TW201809152A - Composition, cured film, color filter, light-blocking film, solid-state imaging device and image display device - Google Patents

Abstract

One objective of the present invention is to provide a composition which is capable of forming a light blocking film that exhibits excellent light blocking performance. Another objective of the present invention is to provide a cured film which exhibits excellent light blocking performance, a color filter which comprises the cured film, a light blocking film, a solid-state imaging device and an image display device. A composition according to the present invention contains an inorganic pigment and a black dye.

Description

Composition, cured film, color filter, light-shielding film, solid-state imaging device, and image display device

The invention relates to a composition, a cured film, a color filter, a light-shielding film, a solid-state imaging device, and an image display device.

Black light-shielding films are used for various applications. For example, a light-shielding film is used in a solid-state imaging device. Generally, a solid-state imaging device includes a solid-state imaging element such as a photographic lens, a CCD (Charge Coupled Device, charge-coupled device), and a CMOS (Complementary Metal-Oxide Semiconductor). The solid-state imaging element is also referred to as an "image sensor.") And a circuit board on which the solid-state imaging element is mounted. In this solid-state imaging device, noise caused by reflection of visible light may occur. Therefore, in order to suppress the occurrence of noise, a predetermined light-shielding film may be provided in the solid-state imaging device. Further, as another application of the light-shielding film, a so-called black matrix may be mentioned.

As a composition for forming such a light-shielding film, various compositions have been proposed. For example, Patent Document 1 discloses "a black resin composition for a resin black matrix, which contains at least a light-shielding material, a resin, and a solvent, and contains at least titanium nitride particles as a light-shielding material. When CuKα rays are used as the X-ray source, The diffraction angle 2θ of the above-mentioned titanium nitride particles originating from the peak at the (200) plane is 42.5 ° or more and 42.8 ° or less. "(Scope of patent application item 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent No. 5136139

The present inventors used a black composition prepared in accordance with Patent Document 1 to fabricate a light-shielding film disposed in a color filter of a solid-state imaging device, a liquid crystal image device, and the like, and studied its various properties. As a result, they found a specific wavelength region The light-shielding performance is relatively low (in other words, the optical density is lower). When a pigment such as titanium nitride particles is generally used, a dispersant is often used from the viewpoint of improving the dispersibility of the pigment. However, when the pigment concentration in the composition is increased in order to improve the light-shielding performance, the content of the dispersant in the composition becomes relatively large. Due to this, the light-shielding performance of the obtained light-shielding film may decrease. Therefore, it is desirable to improve the light-shielding performance of the light-shielding film by means other than increasing the pigment concentration.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition capable of forming a light-shielding film having excellent light-shielding performance. In addition, an object of the present invention is to provide a cured film having excellent light shielding performance, a color filter including the cured film, a light shielding film, a solid-state imaging device, and an image display device.

The present inventors have conducted intensive studies in order to achieve the above-mentioned problems. As a result, they have found that by using an inorganic pigment (more preferably, a black inorganic pigment described later, and a pigment containing a nitride or an oxynitride) and black The composition of the dye can solve the above-mentioned problems and completed the present invention. That is, it was found that the above-mentioned object can be achieved by the following structure.

(1) A composition containing an inorganic pigment and a black dye. (2) The composition according to (1), wherein the inorganic pigment is a pigment containing a nitride or an oxynitride. (3) The composition according to (1) or (2), wherein the black dye has a polymerizable group. (4) The composition according to (3), wherein the polymerizable group is an acrylfluorenyl group or a methacrylfluorenyl group. (5) The composition according to any one of (1) to (4), wherein the black dye is a xanthene-based dye or an azo-based dye. (6) The composition according to any one of (1) to (5), wherein the black dye is a dye multimer. (7) The composition according to any one of (1) to (6), further comprising a dispersant. (8) The composition according to (7), wherein the acid value of the dispersant is 50 mgKOH / g or more. (9) The composition according to (7) or (8), wherein the dispersant has a group selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate, and polymethyl methacrylate At least one structure in the group. (10) The composition according to any one of (1) to (9), further comprising a polymerizable compound and a polymerization initiator. (11) The composition according to any one of (1) to (10), further comprising an organic solvent. (12) The composition according to any one of (1) to (11), further comprising an alkali-soluble resin. (13) The composition according to any one of (1) to (12), wherein the content of the black dye with respect to the content of the inorganic pigment is 0.3 or less by mass ratio. (14) The composition according to any one of (1) to (13), wherein the solid content amount relative to the total mass of the composition is 10 to 40% by mass. (15) The composition according to any one of (1) to (14), wherein a content of the inorganic pigment is 30 to 70% by mass based on a solid content. (16) A cured film obtained using the composition according to any one of (1) to (15). (17) A color filter having the cured film according to (16). (18) A light-shielding film having the cured film according to (16). (19) A solid-state imaging device including the cured film according to (16). (20) An image display device having the cured film according to (16). [Inventive effect]

According to the present invention, it is possible to provide a composition capable of forming a light-shielding film having excellent light-shielding performance. Furthermore, according to the present invention, it is possible to provide a cured film excellent in light shielding performance, a color filter including the cured film, a light shielding film, a solid-state imaging device, and an image display device. [Illustrated simple illustration]

no.

Hereinafter, the present invention will be described. In this specification, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In the description of the group (atomic group) in the present specification, unsubstituted and unsubstituted expressions include those having a substituent together with those having no substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent. In this specification, "actinic rays" or "radiation" means, for example, the bright-line spectrum of a mercury lamp, extreme ultraviolet (EUV), X-rays, and electron beams represented by an excimer laser. In the present invention, light means actinic rays or radiation. Regarding "exposure" in this manual, unless otherwise specified, it includes not only exposure based on far-ultraviolet rays, X-rays, and EUV light represented by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams. Also included in the exposure. In this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acryl" refers to acryl and methyl Acrylic acid. In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in the present invention is different from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable group, and may be a monomer or a polymer. A polymerizable group refers to a group that participates in a polymerization reaction.

[Composition] The composition of the present invention includes an inorganic pigment (preferably a black inorganic pigment to be described later, and a pigment containing a nitride or an oxynitride is more preferable) and a black dye. The composition according to the present invention can form a light-shielding film having excellent light-shielding performance. That is, according to the composition of the present invention, it is possible to form the light-shielding performance in a specific wavelength region without degradation, and in a predetermined region (for example, the visible light region to 1200 nm), the minimum optical concentration (hereinafter, also referred to as "the lowest OD value" ".) A light-shielding film in a range capable of imparting sufficient light-shielding performance. The composition of the present invention is characterized by containing a black dye. When the inorganic pigment concentration is increased in order to increase the minimum optical concentration, the content of the dispersant used in the composition for the purpose of improving the dispersibility of the inorganic pigment becomes relatively large. Due to this, the light-shielding film obtained in some cases The shading performance decreases. However, since the composition of the present invention contains a black dye which has an absorption throughout the entire wavelength range of visible light without a dispersant, the minimum optical concentration of the light-shielding film can be increased without adding other components such as a dispersant. In particular, when using a xanthene-based dye or an azo-based dye as described later, it was found that a light-shielding film having more excellent light-shielding performance and excellent resolution can be formed.

