine) shape. As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used. As these specific examples, the compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012/0068292) of JP 2012-068418 A can be used, and these contents can be incorporated into this specification. In addition, diethylamino-phenylsulfonyl-based ultraviolet absorbers (manufactured by DAITO CHEMICAL CO., LTD., trade name: UV-503) and the like can also be preferably used. As the ultraviolet absorber, the compounds exemplified in paragraphs 0134 to 0148 of JP 2012-32556 A can be cited. The content of the ultraviolet absorber is preferably 0.001 to 15% by mass relative to the total solid content of the composition, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass.

〔Silicane coupling agent (adhesive agent)〕 The composition may contain a silane coupling agent. When the cured film is formed on the substrate, the silane coupling agent functions as an adhesive that improves the adhesion between the substrate and the cured film. Silane coupling agent refers to a compound containing a hydrolyzable group and other functional groups in the molecule. In addition, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by a hydrolysis reaction and/or a condensation reaction. As the hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned. When the hydrolyzable group contains carbon atoms, the carbon number is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms are preferred. In addition, when the cured film is formed on the substrate, in order to improve the adhesion between the substrate and the cured film, the silane coupling agent does not contain fluorine atoms and silicon atoms (excluding silicon atoms bonded by hydrolyzable groups). Preferably, it does not contain fluorine atoms, silicon atoms (except for silicon atoms bonded to hydrolyzable groups), alkylene groups substituted by silicon atoms, straight-chain alkyl groups with 8 or more carbons, and those with 3 or more carbons A branched alkyl group is preferred. The silane coupling agent may contain ethylenic unsaturated groups such as (meth)acryloyl groups. When it contains an ethylenically unsaturated group, the number is preferably 1-10, more preferably 4-8. In addition, silane coupling agents containing ethylenically unsaturated groups (for example, compounds with a molecular weight of 2000 or less containing hydrolyzable groups and ethylenically unsaturated groups) do not meet the above-mentioned polymerizable compounds.

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

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

〔Interface active agent〕 The composition may contain a surfactant. The surfactant helps to improve the coating properties 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 relative to the total solid content of the composition. Better. Surfactant may be used individually by 1 type, and may use 2 or more types. When two or more surfactants are used in combination, the total amount is preferably within the above range.

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

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

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

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

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

Examples of the solvent include water and organic solvents.

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

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

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

As the filler, the composition preferably contains inorganic particles, and more preferably contains silica particles. The silicon dioxide particles may be any one of solid silicon dioxide, hollow silicon dioxide and porous silicon dioxide. The content of silicon dioxide particles in the composition is not particularly limited. From the viewpoint of excellent low reflectivity, it is preferably 1-15% by mass, and more preferably 4-10% by mass relative to the total solid content of the composition. good. The average primary particle size of the silicon dioxide particles is not particularly limited, and it is preferably 40 nm or more and less than 100. The average primary particle size of the silica particles can be measured with a transmission electron microscope (TEM) in the same way as the average primary particle size of the pigment.

The surface of the silica particles can be modified, and silica particles whose surfaces are modified with functional groups are preferred. Examples of functional groups that modify the surface of silica particles include hydrocarbon groups, (meth)acrylic groups, vinyl groups, fluorine-containing groups, groups containing siloxane bonds, hydroxyl groups, acid groups, and Basic base. The synthesis method of the surface-modified silica particles (the surface modification method of the silica particles) is not particularly limited, and a known method using a surface modifier can be used. For example, a method of modifying the surface of silica particles with a silane coupling agent containing a hydrolyzable group and the above-mentioned functional group in the molecule, and making the surface have an ethylenically unsaturated group (such as (meth)acrylic acid) A method of reacting silicon dioxide particles with ethylenic unsaturated groups and the above functional groups in the presence of a polymerization initiator. The amount of surface modifier used in the method of synthesizing surface-modified silica particles is not particularly limited, and the content of the surface modifier relative to the total solid content of the silica particle composition is 1 to 70% by mass It is more preferable, and it is more preferable to become an amount of 5-50 mass %. In addition, the surface modifier may be used singly or in two or more types.

[Method of manufacturing composition] Regarding the composition, first, a dispersion composition in which a black colorant is dispersed is produced, and the obtained dispersion composition is further mixed with other components to form a composition. Regarding the dispersion composition, it is preferable to mix and prepare a black coloring material, a resin (which may be a specific resin or another resin, and a dispersant is preferable) and a solvent. Furthermore, it is also preferable to make the dispersion composition contain a polymerization inhibitor.

The above-mentioned dispersion composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsification device, a wet mill or a wet disperser).

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

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

〔Method of manufacturing cured film〕 The composition layer formed using the above composition can be cured to obtain a cured film (including a patterned cured film). There are no particular restrictions on the method of producing the cured film, but it is preferable to include the following processes. •Composition layer formation process •Exposure process •Development process Hereinafter, each process will be described.

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

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

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

〔Development process〕 The developing process is a process of developing the exposed composition layer to form a hardened film. Through this process, the composition layer of the unirradiated part in the exposure process is dissolved out, leaving only the light-hardened part to obtain a patterned cured film. The type of developer used in the development process is not particularly limited, and an alkaline developer that does not cause damage to the imaging elements and circuits of the substrate is preferred. The development temperature is, for example, 20 to 30°C. The development time is, for example, 20 to 90 seconds. In order to further remove the residue, it has been carried out for 120 to 180 seconds in recent years. Furthermore, in order to further improve the residue removal performance, sometimes the process of spinning off the developer solution every 60 seconds is repeated several times, and further supplying the developer solution again.

As the alkaline developer, an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass) is preferred. Examples of basic compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, hydroxide Tetraethylammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo[5.4.0]- 7-Undecene, etc. (Among them, organic bases are preferred.). In addition, when it is used as an alkali developer, it is usually washed with water after development.