Currently, the present inventors have found that it is particularly preferred that the black dye has a polymerizable group. When the light-shielding film is formed using the composition of the present invention, if the black dye has a polymerizable group, the dye is introduced into the matrix constituting the film via the polymerizable group. It is known that the heat resistance of a dye is generally inferior to that of a pigment. When a dye is used as a component of a light shielding film, the heat resistance of the light shielding film may be poor due to the dye. On the other hand, it was confirmed that, as described above, the matrix constituting the film and the black dye are chemically bonded by the polymerizable group, thereby becoming more excellent in heat resistance. In addition, recently, after a light-shielding film is formed on a predetermined substrate, it is sometimes required to peel the light-shielding film from the substrate due to deviations in the formation position of the light-shielding film and the like. So-called reworkability is required. The present inventors have also found that, as described above, the matrix constituting the film and the black dye are chemically bonded by the polymerizable group, and the reworkability is also improved. That is, for example, a color filter (hardened) produced by using, for example, a composition containing an inorganic pigment, a black dye having a polymerizable group, and an alkali-soluble resin by removing an alkali aqueous solution such as TMAH (tetramethylammonium hydroxide) (hardened) In the case of a film), since the black dye is chemically bonded to a film composed of an alkali-soluble resin, the dye can be removed (peeled) in the entire matrix. On the other hand, black dyes do not have polymerizable groups, that is, when the black dyes are not chemically bonded to the matrix, the dyes are usually insoluble in an aqueous alkali solution, so they are attached to the solid imaging element as residues alone, and are difficult to remove. That is, the reworkability is poor.

In addition, it was also confirmed that when the black dye has an acrylfluorene group or a methacrylfluorene group as a polymerizable group, the pattern forming property of the coating film formed from the composition of the present invention is further improved (hereinafter, also referred to as "resolution" ).

It is preferable that the black dye is a dye multimer. The black dye is a dye multimer, which further improves heat resistance. Among them, it is preferable that the black dye is a dye multimer having a polymerizable group.

Hereinafter, the components contained in the composition and the components that can be contained will be described.

<Inorganic Pigment> The composition of the present invention contains an inorganic pigment. The inorganic pigment is not particularly limited, and a known inorganic pigment can be used. Examples of the inorganic pigment include carbon black, silicon dioxide, zinc white, lead white, zinc barium white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead red, and iron oxide red. , Chrome yellow, zinc yellow (1 zinc yellow, 2 zinc yellow), ultramarine blue, Prussian blue (ferrous potassium ferrocyanide), zircon gray, ochre yellow, chrome titanium yellow, chrome green, peacock, Victoria Green , Iron blue (unrelated to Prussian blue), vanadium zirconium blue, chrome tin red, manganese red and orange red. In addition, black inorganic pigments are preferable. As inorganic pigments, carbon black, titanium black, and metallic pigments are preferable from the viewpoint that a composition capable of forming a hardened film having a high optical concentration can be obtained even if the content is small. . Examples of the metal pigment include one or two or more selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Metal oxides, metal nitrides and metal oxynitrides. The inorganic pigment is selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, chromium oxide, chromium nitride, chromium oxynitride, iron oxide, iron oxynitride, and silver. At least one of the group consisting of metal pigments, metal pigments containing tin, and metal pigments containing silver and tin is preferred. Among them, the inorganic pigment is more preferably at least one selected from pigments containing nitrides or oxynitrides described later. The inorganic pigment may be used alone or in combination of two or more.

In the composition of the present invention, the content of the inorganic pigment is preferably 30 to 70% by mass based on the total solid content of the composition. When the content of the inorganic pigment is 30% by mass or more relative to the solid content, the light-shielding performance of the obtained light-shielding film is further improved, and the heat resistance is also improved. On the other hand, when the content of the inorganic pigment is 70% by mass or less based on the solid content, the reworkability and the pattern formability are further improved. The content of the inorganic pigment is more preferably 35 to 70% by mass, and more preferably 40 to 70% by mass relative to the total solid content of the composition.

The inorganic pigment is preferably in a range of 10 to 80 nm, and more preferably in a range of 10 to 50 nm. The average primary particle diameter can be measured by, for example, the following method.

The average primary particle diameter of the inorganic pigment can be measured using a transmission electron microscope (TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used. Use a transmission electron microscope to measure the maximum length of the obtained particle image (Dmax: maximum length at 2 points on the outline of the particle image) and maximum vertical length (DV-max: 2 parallel to the maximum length) When a straight line clamps the image, the shortest length between the two straight lines is vertically connected), and the multiplied average value (Dmax × DV-max) ^{1/2 is taken} as the particle size. The particle diameter of 100 particles was measured by this method, and the arithmetic average value was taken as the average particle diameter and the average primary particle diameter of the pigment.

(Pigment containing nitride or oxynitride) As described above, the inorganic pigment is preferably a pigment containing nitride or oxynitride. Examples of the pigment containing nitride or oxynitride include pigments such as titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, iron oxynitride, and tungsten oxynitride. Among these, it is preferable to have an absorber in a region of a wavelength of 400 to 1200 nm. The absorption wavelength and optical density of the inorganic pigment and the black dye described later can be measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation.) And the like. From the viewpoint of achieving a high optical concentration in a small amount, for example, titanium nitride, titanium oxynitride, niobium nitride, or vanadium nitride is preferable, and titanium nitride or titanium oxynitride is more preferable. The titanium nitride or titanium oxynitride is not particularly limited, and titanium nitride described in International Publication No. 2008/123097, International Publication No. 2010/147098, and Japanese Patent No. 5577659 can be used. In addition, the content of nitrides or oxynitrides in pigments containing nitrides or oxynitrides (for example, when the pigment contains titanium nitride, the content of titanium nitride) is 10 to 100% by mass relative to the total mass of the pigment. 20 to 100% by mass is more preferred.

・ Titanium black Hereinafter, titanium black particles which are titanium oxynitride pigments will be described. In order to improve dispersibility, suppress cohesion, and the like, the surface of the titanium black particles can be modified as necessary. Titanium black can be plated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconia. Furthermore, the surface treatment of titanium black can also be performed with a hydrophobic substance as shown in Japanese Patent Application Laid-Open No. 2007-302836. Titanium black is typically titanium black particles, and the primary particle size and average primary particle size of each particle are preferably smaller. Specifically, the average primary particle diameter is preferably in a range of 10 nm to 80 nm. The average primary particle diameter can be measured, for example, by the method described above.

The specific surface area of titanium black is not particularly limited. In order to make the hydrophobic property of the titanium black surface treated with a hydrophobic agent to have a predetermined performance, the value measured by the BET (Brunauer, Emmett, Teller) method is 5 m ² / g or more and 150m ² / g or less is preferred, 20m ² / g or more and 120m ² / g or less is more preferred. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade names: manufactured by Mitsubishi Materials Corporation) and Tilack D (trade names: Ako Kasei Co., Ltd.) and so on.

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms. In this form, titanium black is contained as a dispersion in the composition, and the content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is preferably 0.05 or more in mass conversion, and 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is further more preferable. However, the above-mentioned to-be-dispersed body includes both a state in which titanium black is a primary particle and a state in which an aggregate (a secondary particle) is in a state. In order to change the Si / Ti of the dispersion (for example, 0.05 or more), the following means can be adopted. First, a dispersion is obtained by dispersing titanium oxide and silicon dioxide particles with a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C), thereby obtaining titanium black particles as a main component. It contains a dispersion of Si and Ti. The reduction treatment is performed in an atmosphere of a reducing gas such as ammonia. Examples of the titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo Kaisha, Ltd.). Titanium oxide is not limited to this, but a primary particle diameter of 5 nm to 70 nm is preferred, and a diameter of 7 nm to 50 nm is more preferred. As the crystal system, as long as it is rutile or anatase, it can be more than It is best to use, or some mixed crystals. Examples of commercially available products of silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade names: manufactured by Evonik Japan Co., Ltd.) and the like. A dispersant can also be used in the dispersion of titanium oxide and silicon dioxide particles. Examples of the dispersant include those described in the column of dispersant described later. The above dispersion can be performed in a solvent. Examples of the solvent include water or an organic solvent. Examples include those described in the column of organic solvents described later. The titanium black whose Si / Ti is adjusted to, for example, 0.05 or more can be produced, for example, by the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045.

By adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to an appropriate range (e.g., 0.05 or more), light shielding is formed using a composition containing the dispersion In the case of a film, residues derived from the composition outside the region where the light-shielding film is formed are reduced. The residue is a component containing components derived from a composition such as titanium black particles and a resin component. Although the reason for the reduction of the residue is not clear, it is inferred as follows: as described above, the dispersion has a tendency to become smaller in particle size (for example, the particle diameter is 30 nm or less), and the component of the dispersion containing Si atoms increases, As a result, the adhesion between the entire film and the substrate is reduced, which helps to improve the development and removal properties of the unhardened composition (especially, titanium black) when the light-shielding film is formed. In addition, titanium black has excellent light shielding properties over light in a wide range of wavelengths from ultraviolet light to infrared light. Therefore, the above-mentioned dispersion containing titanium black and Si atoms is used (Si / Ti is calculated by mass conversion, and the above is 0.05) Preferably, the light-shielding film formed to exhibit excellent light-shielding properties. The content ratio (Si / Ti) of the Si atom and the Ti atom in the dispersion can be, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of Japanese Patent Application Laid-Open No. 2013-249417. Perform the measurement. In addition, when the dispersion contained in the light-shielding film obtained by curing the composition is judged whether the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is 0.05 or more, Japanese Patent Application Laid-Open No. 2013 is used. The method (2) described in paragraph 0035 of JP-249417.

Among the dispersions containing titanium black and Si atoms, titanium black can be used. In this case, it is preferable that the dispersion containing titanium black accounts for 50% by mass or more of all the dispersions. In addition, in this dispersion, titanium black and other colorants (organic pigments, dyes, and the like) may be used as necessary in order to adjust the light-shielding properties and the like, as long as the effects of the present invention are not impaired. Hereinafter, materials used when introducing Si atoms into the dispersion will be described. When introducing Si atoms into the dispersion, a Si-containing substance such as silicon dioxide may be used. Examples of usable silicon dioxide include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These can be appropriately selected and used. In addition, if the particle diameter of the silicon dioxide particles is smaller than the film thickness when the light-shielding film is formed, the light-shielding property is more excellent. Therefore, it is preferable to use particulate silicon dioxide as the silicon dioxide particles. In addition, examples of the particulate silica include silicon dioxide described in paragraph 0039 of Japanese Patent Application Laid-Open No. 2013-249417, and the contents are incorporated herein.

・ Titanium nitride-containing particles As the pigment containing nitrides or oxynitrides, for example, titanium nitride-containing particles can also be used. In the production of titanium nitride-containing particles, a gas-phase reaction method is generally used, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these manufacturing methods, the thermal plasma method is preferred from the viewpoints of the less mixing of impurities, the easy-to-match particle size, and the higher productivity. Examples of the method for generating thermal plasma include direct current arc discharge, multi-phase arc discharge, high-frequency (RF) plasma, and hybrid plasma. The high-frequency plasma that contains less impurities from the electrode is more suitable. good. As a specific manufacturing method of titanium nitride-containing particles based on the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the device as a carrier gas, and titanium is cooled by a cooling process. Method for nitriding powder to synthesize titanium nitride-containing particles and the like. The thermal plasma method is not limited to the above. In addition, by using a thermal plasma method to obtain titanium nitride-containing particles, it is easy to adjust the diffraction angle 2θ (the details will be described later) originating from the peak of the (200) plane when CuKα rays are used as the X-ray source. It is more than 42.8 ° and less than 43.5 °.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 50 to 85% by mass, more preferably 55 to 85% by mass, and 55 to 80% by mass relative to the total mass of the titanium nitride-containing particles. Further preferred. The content of Ti atoms in titanium nitride-containing particles can be analyzed by ICP (High Frequency Inductively Coupled Plasma) emission spectrometry. The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 15 to 50% by mass, more preferably 15 to 45% by mass, and 20 to 40% by mass relative to the total mass of the titanium nitride-containing particles. Further preferred. The nitrogen atom content can be analyzed by an inert gas fusion thermal conductivity method.

When CuKα ray is used as the X-ray source to measure the X-ray diffraction spectrum, the diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles is more than 42.8 ° and less than 43.5 °. The OD value of a light-shielding film obtained by using a composition containing titanium nitride-containing particles having such characteristics becomes an appropriate value, and the pattern forming property (resolution) is more excellent.

As described above, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.8 ° and less than 43.5 °, more preferably 42.85-43.3 °, and even more preferably 42.9-43.2 °. Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and are usually noticeable when oxygen is mixed during the synthesis and the particle size is small. However, some particles contain oxygen atoms due to the oxidation of the particle surface, etc. Happening. Among them, it is preferable to obtain a higher OD value (optical concentration) when the amount of oxygen contained in the titanium nitride-containing particles is small. It is preferable that the titanium nitride-containing particles do not contain TiO ₂ as a subcomponent. When titanium nitride-containing particles contain titanium oxide TiO ₂ as a sub-component, the peak derived from anatase TiO ₂ (101) as the strongest peak appears at around 2θ = 25.3 ° and originates from rutile TiO ₂ ( 110) The peak appears around 2θ = 27.4 °. However, since TiO ₂ is white, it is a factor that reduces the light-shielding property of the black matrix. Therefore, it is preferable to reduce it to such an extent that it cannot be observed as a peak.

The crystallite size of the titanium nitride-containing particles can be determined from the half-value amplitude of the X-ray diffraction peaks, and calculated using the Scherrer formula.

The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm.

Titanium nitride-containing particles capable of specific surface area determined by BET method, 40 ~ 60m ² / g is preferred, 40 ~ 58m ² / g is more preferably, 42 ~ 55m ² / g is further preferred. When the specific surface area of the titanium nitride-containing particles is set to 40 to 60 m ² / g, the OD (optical density) value of the obtained light-shielding film becomes an appropriate range, and the pattern formability (resolution) is more excellent.

The average primary particle diameter of the titanium nitride-containing particles is preferably 10 to 30 nm, and more preferably 10 to 25 nm. By setting the average primary particle diameter of the titanium nitride-containing particles to 10 to 30 nm, the OD (optical density) value of the obtained light-shielding film becomes an appropriate range, and the pattern formability (resolution) is more excellent. The average primary particle diameter can be measured, for example, by the method described above.