〔Post-baking〕 After the exposure process, heat treatment (post-baking) is better. Post-baking is used for heat treatment after development for complete curing. The heating temperature is preferably 240°C or less, and more preferably 220°C or less. The lower limit is not particularly limited, and if efficient and effective treatment is considered, 50°C or higher is preferable, and 100°C or higher is more preferable. Post-baking can be carried out continuously or in batches using heating mechanisms such as heating plates, flow ovens (hot air circulation dryers) or high-frequency heating machines.

The above-mentioned post-baking can be performed in an atmosphere with a low oxygen concentration. For example, the oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. The lower limit is not particularly limited, but is actually 10 volume ppm or more.

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

[Physical properties of cured film and uses of cured film] [Physical properties of cured film]

As illustrated in Figure 1 above, the cured film formed is typically a black layer (lower layer) containing a black coloring material and a coating layer (upper layer) made of a specific resin (cured material containing a specific resin) 2-layer structure. In addition, generally, the coating layer is a layer arranged on the side (air side) opposite to the substrate in the cured film arranged on the substrate. The black layer mainly contains the above-mentioned black coloring material. The coating layer is a layer formed by hardening the specific resin near the surface of the coating film obtained by applying the composition. In addition, the coating layer may contain unreacted specific resin. In addition, the coating layer may contain components other than the components derived from the specific resin (the cured product of the specific resin, the unreacted specific resin, etc.). However, it is preferable that the coating layer does not substantially contain a black coloring material. Specifically, the content of the black coloring material in the coating layer is preferably 5% by mass or less with respect to the total mass of the coating layer, and more preferably 1% by mass or less. The refractive index of the clad layer is preferably lower than the refractive index of the black layer. The thickness of the cured film is, for example, preferably 0.1 to 4.0 μm, and more preferably 1.0 to 2.5 μm. Moreover, depending on the application, the cured film may be a thin film or a thick film compared to this range. Moreover, when a cured film is used as a light attenuation film, it is better to set it as a thin film (for example, 0.1-0.5 micrometer) than the said range, and to adjust the light-shielding property. The film thickness of the coating layer depends on the film thickness of the entire cured film, but for example, 5 to 300 nm is preferable, 10 to 200 nm is more preferable, 20 to 200 nm is more preferable, and 20 or more and less than 175 nm is particularly preferable. The film thickness of the cured film and the coating layer can be measured from the cross-sectional SEM (Scanning Electron Microscope) image of the cured film.

From the viewpoint of having excellent light-shielding properties, the cured film obtained by using the composition of the present invention preferably has an optical density (OD: Optical Density) of 2.0 or more per 1.0 μm film thickness in the wavelength region of 400 to 1200 nm , 3.0 or more is better. In addition, the upper limit is not particularly limited, but 10 or less is generally preferred. The above-mentioned cured film can be preferably used as a light-shielding film. Moreover, when a cured film (light-shielding film) is used as a light attenuation film, the optical density per 1.0 μm film thickness in the wavelength region of 400 to 1200 nm is preferably 0.1 to 1.5, and more preferably 0.2 to 1.0. In addition, in this specification, the optical density per 1.0 μm film thickness in the wavelength region of 400 to 1200 nm of 3.0 or more means that the optical density per 1.0 μm film thickness in the entire wavelength region of 400 to 1200 nm is 3.0 or more . In addition, in this specification, as a method of measuring the optical density of the cured film, the cured film is first formed on the glass substrate and then measured with a transmission densitometer (X-rite 361T (visual) densitometer), and the film at the measured part is also measured. Thickness, and calculate the optical density per predetermined film thickness.

In addition, it is also preferable that the cured film has a surface uneven structure. If so, the reflectance of the cured film when the cured film is used as the light shielding film can be reduced. The surface of the cured film itself may have an uneven structure, or another layer may be provided on the cured film to give the uneven structure. The shape of the surface uneven structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm or more and 1.5 μm or less. The reflectance of the cured film is preferably 5% or less, more preferably 3% or less, and even more preferably 2% or less. The method of making the surface uneven structure is not particularly limited, and it may be a method of containing organic fillers and/or inorganic fillers in the cured film or other layers, the lithography method using exposure and development, or the etching method, sputtering method, and A method of roughening the surface of the cured film or other layers such as rice stamping. In addition, as a method of reducing the reflectance of the cured film, in addition to the above, a method of providing a low refractive index layer on the cured film, and further providing a plurality of layers with different refractive indexes (for example, a high refractive index layer) The method and the method of forming the low optical density layer and the high optical density layer described in JP 2015-001654 A, etc.

In addition, the above-mentioned cured film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smart phones, and digital cameras; OA (Office Automation) devices such as multifunction printers and scanners; surveillance cameras, barcode reading Industrial equipment such as automated teller machines (ATM: automated teller machine), high-speed cameras, and personal authentication functions that use portrait authentication; automotive camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters ; And aerospace machines such as living body sensors, biosensors, military reconnaissance cameras, stereo map cameras, meteorological and ocean observation cameras, terrestrial resources reconnaissance cameras, and exploration cameras for astronomical and deep space targets in the universe ; The light-shielding member and light-shielding film of optical filters and modules used in etc., and further suitable for anti-reflection members and anti-reflection films.

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

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

[Light-shielding film, and solid-state imaging element and solid-state imaging device] The light-shielding film of the present invention is also suitable for solid-state imaging devices. In addition, the light-shielding film is one of the preferable applications of the cured film of the present invention, and the production of the light-shielding film of the present invention can also be performed by the method described as the method of manufacturing the cured film. Specifically, the composition can be coated on a substrate to form a composition layer, and exposure and development can be performed to produce a light-shielding film. In addition, the solid-state imaging element of the present invention is a solid-state imaging element including the cured film (light-shielding film) of the present invention. As described above, the solid-state imaging device of the present invention contains the above-mentioned cured film (light-shielding film). The solid-state imaging element contains a hardened film (light-shielding film), and there is no particular limitation. For example, a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) having a light-receiving area on the substrate may be mentioned. Multiple light-receiving elements such as photodiodes and polysilicon, and have a hardened 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 pixels for color adjustment, etc.) or the opposite side of the forming surface form. In addition, when a cured film (light-shielding film) is used as the light attenuation film, for example, if the light attenuation film is arranged so that a part of light enters the light receiving element after passing through the light attenuation film, the dynamic range of the solid-state imaging element can be improved. The solid-state imaging device includes the above-mentioned solid-state imaging element.