(Other pigments) The composition of the present invention may contain, as the inorganic pigment, an inorganic pigment other than those listed above. Examples of other pigments include tungsten compounds and metal borides. Tungsten compounds and metal borides have a characteristic of high absorption of infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light shielding properties (shielding properties) against infrared rays). In addition, the tungsten compound and the metal boride have lower absorption with respect to visible light than the light-shielding property with respect to infrared rays. In addition, tungsten compounds and metal borides also have a smaller absorption of light in the visible region than those used in the exposure of high-pressure mercury lamps, KrF, and ArF used for image formation.

Examples of the tungsten compound include a tungsten oxide-based compound, a tungsten boride-based compound, and a tungsten sulfide-based compound. The tungsten oxide-based compound represented by the following general formula (compositional formula) (I) is preferred. M _x W _y O _z (I) M represents metal, W represents tungsten, and O represents oxygen. 0.001≤x / y≤1.1 2.2≤z / y≤3.0

Examples of the metal of M include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, and Cd. Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os and Bi, etc., among which alkali metals are preferred. The metal of M may be one type, or two or more types.

M is preferably an alkali metal, Rb or Cs is more preferred, and Cs is further preferred.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in a tungsten compound can be reliably avoided. When z / y is 2.2 or more, the chemical stability of the material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide-based compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ or Ba _0.33 WO ₃ and the like, and Cs _0.33 WO ₃ or Rb _0.33 WO. ₃ is more preferable, and Cs _0.33 WO ₃ is more preferable.

The tungsten compound is preferably fine particles. The average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. For reasons such as ease of handling at the time of production, the average particle diameter of the tungsten fine particles is usually 1 nm or more.

In addition, two or more tungsten compounds can be used.

The tungsten compound can be obtained as a commercial product. When the tungsten compound is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent) No. 4096205). The tungsten oxide-based compound can also be obtained as a dispersion of tungsten particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Examples of the metal boride include lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), Titanium boride (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), One or more of molybdenum boride (MoB ₂ , Mo ₂ B ₅ , MoB) and tungsten boride (W ₂ B ₅ ), etc., and lanthanum boride (LaB ₆ ) is preferred.

It is preferable that the metal boride is a fine particle. The average primary particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. The average particle diameter of the metal boride fine particles is generally 1 nm or more for reasons such as ease of handling during production.

In addition, two or more kinds of metal borides can be used.

The metal boride can be obtained as a commercial product, for example, it can also be obtained as a dispersion of metal boride fine particles such as KHF-07AH manufactured by Sumitomo Metal Mining Co., Ltd.

The inorganic pigment may be an extender pigment. Examples of such constitution pigments include barium sulfate, barium carbonate, calcium carbonate, silicon dioxide, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. When an extender pigment is used as the inorganic pigment, an extender pigment and a coloring pigment (for example, a black inorganic pigment) are preferably used. These extender pigments can be used individually or in mixture of 2 or more types. The usage-amount of an extender pigment is 0-100 mass parts normally with respect to 100 mass parts of colorants, 5-50 mass parts is preferable, 10-40 mass parts is more preferable. Depending on the circumstances, the surface of the colorant and extender pigment can be modified by a polymer and used.

<Black dye> The composition of the present invention contains a black dye. As the black dye, it is preferable that it has absorption over the entire wavelength range of visible light (380 nm to 780 nm). As a black dye, for example, except C. I. In addition to direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, and 171, well-known black dyes can also be mentioned. Examples of the black dye include xanthene-based dyes, azo-based dyes, and aniline-based dyes. The black dye has an optical concentration of preferably 2 or more, and more preferably 4 or more in the entire wavelength range of 400 to 500 nm.

The black dye preferably has a polymerizable group. Since the black dye has a polymerizable group, heat resistance and reworkability can be improved. The polymerizable group is a functional group capable of forming a chemical bond by energy, and examples thereof include a radical polymerizable group and a cation polymerizable group. Among them, a radical polymerizable group is preferred from the viewpoint of more excellent reactivity. As the radical polymerizable group, for example, in addition to an acryl group, a methacryl group, an acrylate group (acryl group), a methacrylate group (methacryl group), and an itaconic acid group In addition to unsaturated carboxylic acid ester groups such as crotonate group, isocrotonate group, and maleate group, styryl group, vinyl group, acrylamino group, and methacrylamino group, etc. may be mentioned. Among them, from the viewpoint of further improving the resolution of the coating film, a methacryl group or an acryl group is more preferable. The black dye may contain two or more polymerizable groups. The number of polymerizable groups contained in the black dye is not particularly limited, and it may be one or two or more.

The black dye may be either a dye monomer or a dye multimer, and a dye multimer is preferred from the viewpoint of further improving heat resistance. Among them, a dye polymer having a structural unit represented by the following general formula (1) is preferable, and a dye polymer having a polymerizable group and a structural unit represented by the following general formula (1) is more preferable.

[Chemical Formula 1]

[In the general formula (1), R ^A to R ^C each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, L represents a single bond or a divalent linking group, and Dye represents removal of any one hydrogen from a black dye Atomic dye residues. A

R ^A to R ^C each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Among them, a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. L represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, -S-, -NR ^1- , -CO-, vinylidene, ethynyl, and alkylene (which may be cyclic, branched, Any one of linear), arylidene, heteroarylidene, or a divalent group formed by combining them. Examples of R ¹ include a hydrogen atom, an alkyl group (a linear or branched alkyl group having 1 to 10 carbon atoms is preferred), and a halogen atom (F atom, Cl atom, Br atom, and I atom are more preferable). Good), aryl (preferably aryl having 6 to 20 carbon atoms). Among these, a hydrogen atom or an alkyl group is preferred.

Dye means a dye residue that removes any one hydrogen atom from a black dye. The black dye is not particularly limited, and examples thereof include the above-mentioned black dye. Among them, a xanthene-based dye or an azo-based dye is preferred from the viewpoint of being capable of forming a light-shielding film having more excellent light-shielding performance. When the dye multimer having a structural unit represented by the general formula (1) has a polymerizable group, the position of the polymerizable group in the dye multimer is not particularly limited. As the position of the polymerizable group in the dye multimer, for example, Dye may have a polymerizable group or may have a structural unit containing a polymerizable group. In addition, Dye has a polymerizable group means that a dye residue represented by Dye which removes any one hydrogen atom from a black dye has a polymerizable group.

When the black dye is a dye multimer, the content of the structural unit represented by the general formula (1) in the dye multimer is preferably 80% by mass or more, and more preferably 85% by mass or more. 90% by mass or more is more preferable, and 95% by mass or more is particularly preferable. A dye multimer having a structural unit represented by the general formula (1) can be produced by a known method.

When the black dye is a dye multimer, its molecular weight is not particularly specified. As a polystyrene conversion value based on the GPC (gel permeation chromatography) method, a weight average molecular weight (Mw) of 1,000 or more and 20,000 or less is preferable. More than 2,000 and less than 15,000 are more preferable, and more than 2,000 and less than 10,000 are more preferable. The GPC method is based on a method that uses HLC-8020GPC (manufactured by TOSOH CORPORATION.), And uses TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID × 15cm) as the column, and uses it as an eluent THF (tetrahydrofuran).

Examples of commercially available black dyes having a polymerizable group include RDW series manufactured by Wako Pure Chemical Industries, Ltd., and specific examples include RDW-K01 and the like.

Regarding the content of the black dye, from the viewpoint of further improving the reworkability, relative to the content of the inorganic pigment, the mass ratio (black dye / inorganic pigment) is preferably 0.3 or less, more preferably 0.25 or less, and 0.2 or less Further preferred. The lower limit of the content of the black dye is not particularly limited, and it is preferably 0.01 or more in terms of mass ratio to the inorganic pigment.

In the composition of the present invention, the content of the black dye relative to the total solid content of the composition is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, and even more preferably 1 to 8% by mass. In the composition of the present invention, the black dye may be used singly or in combination of two or more kinds.

<Dispersant> The composition of the present invention preferably contains a dispersant. The dispersant helps to improve dispersibility of pigment components such as the inorganic pigments. In this invention, a dispersing agent is a component different from the binder resin mentioned later. As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Among them, a polymer compound is preferred. Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated esters, modified polyurethanes, modified polyesters, modified poly (methyl Group) acrylic acid esters, (meth) acrylic acid copolymers and formalin naphthalenesulfonic acid condensates, etc.], polyoxyethylene alkyl phosphates, polyoxyethylene alkylamines, and pigment derivatives. Polymer compounds can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers according to their structure.

The polymer compound is adsorbed on the surface of the dispersion such as an inorganic pigment and a pigment to be used as required, and plays a role of preventing re-aggregation of the dispersion. Therefore, it is preferable to have a terminal modified polymer, a graft polymer, and a block polymer that are fixed to the pigment surface. On the other hand, by modifying the surface of the inorganic pigment, it is also possible to promote the adsorption of polymer compounds on this.

The polymer compound preferably has a structural unit having a graft chain. In addition, in this specification, a "structural unit" has the same meaning as a "repeating unit." A polymer compound having a structural unit having such a graft chain has an affinity with a solvent due to the graft chain, and is therefore excellent in dispersibility of the above-mentioned inorganic pigments such as the inorganic pigment and dispersion stability over time. In addition, with the presence of the graft chain, the polymer compound having a structural unit having the graft chain has affinity with a polymerizable compound or another resin that can be used. As a result, residues are less likely to be generated during alkali development. When the graft chain becomes longer, the steric repulsion effect increases and the dispersibility of pigments and the like improves. On the other hand, when the graft chain is too long, the adsorption force to the above-mentioned inorganic pigment such as an inorganic pigment decreases, and the dispersibility of the pigment or the like tends to decrease. Therefore, the number of atoms other than hydrogen atoms in the graft chain is preferably 40 to 10,000, the number of atoms other than hydrogen atoms is more preferably 50 to 2,000, and the number of atoms other than hydrogen atoms is more preferably 60 to 500. good. Herein, the graft chain represents the root of the main chain of the copolymer (the atom bonded to the main chain from the main chain branched group) to the end of the main chain branched group.

The graft chain preferably has a polymer structure. Examples of the polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, and a poly (meth) acrylate structure. Urea structure, polyamine structure and polyether structure. In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility, the graft chain has at least one selected from the group consisting of a polyester structure, a polyether structure, and a poly (meth) acrylate structure. The graft chain of the seed is more preferable, and the graft chain having at least one of a polyester structure and a polyether structure is more preferable.

The macromonomer having such a graft chain is not particularly limited, and a macromonomer having a reactive double bond group can be appropriately used.

Corresponding to the structural unit with a graft chain possessed by a polymer compound, AA-6 (trade name, TOAGOSEI CO., LTD ..), a commercially available macromonomer suitable for the synthesis of polymer compounds, AA-10 (trade name, manufactured by TOAGOSEI CO., LTD ..), AB-6 (trade name, manufactured by TOAGOSEI CO., LTD ..), AS-6 (trade name, 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, manufactured by 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 NOF COR PORATION.), 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.), Blemmer 43PAPE- 600B (trade name, manufactured by NOF CORPORATION.) And the like. Among them, AA-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), And AB-6 (trade name, manufactured by TOAGOSEI CO., LTD ..) are used. ), AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), And Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.) good.

The dispersant preferably has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. Among them, it is preferable to have at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain-shaped polyester, and to have at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, At least one structure in the group consisting of polymethyl acrylate and polymethyl methacrylate is further preferred. The dispersant may be one having the above structure alone in one dispersant, or one having a plurality of such structures in one dispersant. Here, the polycaprolactone structure means a structure having a ring-opening of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure having a ring opening of δ-valerolactone as a repeating unit. Specific examples of the dispersant having a polycaprolactone structure include those in which j and k in the following formula (1) and the following formula (2) are five. In addition, specific examples of the dispersant having a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are four. Specific examples of the dispersant having a polymethyl acrylate structure include those in which X ⁵ in the following formula (4) is a hydrogen atom and R ⁴ is a methyl group. Further, as specific examples of the dispersant having a polymethyl methacrylate structure, those in which X ⁵ is a methyl group and R ⁴ is a methyl group in the following formula (4) can be mentioned.

The polymer compound as a structural unit having a graft chain preferably includes a structural unit represented by any one of the following formulae (1) to (4), and includes the following formulae (1A) and (2A) The structural unit represented by any one of the following formula (3A), (3B), and (4) below is more preferred.

[Chemical Formula 2]

In Formulae (1) to (4), W ¹ , W ² , W ^3, and W ⁴ each independently represent an oxygen atom or NH. It is preferable that W ¹ , W ² , W ³ and W ⁴ are oxygen atoms. In the formulae (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 limitation in synthesis, it is preferable that they are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each is independently hydrogen An atom or a methyl group is more preferable, and a methyl group is more preferable.

In the formulae (1) to (4), Y ¹ , Y ² , Y ^3, and Y ⁴ each independently represent a divalent linking group, and the structure of the linking group is not particularly limited. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following linking groups (Y-1) to (Y-21). In the structure shown below, A and B each represent a bonding site with the left terminal group and the right terminal group in Formulas (1) to (4), respectively. Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of simplicity of synthesis.

[Chemical Formula 3]

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, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group. And amine groups. Among these, as the organic group represented by Z ¹ , Z ² , Z ^3, and Z ⁴ , especially from the viewpoint of improving dispersibility, those having a steric repulsive effect are preferred, and each independently has 5 to 6 carbon atoms. An alkyl group or alkoxy group of 24 is preferable. Among them, each is independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or a cyclic alkyl group having 5 to 24 carbon atoms. Alkoxy is particularly preferred. The alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic groups.

In Formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500. In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. From the viewpoint of the dispersion stability and developability of the composition, j and k in the formulae (1) and (2) are preferably integers of 4 to 6, and 5 is the most preferable.

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

In addition, the polymer compound may have two or more different structural units and a structural unit having a graft chain. That is, the molecules of the polymer compound may include structural units represented by formulas (1) to (4), which are different from each other. In formulas (1) to (4), n, m, p, and When q represents an integer of 2 or more, in the formulae (1) and (2), the side chains may include structures in which j and k are different from each other. In the formulae (3) and (4), there are plural numbers in the molecule Each of R ³ , R ⁴ and X ⁵ may be the same as each other 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 dispersion stability and developability of the composition. 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 dispersion stability and developability of the composition.