2 to 3, a configuration example of a solid-state imaging device and a solid-state imaging element will be described. In addition, in FIG. 2 to FIG. 3, in order to make each part clear, the mutual ratio of thickness and/or width is ignored, and a part is exaggerated and shown. As shown in FIG. 2, the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Furthermore, the lens layer 111 is superposed on this cover glass 103 via the spacer 104. As shown in FIG. The lens layer 111 is composed of a support 113 and a lens material 112. The lens layer 111 may be integrally formed by the support 113 and the lens material 112. If stray light enters the peripheral region of the lens layer 111, the light condensing effect on the lens material 112 due to the diffusion of the light is weakened, and the light reaching the imaging unit 102 is reduced. In addition, noise caused by stray light also occurs. Therefore, a light shielding film 114 is provided in the peripheral region of the lens layer 111 to shield light. The cured film of the present invention can also be used as the light shielding film 114 described above.

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

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

An imaging unit 102 is provided in the center of the surface of the wafer substrate 106. In addition, if stray light enters the peripheral region of the imaging unit 102, dark current (noise) is generated from the circuit in the peripheral region, so the light shielding film 115 is provided in the peripheral region to shield light. The cured film of the present invention is preferably used as the light-shielding film 115.

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

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

As shown in FIG. 3, the imaging unit 102 is composed of a light-receiving element 201, a color filter 202, a microlens 203, and other units provided on a substrate 204. The color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The cured film of the present invention can be used as the black matrix 205bm.

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

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

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

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

[Image display device] The cured film of the present invention can also be applied to image display devices. As a form in which the image display device has a cured film, for example, a form in which the cured film is contained in a black matrix and a color filter containing such a black matrix is used in the image display device can be cited. Next, the black matrix and the color filter including the black matrix will be described, and further, as a specific example of the image display device, a liquid crystal display device including such a color filter will be described.

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

The black matrix manufacturing method is not particularly limited, and it can be manufactured by the same method as the manufacturing method of the cured film described above. Specifically, the composition can be coated on a substrate to form a composition layer, and exposure and development can be performed to produce a patterned cured film (black matrix). In addition, the thickness of the cured film used as the black matrix is preferably 0.1 to 4.0 μm.

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

＜Color filter＞ It is also preferable that the cured film of the present invention is included in a color filter. The form of the color filter containing a cured film is not particularly limited, and a color filter provided with a substrate and the above-mentioned black matrix is mentioned. That is, it is possible to exemplify a color filter having red, green, and blue colored pixels formed in the opening of the black matrix formed on the substrate.

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

＜Liquid crystal display device＞ It is also preferable that the cured film of the present invention is included in a liquid crystal display device. There are no particular limitations on the form in which the liquid crystal display device includes a cured film, and a form including a color filter including the black matrix (cured film) described above can be mentioned.

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

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

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

〔Infrared sensor〕 It is also preferable that the cured film of the present invention is included in an infrared sensor. The infrared sensor of the above embodiment will be described using FIG. 4. In the infrared sensor 300 shown in FIG. 4, the figure number 310 is a solid-state image sensor. The imaging area provided on the solid-state imaging element 310 is configured by combining the infrared absorption filter 311 and the color filter 312 of the embodiment of the present invention. The infrared absorption filter 311 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and shields light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm, and more preferably a wavelength For the film of 900-1000nm light), as the coloring agent, a cured film containing an infrared absorber (the form of the infrared absorber is as described above) can be used. The color filter 312 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible light region, such as a color filter formed with pixels of red (R), green (G), and blue (B) The form of the device is as described above. Between the infrared transmission filter 313 and the solid-state imaging element 310, a resin film 314 (for example, a transparent resin film, etc.) which transmits light of the wavelength of the infrared transmission filter 313 is arranged. The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and can use coloring agents that absorb light in the visible light region (for example, perylene compounds and/or dibenzofuranone compounds) and The cured film of the present invention of an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, a polymethine compound, etc.). The infrared transmission filter 313 shields light having a wavelength of 400 to 830 nm, and preferably transmits light having a wavelength of 900 to 1300 nm. The color filter 312 and the infrared transmission filter 313 are provided with a microlens 315 on the hν side of the incident light. A planarization film 316 is formed to cover the microlens 315. In the form shown in FIG. 4, a resin film 314 is arranged, but an infrared transmission filter 313 may be formed instead of the resin film 314. In other words, the infrared transmission filter 313 may be formed on the solid-state imaging element 310. Furthermore, in the form shown in FIG. 4, the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thicknesses of the two may be different. Furthermore, in the form shown in FIG. 4, the color filter 312 is provided at a position closer to the incident light hν side than the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 can also be changed. The infrared absorption filter 311 is provided at a position closer to the hν side of the incident light than the color filter 312. Furthermore, in the form shown in FIG. 4, the infrared absorption filter 311 and the color filter 312 are laminated adjacently, but the two filters need not necessarily be adjacent, and another layer may be provided between the two filters. The cured film of the present invention can be used as a light-shielding film for the end and/or side surface of the infrared absorption filter 311, and if used on the inner wall of the infrared sensor device, it can also prevent internal reflection and/or Unintended light incident on the light receiving part improves sensitivity. According to this infrared sensor, since image information can be acquired at the same time, it is possible to perform motion sensing for identifying and detecting the object of motion. Furthermore, distance information can be acquired, and therefore, images including 3D information can be photographed.