[Chemical Formula 4]

In the formula ^{(1A), X 1, X} Y 1, Z 1 and n are as defined in the formula (1) is ^1, Y ^1, Z ¹ and n, respectively, preferred ranges are also the same. In formula ^{(2A), X 2, Y} 2, Z 2 and m are as defined for the formula X (2) is ^2, Y ^2, Z ² and the same as m, the preferred range is 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 dispersion stability and developability of the composition.

[Chemical Formula 5]

Formula (3A) or (3B) in, ^3, Y ^3, Z ³ and same ^{p X 3, Y 3, Z} 3 and p are defined for the formula X (3) is, preferred ranges are also the same.

As a structural unit having a graft chain, the polymer compound preferably has a structural unit represented by formula (1A).

In the polymer compound, the structural unit having a graft chain (for example, the structural unit represented by the above formula (1) to formula (4)) is 2 to 90% by mass conversion with respect to the total mass of the polymer compound. The range is preferable, and the range of 5 to 30% is more preferable. When the structural unit having a graft chain is included in this range, the dispersibility of the inorganic pigment is high, and the developability when forming a light-shielding film is good.

In addition, it is preferable that the polymer compound has a hydrophobic structural unit different from the structural unit having a graft chain (that is, does not correspond to the structural unit having a graft chain). In the present invention, the hydrophobic structural unit is a structural unit that does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphate group, a phenolic hydroxyl group, and the like).

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

The ClogP value is a value calculated by a program "CLOGP" which can be obtained from Daylight Chemical Information System, Inc .. This program provides the value of "calculated logP" calculated by the fragmentapproach (see below) of Hansch, Leo. Fragmentapproach divides the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and totals the logP contribution amount allocated to the fragment to estimate the logP value of the compound. The details are described in the following documents. In the present invention, 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). It is a quantitative value that expresses how the physical properties of an organic compound are distributed in the two-phase equilibrium between oil (usually 1-octanol) and water. Expression. logP = log (Coil / Cwater) In the formula, Coil represents the Mohr concentration of the compound in the oil phase, and Cwater represents the Mohr concentration of the compound in the water phase. If the value of logP increases with a positive (plus) value between 0, it means that the oil solubility increases, and if the absolute value increases with minus (minus), it means an increase in water solubility, which has a negative correlation with the water solubility of organic compounds. Parameters for estimating the hydrophobicity of organic compounds are widely used.

The polymer compound, as the hydrophobic structural unit, preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulae (i) to (iii).

[Chemical Formula 6]

In the formulae (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 atom having 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 a hydrogen atom. X represents an oxygen atom (-O-) or an imine group (-NH-), and an oxygen atom is preferred.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group), a divalent Aromatic group (eg, arylene, substituted arylene), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted An amine group (-NR ^31- , wherein R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but a saturated aliphatic group is preferred. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15 and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has 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. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ³²⁾ . ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group or a heterocyclic group.

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

Examples of Z include an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, and a substituted arylene group). Aryl), heterocyclyl, or a combination of these. These groups may include an oxygen atom (-O-), a sulfur atom (-S-), an imine group (-NH-), a substituted imine group (-NR ^31- , wherein R ³¹ is an aliphatic group , Aromatic or heterocyclic) or carbonyl (-CO-).

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 10. The aliphatic group also includes a ring group hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the ring group hydrocarbon group include dicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the crosslinked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, and bicyclic octane ring (bicyclic [2.2.2 ] Octane ring, bicyclic [3.2.1] octane ring, etc.) and other bicyclic hydrocarbon rings; homoblane (homobledane), adamantane, tricyclic [5.2.1.0 ^2,6 ] decane, tricyclic [4.3 .1.1 ^2,5 ] tricyclic hydrocarbon rings such as undecane ring, and tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, and perhydro-1,4-methylene-5 , 8-methylene naphthalene ring and other 4-ring hydrocarbon rings. In addition, the cross-linked cyclic hydrocarbon ring also includes a fused ring hydrocarbon ring, such as perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroperylene, perhydroperylene, perhydroindene, and perhydro Condensed rings such as fluorene rings are condensed with a plurality of 5 to 8-membered cycloalkane rings. It is more preferable that the aliphatic group is a saturated aliphatic group than the unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

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

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

In the formula (iii), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), and an alkyl group having 1 to 6 carbon atoms (for example, , Methyl, ethyl, propyl, etc.), Z or LZ. Here, the meanings of L and Z are the same as those of L and Z described above. 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.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ^2, and R ³ are a hydrogen atom or a methyl group, L is a single bond or an alkylene group, or a divalent link including an alkylene oxide structure Compounds in which X is an oxygen atom or an imine group, and Z is an aliphatic group, a heterocyclic group or an aromatic group are preferred. In addition, as the monomer represented by the general 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. Further, as the monomer represented by the general formula (iii), a compound in which R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferred.

Examples of the representative compounds represented by the formulae (i) to (iii) include radical polymerizable compounds selected from the group consisting of acrylates, methacrylates, and styrenes. In addition, as examples of the representative compounds represented by the formulae (i) to (iii), the compounds described in paragraphs 0089 to 0093 of Japanese Patent Application Laid-Open No. 2013-249417 can be referred to, and these contents are incorporated herein.

In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90% with respect to the total mass of the polymer compound in terms of mass, and more preferably contained in a range of 20 to 80%. When the content is in the above range, sufficient pattern formation can be achieved.

The polymer compound can introduce a functional group that can interact with a colored pigment such as the inorganic pigment. Among them, it is preferable that the polymer compound further includes a structural unit having a functional group capable of interacting with the above-mentioned inorganic pigment such as a pigment. Examples of the functional group capable of forming an interaction with a colored pigment such as the above-mentioned inorganic pigment include an acid group, a basic group, a coordinating group, and a reactive functional group. When a polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, it contains a structural unit having an acid group, a structural unit having a basic group, and a structural unit having a coordinating group. Or it is preferable to include a structural unit having reactivity. In particular, the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, whereby the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into a polymer compound, in the composition of the present invention, the polymer compound that is a dispersant that facilitates the dispersion of the color pigment such as the inorganic pigment described above has alkali-solubility. A composition containing such a polymer compound becomes an excellent light-shielding property of the exposed portion, and the alkali developability of the unexposed portion is improved. In addition, since the polymer compound has a structural unit containing an acid group, the polymer compound tends to be easily fused with a solvent and the coating property is also improved. It is presumed that this is because the acid group in the structural unit having an acid group easily interacts with the above-mentioned inorganic pigment and the like, the polymer compound stably disperses the above-mentioned inorganic pigment and the like, and disperses the above-mentioned inorganic pigment and the like. The viscosity of the polymer compound becomes low, and the polymer compound itself is easily and stably dispersed.

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

As the functional group that can interact with the color pigments such as the inorganic pigment, that is, an acid group, for example, there are a carboxylic acid group, a sulfonic acid group, a phosphate group, or a phenolic hydroxyl group. At least one type is preferred, and from the viewpoints of good adsorption of the pigments such as the inorganic pigments described above and high dispersibility of the pigments, carboxylic acid groups are more preferred.