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

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

[Preparation of light-shielding composition] As shown in Table 4, each component was mixed in each part by mass to prepare compositions 1 to 41. 〔Preparation of dispersion composition〕 In order to prepare a light-shielding composition (hereinafter, also simply referred to as "composition"), first, a dispersion composition is prepared.

<Preparation of Titanium Black Dispersion A (Dispersion A)> The following raw materials were subjected to dispersion treatment using NPM Pilot manufactured by SHINMARU ENTERPRISES CORPORATION, whereby titanium black dispersion A was obtained.

•Titanium black (T-1) (details will be described later); 25 parts by mass • Resin (X-1) (details will be described later) PGMEA 30% by mass solution (pigment dispersant); 25 parts by mass •PGMEA; 23 parts by mass • Butyl acetate; 27 parts by mass

In addition, PGMEA means propylene glycol monomethyl ether acetate. In addition, the PGMEA 30% by mass solution of the resin (X-1) means a solution in which the resin (X-1) is dissolved in PGMEA so that the content of the resin (X-1) becomes 30% by mass relative to the total mass of the solution. Hereinafter, the case of “(solvent name) (number) mass% solution of (substance name)” is based on the same meaning.

(Production of titanium black (T-1)) Weigh titanium oxide MT-150A (trade name: manufactured by TAYCA CORPORATION) (100g) with an average particle diameter of 15nm, and silicon dioxide particles AEROGIL (registered trademark) with a BET surface area of 300m ² /g ) 300/30 (manufactured by EVONIK) (25g) and dispersant DISPERBYK-190 (trade name: manufactured by BYK-Chemie GmbH) (100g), ion-exchange water (71g) is added, MAZERSTAR KK-400W manufactured by KURABO is used to The revolution speed of 1360 rpm and the rotation speed of 1047 rpm were processed for 20 minutes, thereby obtaining a homogeneous mixture aqueous solution. This aqueous solution was filled into a quartz container, heated to 920°C in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), and then replaced with nitrogen. At the same temperature, the ammonium gas was adjusted to 100 mL/min After being circulated for 5 hours, the nitriding reduction treatment was carried out. After the end, the recovered powder was crushed with a mortar, thereby obtaining a powdery titanium black (T-1) with a specific surface area of 73 m ² /g containing Si atoms.

(Production of resin (X-1)) A resin P containing 15% by mass and 85% by mass of repeating units derived from the following monomer A and repeating units derived from the following monomer B, with respect to all repeating units of the resin, was synthesized. Using 4-hydroxybutyl acrylate glycidyl ether, resin X-1 in which an ethylenically unsaturated group was introduced into the obtained resin P was produced. The weight average molecular weight of the obtained resin X-1 was 15000, the acid value was 70 mgKOH/mg, and the C=C value was 1.1 mmol/g.

•Monomer A (a giant monomer with a weight average molecular weight of 3000, and the value marked in 9 of the repeating unit is the average value of each monomer)

[Chemical formula 22]

•Monomer B (ARONIX M5300 (manufactured by TOAGOSEI CO., LTD.)) CH ₂ =CHCOO-(C ₅ H ₁₀ COO) _n -Hω-carboxy-polycaprolactone (n≈2) monoacrylate

<Preparation of titanium black dispersion B (dispersion B)> The resin (X-1) PGMEA 30% by mass solution (pigment dispersant) was changed to the resin (X-2) PGMEA 30% by mass solution (pigment dispersant), except that it was produced in the same manner as the dispersion A Dispersion B. The structure of resin (X-2) is as follows. The weight average molecular weight is 33000, the acid value is 60 mgKOH/mg, and the C=C value is 0 mmol/g. In addition, the number marked on each repeating unit represents the molar ratio of each unit.

[Chemical formula 23]

<Preparation of Carbon Black (CB) Dispersion Liquid C (Dispersion Liquid C)> The dispersion obtained by mixing the following raw materials was further thoroughly stirred with a mixer to perform premixing. Furthermore, using ULTRA APEX MILL UAM015 manufactured by KOTOBUKI KOGYOU CO., LTD., the dispersion was subjected to dispersion treatment under the dispersion conditions described below to obtain a dispersion liquid. After the dispersion was completed, the beads and the dispersion were separated by a filter, whereby dispersion C was obtained.

•Coated carbon black (details will be described later); 20 parts by mass • DISPERBYK-167 (pigment dispersant, manufactured by BYK-Chemie GmbH, solid content 52% by mass); 8.7 parts by mass •SOLSPERSE 12000 (pigment derivative, manufactured by Lubrizol Japan Ltd.); 1 part by mass •PGMEA; the solid content of dispersion C becomes 35 mass%

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

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

<Preparation of black dispersion D (dispersion D)> Except that the coated carbon black was changed to Irgaphor Black S 0100 CF (manufactured by BASF Corporation), dispersion D was produced in the same manner as dispersion C.

<Preparation of black dispersion E (dispersion E)> The red pigment dispersion liquid R1 and the blue pigment dispersion liquid B1 shown below were mixed at a ratio of 1:1 (mass ratio) as the dispersion liquid E.

(Red pigment dispersion liquid R1) The following raw materials were subjected to dispersion treatment using NPM Pilot manufactured by SHINMARU ENTERPRISES CORPORATION to obtain a red pigment dispersion liquid R1.

• Pigment Red 254; 8.3 parts by mass • Pigment Yellow 139; 3.7 parts by mass • DISPERBYK-161 (dispersant, manufactured by BYK-Chemie GmbH, solid content 30% by mass); 16.0 parts by mass •PGMEA; 72.0 parts by mass

(Blue pigment dispersion B1) The following raw materials were subjected to dispersion treatment using NPM Pilot manufactured by SHINMARU ENTERPRISES CORPORATION to obtain a blue pigment dispersion liquid B1.

•Pigment Blue 15:6; 9.5 parts by mass •Pigment Violet 23; 2.4 parts by mass • DISPERBYK-161 (dispersant, manufactured by BYK-Chemie GmbH, solid content 30% by mass); 18.7 parts by mass •PGMEA; 69.4 parts by mass

〔Raw materials of composition〕 The raw materials used for the preparation of the composition are shown below.

＜Dispersed composition＞ The above-mentioned dispersion liquids A to E are used as dispersion compositions.

＜Resin＞ •A-1: A polymer synthesized by the method shown below. Put MEK (2-butanone) (420.0g), X-22-174DX (manufactured by Shin-Etsu Chemical Co., LTD.) into a 1L autoclave equipped with a stirrer, containing methacrylic acid at one end Linear dimethylpolysiloxane) (5.4g), MAA (methacrylic acid) (18.0g), 2-HEMA (2-hydroxyethyl methacrylate) (99.0g), IBMA (isobornyl methacrylate) (57.6g) and polymerization initiator V-70 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2'-azobis(4-methoxy-2, 4-Dimethylvaleronitrile)) (2.0 g) was polymerized at 30°C for 24 hours while stirring in a nitrogen atmosphere, thereby synthesizing a crude copolymer. After adding heptane to the solution of the obtained crude copolymer, performing reprecipitation purification, vacuum drying was performed, thereby obtaining copolymer 1 (149.2 g). Copolymer 1 has a number average molecular weight of 17,100 and a weight average molecular weight of 50,500. Put copolymer 1 (40.0g), BEI (Karenz BEI, manufactured by Showa Denko KK, 1,1-bis(acryloxymethyl)) into a 300mL glass flask equipped with a thermometer, a stirrer, and a heating device. Ethyl isocyanate) (42.0g), DBTDL (dibutyltin dilaurate) (0.17g), BHT (2,6-di-t-butyl-p-cresol) (2.1g) and MEK (115.4g) The reaction was carried out at 40°C for 48 hours while stirring, thereby synthesizing a crude polymer. After adding heptane to the solution of the obtained crude polymer and performing reprecipitation purification, it was vacuum-dried to obtain resin (A-1) (66.0 g). The number average molecular weight of the resin (A-1) was 42,300, and the weight average molecular weight was 119,990.

•A-2: X-22-164B (manufactured by Shin-Etsu Chemical Co., LTD., linear dimethylpolysiloxane containing groups containing methacryloyl groups at both ends) •A-3: X-22-2445 (manufactured by Shin-Etsu Chemical Co., LTD., linear dimethylpolysiloxane containing acrylic group-containing groups at both ends) •A-4: KF-6001 (manufactured by Shin-Etsu Chemical Co., LTD., linear dimethylpolysiloxane containing hydroxyl-containing groups at both ends) •A-5: X-22-164 (manufactured by Shin-Etsu Chemical Co., LTD., linear dimethylpolysiloxane containing groups containing methacryloyl groups at both ends) •A-6: X-22-164AS (manufactured by Shin-Etsu Chemical Co., LTD., linear dimethylpolysiloxane containing groups containing methacryloyl groups at both ends) •A-7: X-22-164A (manufactured by Shin-Etsu Chemical Co., LTD., linear dimethylpolysiloxane containing groups containing methacryloyl groups at both ends) •A-8: X-22-164C (manufactured by Shin-Etsu Chemical Co., LTD., linear dimethyl polysiloxane containing groups containing methacryloyl groups at both ends) •A-9: X-22-164E (manufactured by Shin-Etsu Chemical Co., LTD., linear dimethylpolysiloxane containing groups containing methacryloyl groups at both ends)

•A-10: Resin synthesized by the method shown below.

[Chemical formula 24]

Put KF-6001 (A-4) (20.78g), 1,1-(bisacryloxymethyl)ethyl isocyanate (Karenz BEI made by Showa Denko KK) (8.13g) into a single-necked eggplant flask ), PGMEA (96.4g), 2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by KOEI CHEMICAL CO., LTD.) (16.3mg) and tris(2-ethylhexanoic acid) Bismuth (NEOSTANN U-600 manufactured by NITTOH CHEMICAL Co. Ltd.) (16.3 mg) was heated to 90° C. and stirred for 72 hours to obtain a 30% PGMEA solution of silicone resin XX-1. To the obtained solution, mercaptosuccinic acid (manufactured by Tokyo Chemical Industry Co., LTD.) (2.55 g) and ethanol (41.6 g) were added, and triethylamine (172 mg) was added dropwise while stirring at room temperature. Stir for 24 hours at low temperature. Next, ethyl acetate (150 g) was added to the above solution, and 0.1N HCl aqueous solution (150 g) and distilled water (150 g) were added to the solution and mixed, and then the organic phase in the solution was extracted. Sodium sulfate was added to the obtained organic phase, stirred for 10 minutes, sodium sulfate was filtered, and the obtained filtrate was distilled off under reduced pressure, thereby obtaining XX-2 (28.5 g). The obtained XX-2 is referred to as resin A-10.

•A-11～A-15: Resins synthesized by the method shown below. PGMEA (62.9 g) (further, chain transfer agent 2-mercaptoethanol (Yg), if necessary) was put into a three-necked eggplant-shaped flask, and the temperature was raised to 75° C. in a nitrogen atmosphere. Into this flask, X-22-2404 (manufactured by Shin-Etsu Chemical Co., LTD., linear dimethyl polysiloxane containing a methacrylic group-containing group at one end) was dropped and mixed over 2 hours. Oxyane) (60.0g), HO-MS (manufactured by KYOEISHA CHEMICAL Co., LTD., 2-methacryloxyethyl succinic acid) (29.8g), PGMEA (146.7g) and initiator V -601 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2'-azobis(2-methylpropionic acid) dimethyl ester) (Xg) solution. After dripping, after further stirring the said flask at 75 degreeC for 2 hours, V-601 (0.75g) and PGMEA (23.8g) were added. Furthermore, the said flask was heated up to 90 degreeC, and it stirred for 3 hours. The obtained solution was replaced with air, and after confirming that the oxygen concentration in the atmosphere in the flask became 18% by mass or more, GMA (manufactured by Tokyo Chemical Industry Co., Ltd., glycidyl methacrylate) (10.2 g) was added , TEMPO (2,2,6,6-tetramethylpiperidine 1-oxy) (0.11g) and dimethyldodecylamine (4.4g), stirred at 90°C for 48 hours, thereby obtaining a resin containing的polymer solution. The amount X (g) of the above-mentioned V-601 and the value of 2-mercaptoethanol Y (g) were set to the amounts shown in Table 1 below, and resins A-11 to A-15 were synthesized. In addition, the obtained resins A-11 to A-15 were used in the preparation of the composition in the form of a PGMEA solution with a solid content of 30% of the resins A-11 to A-15.