When the polymer compound has an acid group, it is preferable to further include a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. The polymer compound may have one or two or more kinds of structural units having an acid group. The polymer compound may or may not contain a structural unit having an acid group, but when contained, the content of the structural unit having an acid group is calculated in terms of mass, and it is preferably 5 to 80% relative to the total mass of the polymer compound. From the viewpoint of suppressing damage to the image intensity due to alkali development, 10 to 60% is more preferable.

Basic groups that are functional groups that can interact with color pigments such as the above-mentioned inorganic pigments, that is, basic groups, include, for example, a first-order amino group, a second-order amino group, a third-order amino group, a heterocyclic ring containing N atom, and fluorene Amine groups and the like are preferred from the viewpoints of good adsorption of the color pigments such as the inorganic pigments and high dispersibility of the color pigments. The polymer compound may have one or more of these basic groups. The polymer compound may or may not contain a structural unit having a basic group. When contained, the content of the structural unit having a basic group is calculated in terms of mass, and is 0.01% or more and 50% or less with respect to the total mass of the polymer compound. Preferably, from the viewpoint of suppressing the development resistance, 0.01% or more and 30% or less are more preferable.

Examples of the functional group that can interact with the colored pigments such as the above-mentioned inorganic pigment, that is, a coordinating group and a reactive functional group include, for example, acetamidine, trialkoxysilyl, Isocyanate groups, acid anhydrides, fluorenyl chloride, etc. From the viewpoints of good adsorption of the color pigments such as the above-mentioned inorganic pigments and high dispersibility of the color pigments, acetamidine is preferred. The polymer compound may have one or two or more of these groups. The polymer compound may contain a structural unit having a coordinating group or a functional group having a reactivity, or it may not be contained, but when it is contained, the content of these structural units is expressed in terms of mass relative to the total mass of the polymer compound, 10 % Or more and 80% or less is more preferable, and from the viewpoint of suppressing the obstructive development property, 20% or more and 60% or less is more preferable.

When the polymer compound in the present invention has a functional group capable of interacting with a coloring pigment such as the above-mentioned inorganic pigment in addition to the graft chain, it contains various functional groups that can interact with the coloring pigment such as the above-mentioned inorganic pigment. The polymer compound may be a group, and it is not particularly limited how these functional groups are introduced, but the polymer compound has a structure selected from one or more types of structural units derived from a monomer represented by the following general formulae (iv) to (vi). The unit is preferred.

[Chemical Formula 7]

In the general formulae (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, or the like) or a carbon number of 1 to 6 alkyl (eg, methyl, ethyl, propyl, etc.). In the general formulae (iv) to (vi), it is preferable that R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each is independently a hydrogen atom or a methyl group. The base is better. In the general formula (iv), R ¹² and R ¹³ are each preferably a hydrogen atom.

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

In addition, L ₁ in the general formulae (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, an alkylene group, and a substituted alkylene group), 2 Valence aromatic group (for example, arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), Substituted imine bond (-NR ³¹ '-, wherein R ³¹ ' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 10. It is preferable that the aliphatic group is a saturated aliphatic group compared with an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. In the heterocyclic ring, one or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ³²⁾ . ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

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

In the general formulae (iv) to (vi), Z ₁ represents a functional group other than the graft chain that can interact with the above-mentioned inorganic pigments and other colored pigments. A carboxylic acid group and a tertiary amine group are preferred. Acid groups are more preferred.

In the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), and 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 meaning the same as the above L ₁ and Z _1, preferred embodiments are also the same. R ¹⁴ , R ^15, and R ¹⁶ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as the monomer represented by the general 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 link including an alkylene oxide structure. A compound in which X ₁ is an oxygen atom or an imine group, and Z ₁ is a carboxylic acid group is preferred. Further, as the monomer represented by the general formula (v), a compound in which R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine group is preferable. Further, as the monomer represented by the general formula (vi), compounds in which 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 compound Is better.

Representative examples of the monomer (compound) represented by the general formulae (iv) to (vi) are shown below. Examples of the monomer include a reaction of methacrylic acid, crotonic acid, isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. Reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and phthalic anhydride, reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and tetrahydroxyphthalic anhydride, Reactant of compound having addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, reactant of compound having addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid Oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol, 4-hydroxybenzylpropene, and the like.

The content of the structural unit having a functional group that can interact with the color pigments such as the above-mentioned inorganic pigments is relatively high from the viewpoint of interaction with the color pigments such as the above-mentioned inorganic pigments, dispersion stability, and permeability to the developer. The total mass of the molecular compound is preferably from 0.05 to 90% by mass, more preferably from 1.0 to 80% by mass, and even more preferably from 10 to 70% by mass.

In addition, in order to improve various properties such as image strength, the polymer compound may further include a structural unit having a graft chain, a hydrophobic structural unit, and a coloring agent capable of being colored with the above-mentioned inorganic pigments, as long as the effects of the present invention are not impaired. The structural unit of the functional group that the pigment forms interacts with is different from other structural units having various functions (for example, a structural unit having a functional group having an affinity with the dispersion medium used for the dispersion, etc.). Examples of such other structural units include structural units derived from a radical polymerizable compound selected from acrylonitrile and methacrylonitrile. The polymer compound can use one or two or more of these other structural units, and its content is expressed in terms of mass, and relative to the total mass of the polymer compound, 0% to 80% is preferred, and 10% to 60% is preferred. The following are particularly good. When the content is within the above range, sufficient pattern-formability can be maintained.

The acid value of the polymer compound is preferably in a range of 0 mgKOH / g or more and 160 mgKOH / g or less. From the standpoint of making alkali developability better, the lower limit value is more preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. If the polymer compound has an acid value of 50 mgKOH / g or more, it is possible to further suppress the sedimentation of colored pigments such as the inorganic pigments, further reduce the number of coarse particles (in other words, reduce the amount of particles in the liquid), and further increase the composition. Stability over time. In addition, from the viewpoint of more effectively suppressing pattern peeling during development when the light-shielding film is formed, the upper limit value thereof is preferably 140 mgKOH / g or less, and further preferably 120 mgKOH / g or less.

In the present invention, the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. In addition, a resin having a desired acid value can be obtained by changing the content of a structural unit that is a component containing a polymer compound, that is, an acid group.

When the light-shielding film is formed, the weight average molecular weight of the polymer compound in the present invention is a polystyrene conversion value based on the GPC (gel permeation chromatography) method from the viewpoints of suppression of pattern peeling during development and developability, and is 4,000. Above and below 300,000 are preferred, above 5,000 and below 200,000 are more preferred, above 6,000 and below 100,000 are further preferred, and above 10,000 and below 50,000 are particularly preferred. The GPC method is based on a method using HLC-8020GPC (manufactured by TOSOH CORPORATION.), Using TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID × 15cm) as the column, and using THF as the eluent (Tetrahydrofuran).