[Table 1]

The molecular weight (number average molecular weight (Mn), weight average molecular weight (Mw)), acid value, and C=C value of resins A-1 to A-15 are shown below.

[Table 2]

In addition, among the above resins, A-2, A-3, and A-5 to A-15 are specific resins. Among them, A-2, A-3, A-5 to A-10 are main chain type specific resins, and A-11 to A-15 are side chain type specific resins.

＜Polymerization initiator＞ •I-1: The following compounds • I-2: The following compounds •I-3: The following compounds •I-4: The following compounds The polymerization initiators I-1 to I-4 are all oxime compounds. In addition, in the above-mentioned polymerization initiator, when I-1 to I-3 are dissolved in acetonitrile 0.001% by mass, the obtained solution has an absorbance of 0.45 or more at a wavelength of 340 nm with an optical path length of 10 mm. On the other hand, when using I-4 for the same test, the obtained solution has an absorbance of less than 0.45 at a wavelength of 340 nm.

[Chemical formula 25]

＜Polymerizable compound＞ •M-1: NK ester A-TMMT (manufactured by Shin Nakamura Chemical Co., Ltd., a compound represented by the following structure)

[Chemical formula 26]

•M-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of compounds represented by the following structure)

[Chemical formula 27]

•M-3: VISCOAT #802 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., a compound represented by the following structure)

[Chemical formula 28]

＜Polymerization inhibitor＞ •PI-1: p-methoxyphenol

＜Solvent＞ •PGMEA: Propylene glycol monomethyl ether acetate

The above components were mixed to prepare the composition shown in Table 3 below.

＜Silica Particle Dispersion Liquid＞ (Synthesis of silicon dioxide particles PS-1) To a dispersion of hollow silica particles ("THRULYA 4110" manufactured by JGC Catalysts and Chemicals Ltd., solid content: 20% by mass, dispersion medium: isopropanol, average primary particle size: 60 nm) 100 g of KBM-503 ( Shin-Etsu Chemical Co., LTD., 3-methacryloxypropyltrimethoxysilane) 4 g, 10% formic acid aqueous solution 0.5 g, and water 1 g, and stirred at 60°C for 3 hours. Using Rotavapor, after replacing the dispersion medium with 1-methoxy-2-propanol, the solid content concentration was adjusted by adding 1-methoxy-2-propanol to obtain a solid content concentration of 20 mass. % Silica particles PS-1 (surface-treated hollow silica) dispersion.

(Preparation of modified silica dispersion liquid S-1) Into a three-necked flask were put a dispersion of silica particles PS-1 (solid content 20% by mass, 30.0 g) and a surface modifier MA-1 (manufactured by Shin-Etsu Chemical Co., LTD., trade name "X-22"). -2404", single-ended methacrylic modified silicone oil) (1.8g) and PGMEA (28.2g), heated to 80°C in a nitrogen atmosphere. 0.01 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to the flask, and the flask was stirred for 3 hours. V-601 (0.02 g) was further added to this flask, and after stirring for 2 hours, precision filtration of the dispersion liquid was performed. 1-Methoxy-2-propanol was added to the obtained filter to obtain a modified silica dispersion S-1 (31.3 g) containing surface-modified silica particles and a solid content of 20% by mass. ).

(Preparation of modified silica dispersion S-2～S-14) The silica particles and surface modifiers described in Table 3 were used respectively. In addition, modified silica dispersions S-2 to S-14 were prepared according to the above-mentioned preparation method of modified silica dispersion S-1. . The silica particles and surface modifiers used in the preparation of each modified silica dispersion are shown below.

-Silica particles- • PS-2: Surface-treated solid silica particle gel ("PGM-AC-4130Y" manufactured by Nissan Chemical Corporation, solid content: 32% by mass, dispersion medium: 1-methoxy-2-propanol , Average primary particle size: 45nm) • PS-3: Hollow silica particle dispersion ("THRULYA 4320" manufactured by JGC Catalysts and Chemicals Ltd., solid content: 20% by mass, dispersion medium: methyl isobutyl ketone, average primary particle size: 60 nm ) In addition, after adding 1-methoxy-2-propanol to the silica particle PS-2 as a dispersion with a solid content concentration of 20% by mass, it was used for the preparation of a modified silica dispersion.

-Surface modifier- •MA-2: X-22-174ASX (manufactured by Shin-Etsu Chemical Co., LTD., single-ended methacrylic acid modified silicone oil) •MA-3: X-22-174BX (manufactured by Shin-Etsu Chemical Co., LTD., single-ended methacrylic modified silicone oil) •MA-4: iBMA (manufactured by Tokyo Chemical Industry Co., LTD., isobutyl methacrylate) •MA-5: MAC6F13 (manufactured by Tokyo Chemical Industry Co., LTD., 1H, 1H, 2H, 2H-tridecafluoro n-octyl methacrylate) •MA-6: HEMA (manufactured by Tokyo Chemical Industry Co., LTD., 2-hydroxyethyl methacrylate) •MA-7: HO-MS (manufactured by KYOEISHA CHEMICAL Co., LTD., 2-methacryloxyethyl succinic acid)

[table 3]

[Evaluation] 〔test〕 Using each of the above-mentioned compositions, the following tests were conducted.

<Evaluation of light-shielding properties> The compositions were respectively coated on a glass substrate by a spin coating method, and then heated on a hot plate at 100° C. for 2 minutes to obtain a composition layer. Next, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon), the obtained composition layer was exposed at 200 mJ/cm ² through a mask having an angular pattern of 2 cm square. The exposed composition layer was subjected to spin immersion development with a developer "CD-2060" (manufactured by FUJIFILM Electronic Materials Co., Ltd.) for 60 seconds, followed by spin drying. After that, it was heated at 220° C. for 5 minutes on a hot plate to obtain a light-shielding film (cured film) with a film thickness of 1.5 μm. Using UV-3600 (manufactured by Hitachi, Ltd.: spectrophotometer), the light-shielding properties of the obtained light-shielding film were evaluated in accordance with the following evaluation criteria. Set A and B within the allowable range.

"A": The maximum transmittance in the wavelength 400～700nm is 0.5% or less "B": The maximum transmittance in the wavelength of 400～700nm is higher than 0.5% and less than 2% "C": The transmittance in wavelength 400～700nm is higher than 2%

<Evaluation of reflectance before development (evaluation of low reflectivity before development)> The composition was coated on a glass substrate by a spin coating method, and then heated at 100°C for 2 minutes on a hot plate to obtain the composition物层。 The material layer. Next, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon), the obtained composition layer was exposed at 200 mJ/cm ² through a mask having an angular pattern of 2 cm square. After that, it was heated at 220° C. for 5 minutes on a hot plate to obtain a light-shielding film (cured film) with a film thickness of 1.5 μm. To the obtained substrate with a light-shielding film, light of 400 to 700 nm was incident at an incident angle of 8°, and the reflectance was measured using a spectroscope V7200 (trade name) manufactured by JASCO Corporation. The obtained measurement values were divided according to the following evaluation criteria, and the reflectance before development (low reflectivity before development) was evaluated. Set A and B within the allowable range. "A": The maximum reflectance in the wavelength 400-700nm is 2% or less "B": The maximum reflectance in the wavelength 400-700nm is higher than 2% and 5% or less "C": The maximum reflectance in the wavelength 400-700nm Rate higher than 5%

<Evaluation of reflectance after development (evaluation of low reflectivity after development)> In the above-mentioned "evaluation of reflectance before development" step, after exposing the composition layer, the exposed composition layer was subjected to 60% exposure with a developer "CD-2060" (manufactured by FUJIFILM Electronic Materials Co., Ltd.). Spin-drying was carried out after immersion development in seconds. Then, it heated at 220 degreeC for 5 minutes on a hotplate, and obtained the light-shielding film (cured film). Hereinafter, the measurement and evaluation of reflectance were carried out according to the same method and criteria as evaluation of reflectance after development (low reflectance after development). When both the reflectance before development (low reflectivity before development) and the reflectance after development (low reflectivity after development) are both A or B, it is judged that the low reflectivity of the light-shielding film is excellent.

<Evaluation of light resistance> Using a Super Xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.), the substrate with a light-shielding film prepared in the above-mentioned "evaluation of reflectance before development" was subjected to the following irradiation treatment: 7.5 The light with a wavelength of 300nm or more of a kw xenon lamp is irradiated with an illuminance of 50mW/cm ² and a cumulative exposure of 50 million Lux•h. After that, the reflectance was measured using a spectroscope V7200 (trade name) manufactured by JASCO Corporation, the reflectance change with respect to light of each wavelength before and after the irradiation treatment was calculated, and the light resistance was evaluated according to the following criteria. The reflectance change is calculated using the following formula. Reflectance variation (%)=丨(Reflectance after irradiation treatment (%)-Reflectance before irradiation treatment (%))丨"A": The maximum value of reflectance change in wavelength 400～700nm is less than 1% "B": The maximum value of the reflectance change in the wavelength of 400-700nm is higher than 1% and 3% or less "C": The maximum value of the reflectance change in the wavelength of 400-700nm is higher than 3%

〔result〕 The compounding of the composition used in the test and the test results performed with the corresponding composition are shown in the following table. In Table 4, the numbers described in the table corresponding to the column of each raw material name indicate the content (parts by mass) of each raw material in each composition. For example, composition 1 represents dispersion A containing 78.00 parts by mass. In addition, in the table, regarding the raw materials used for the preparation of the composition in a form where the solid content is not 100%, the addition amount (parts by mass) that also includes the mass of the components other than the solid content is described. For example, in more detail, the composition 34 contains 3.25 parts by mass of a resin solution containing 30% by mass of resin A-11. The "color material" column shows the type of black color material contained in the composition used for the test. "TB" means titanium black (T-1), "CB" means coated carbon black, "IB" means Irgaphor Black S 0100 CF, and "RB" means a mixed pigment of red pigment and blue pigment. The "resin type" column indicates the type of specific resin contained in the composition used for the test. "Main chain" means a main chain type specific polymer, and "side chain" means a side chain type specific polymer. The "resin addition amount" column indicates the content of the resin contained in the composition used for the test. The content of the resin is expressed as a mass percentage (mass %) relative to the total solid content of the composition. In addition, as the resin referred to here, the resin shown in the column of the above-mentioned <resin> is shown. For example, the dispersant contained in the composition is not counted as the content of the resin used to calculate the "resin addition amount". The column of "initiator light absorption characteristics" indicates whether or not the absorbance at a wavelength of 340 nm of a solution obtained when the polymerization initiator contained in the composition used for the test is dissolved in acetonitrile at a concentration of 0.001% by mass becomes 0.45 or more. Record the case that meets this requirement as A, and the case that does not meet it as B. The "coating layer film thickness" column indicates the film thickness of the coating layer in the light-shielding film produced in the evaluation of light-shielding properties. The film thickness of the coating layer was measured by cross-sectional SEM. In addition, in the light-shielding film described as unmeasurable, the surface of the light-shielding film in the coating layer became rough, and therefore the film thickness of the coating layer could not be measured.

[Table 4-1]

[Table 4-2]

[Table 4-3]

[Table 4-4]

[Table 4-5]

As shown in the table, it was confirmed that the problem of the present invention can be solved if the composition of the present invention is used.

In addition, it was confirmed that when the black coloring material was a metal nitride pigment such as titanium black, the obtained light-shielding film was more excellent in low reflectivity (comparison of Examples 6 to 10, etc.). In Example 6, the titanium black was changed to vanadium nitride VN-O (manufactured by Japan New Metals Co., Ltd.), niobium nitride NbN-O (manufactured by Japan New Metals Co., Ltd.), and The zirconium nitride prepared by the method of (Example 1) in JP 2017-222559 A was evaluated in the same manner, and the results were the same as in Example 6, respectively. In Example 6, the titanium black was changed to silicon dioxide-coated zirconium nitride (Japanese Patent Application Laid-Open No. 2015-117302), and the result of the same evaluation was the same as that of Example 6. In Example 6, even if the titanium black is replaced by titanium black: zirconium nitride=1:9, 3:7, 5:5, 7:3, 9:1, the same effect is obtained (the ratio is weight ratio) . Also, even if it is replaced with titanium black: silicon dioxide coated zirconium nitride=1:9, 3:7, 5:5, 7:3, 9:1, the same effect is obtained (the ratio is weight ratio).

When the specific resin-based main chain type specific resin (specific resin represented by the general formula (2)) is confirmed, the low reflectivity of the obtained light-shielding film is more excellent (Comparison of Examples 1 to 2 and Examples 6 to 7, etc. ). In addition, in Example 6, A-10 was changed to the following compound synthesized in the same manner as XX-1 (main chain type specific resin, Mn3000, Mw5100, acid value 0mgKOH/g, C=C value 0.67mmol/g ), the result of the same evaluation was the same as that of Example 6.

【Chemical formula 29】

When the specific resin-based side chain type specific resin is confirmed, when the content of the side chain type specific resin is 5.0% by mass or more with respect to the total mass of the solid content, the obtained light-shielding film has more excellent low reflectivity after development ( Comparison of Example 1 and 21, etc.).

When the specific resin-based side chain type specific resin is confirmed, when the content of the side chain type specific resin is 10.0% by mass or less relative to the total mass of the solid content, the obtained light-shielding film has more excellent low reflectivity after development ( Comparison of Examples 21 and 22, etc.).

It is confirmed that when the polymerization initiator contained in the composition is dissolved in acetonitrile at a concentration of 0.001% by mass, the obtained solution has an optical path length of 10 mm and an absorbance at a wavelength of 340 nm of 0.45 or more. The obtained light-shielding film is more excellent in low reflectivity after development (the result of Example 14, etc.). In Example 6, the polymerization initiator I-1 was changed to IRGACURE 369 (trade name, manufactured by BASF Corporation), and the results of the same evaluation showed that the light-shielding properties and low reflectivity after development were B. Other than that, the same Example 6 is the same.

In Example 1, the same results as in Example 1 were also obtained without adding a polymerization inhibitor. In addition, in Example 6, the same results as in Example 6 were also obtained without adding a polymerization inhibitor.

The light-shielding film of Example 6 was used to produce a solid-state imaging element according to the method described in International Publication WO2018/061644, and the result showed good performance.

13 parts by mass of silica particle dispersion S-1 (solid content 20% by mass) prepared by the above method was added to composition 6, and then PGMEA was added to prepare a composition having the same solid content concentration as composition 6物101. The content of the surface-modified silica particles in the composition 101 was 8% by mass relative to the solid content in the composition 6. The composition 6 was changed to the composition 101, and as a result of evaluation in the same manner as in Example 6, the same evaluation as in Example 6 was obtained. Silica particle dispersion S-2 to S-14 (both solid content of 20% by mass) were used instead of silica particle dispersion S-1. In addition, the solid content concentration was prepared according to the above method. Compositions 102 to 114 same as composition 6. The composition 6 was changed to the compositions 102 to 114, and the results were evaluated in the same manner as in Example 6, and the same evaluations as in Example 6 were obtained.

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

Fig. 1 shows a cross-sectional view of a preferred embodiment of the cured film of the present invention. Fig. 2 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device. Fig. 3 is an enlarged schematic cross-sectional view showing the imaging unit of Fig. 2. Fig. 4 is a schematic cross-sectional view showing a configuration example of an infrared sensor.

Claims (9)

A light-shielding composition containing a black coloring material, a polymerizable compound, a photopolymerization initiator, and a resin, the resin containing a polymerizable group and a group represented by the general formula (1), and the number average molecular weight of the resin is 100 ～15000, the content of the resin is 2.0-15.0% by mass relative to the total mass of the solid content of the light-shielding composition, *-(SiR ¹ R ² -O) _na -* (1) In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, na represents an integer of 1 to 200, and * represents a bonding position. The light-shielding composition according to claim 1, wherein the resin is a compound represented by the general formula (2), R ³ -(SiR ¹ R ² -O) _nb -SiR ¹ R ² -R ³ (2) In formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, R ³ represents an ethylenically unsaturated group-containing group, and nb represents an integer of 3 to 200. The light-shielding composition according to claim 2, wherein at least one of the R ³ has an acid group. The light-shielding composition according to claim 2 or 3, wherein at least one of R ³ has at least one selected from the group consisting of an ether bond, an ester bond, a urethane bond, and a thioether bond . The light-shielding composition according to any one of claims 1 to 3, wherein The black coloring material is one or more selected from the group consisting of metal nitrides and metal oxynitrides. A cured film obtained using the light-shielding composition described in any one of claims 1 to 5. The hardened film as described in claim 6, wherein The hardened film contains a black layer and a coating layer arranged on the surface of the black layer, The thickness of the coating layer is 20-200nm, The coating layer contains a cured product of the resin. The cured film according to claim 6 or 7, which is a light-shielding film. A solid-state imaging device containing the cured film according to any one of claims 6 to 8.

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