The polymer compound can be synthesized by a known method. Examples of the solvent used in the synthesis of the polymer compound include dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethyl Methylformamide, N, N-dimethylacetamide, dimethylmethylene, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound that can be used in the present invention include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., and "Disperbyk-101 (polyamidamine phosphate)" and 107 (carboxylate) manufactured by BYK Chemie. Acid ester), 110 (copolymers containing acid groups), 111 (phosphoric acid-based dispersant), 130 (polyamidamine), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymers) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified Polyacrylic acid ester), 5010 (polyamidate), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto "AJISPER PB821, PB822, PB880, PB881" manufactured by Fine-Techno Co., Inc., "Floren TG-710 (amine ester oligomer)" manufactured by KYOEISHA CHEMICAL Co., LTD, "Polyflow No. 50E, No. 300" (Acrylic Copolymer) "," Disparlon KS-86 "manufactured by Kusumoto Chemicals, Ltd. 0, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "," DEMOL RN, N (naphthalenesulfonate) manufactured by Kao Corporation Acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (polymeric polycarboxylic acid) "," EMULGEN 920, 930, 935, 985 ( Polyoxyethylene nonylphenyl ether) "," ACETAMIN 86 (stearylamine acetate) "," SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester manufactured by The Lubrinzol Corporatin) Amine), 3000, 12000, 17000, 20000, 27000 (polymers with functional units at the ends), 24000, 28000, 32000, 38500 (graft copolymers) "," Nikkor T106 manufactured by Nikko Chemicals Co., Ltd. " (Polyoxyethylene sorbitol monooleate), MYS-IEX (polyoxyethylene monostearate) ", Hinoakuto T-8000E manufactured by Kawaken Fine Chemicals Co., Ltd., etc., Shin-Etsu Chemical Co., Ltd .Production of polyorganosiloxane polymer KP341, "W001: cationic surfactant" by Yusho Co Ltd. Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene Non-ionic surfactants such as diol distearate and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA" manufactured by MORISHITA & CO., LTD. -47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", SAN NOPCO LIMITED made" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 ", etc. Polymer dispersant, `` Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 '' manufactured by ADEKA CORPORATION, and Sanyo Chemical Industries, Ltd. manufactures "Ionet (trade name) S-20" and the like. In addition, Acrylicbase FFS-6752, Acrylicbase FFS-187, Akurikuya-RD-F8, and Cyclomer P can also be used. Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, manufactured by BYK Additives & Instruments. DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822, and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. and the like. These polymer compounds may be used alone or in combination of two or more kinds.

In addition, as an example of a specific example of the polymer compound, the polymer compound described in paragraphs 0127 to 0129 of Japanese Patent Application Laid-Open No. 2013-249417 can be referred to, and these contents are incorporated herein.

In addition, as the dispersant, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of Japanese Patent Application Laid-Open No. 2010-106268 (corresponding to columns 0075 to 0133 of US2011 / 0124824) can be used. These contents can be referred to and incorporated into this manual. Furthermore, in addition to the above, paragraphs 0028 to 0084 of Japanese Patent Application Laid-Open No. 2011-153283 (corresponding to columns of paragraphs 0075 to 0133 of US2011 / 0279759) can be used, which include a side chain structure having an acidic group bonded via a linking group The constituent polymer compounds can be referred to and incorporated in this specification.

When the composition contains a dispersant, the content of the dispersant relative to the inorganic pigment is preferably in a range of 0.1 to 1 in terms of mass ratio, and more preferably in a range of 0.1 to 0.4. The content of the dispersant is in the range of 0.1 to 0.4 based on the mass ratio of the inorganic pigment. In addition to reducing the amount of coarse particles in the composition, the light-shielding performance of the obtained light-shielding film is also excellent.

When the composition contains a dispersant, the content of the dispersant relative to the total solid content of the composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass. The dispersant may be used singly or in combination of two or more kinds. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

<Binder resin> The composition of the present invention preferably contains a binder resin. As the binder resin, a linear organic polymer is preferably used. As such a linear organic polymer, a known one can be arbitrarily used. In order to achieve water development or weak alkaline water development, it is preferable to select a linear organic polymer that is soluble or swellable to water or weak alkaline water. Among them, alkali-soluble resins (resins having a group that promotes alkali-solubility) are particularly preferred as the binding resin. As the binder resin, it is possible to have at least one group that promotes alkali solubility from a linear organic polymer and a molecule (preferably a molecule having a (meth) acrylic copolymer or a styrene copolymer as a main chain). The alkali-soluble resin is appropriately selected. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, (meth) acrylic acid / (meth) acrylic resin Amine copolymer resins are preferred, and from the viewpoint of controllability of developability, (meth) acrylic resins, (meth) acrylamide resins, and (meth) acrylic acid / (meth) acrylamide copolymer resins are Better. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphate group, a sulfonic acid group, and a phenolic hydroxyl group. Among them, those which are soluble in an organic solvent and can be developed with a weakly alkaline aqueous solution are preferred, and more preferred are alkali-soluble resins having a structural unit derived from (meth) acrylic acid. These acid groups may be only one kind, or two or more kinds.

Examples of the binder resin include a radical polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Laid-Open No. 54-34327, Japanese Patent Laid-Open No. 58-12577, and Japanese Patent No. As disclosed in Kosho 54-25957, Japanese Unexamined Patent Application No. 54-92723, Japanese Unexamined Patent Application No. 59-53836, and Japanese Unexamined Patent Application No. 59-71048, that is, monomers having a carboxyl group alone or copolymerized therewith Resin, monomer having acid anhydride alone or copolymerized, and resin having acid anhydride unit hydrolyzed or semi-esterified or semi-fluorinated, and epoxy acrylic acid modified by unsaturated monocarboxylic acid and anhydride Esters, etc. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include: Examples include maleic anhydride. Moreover, the acidic cellulose derivative which similarly has a carboxylic acid group in a side chain is mentioned as an example. It is also useful to add a cyclic acid anhydride to a polymer having a hydroxyl group. In addition, European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 have excellent balance between film strength and developability of the acetal-modified polyvinyl alcohol-based adhesive resin having an acid group and the like. Is better. Moreover, as a water-soluble linear organic polymer, polyvinylpyrrolidone, polyethylene oxide, etc. are useful. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon and polyether, which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, are also useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable ethylene monomers as necessary] copolymers) and [allyl (meth) acrylate / (methyl) ) Acrylic acid / other addition polymerizable ethylene monomers as required] Copolymers are excellent in film strength, sensitivity, and developability, and are preferred. Examples of commercially available products include Acrylicbase FF-187, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.), Acrycure-RD-F8 (NIPPON SHOKUBAI CO., LTD.), And DAICEL-ALLNEX LTD. Cyclomer P (ACA) 230AA, etc.

In the production of the binder resin, for example, a method based on a known radical polymerization method can be applied. Those skilled in the art can easily set polymerization conditions such as temperature, pressure, the type and amount of the radical initiator, and the type of the solvent when the alkali-soluble resin is produced by the radical polymerization method.

In addition, as the binder resin, it is also preferable to use a polymer containing a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group). The definition of the structural unit having a graft chain is the same as the structural unit having a graft chain in the dispersant described above, and the preferred range is also the same. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphate group, and a phenolic hydroxyl group. At least one kind of the carboxylic acid group, the sulfonic acid group, and the phosphoric acid group is preferable, and the carboxylic acid group is more preferable.

As the structural unit having an acid group, it is preferable to have one or more structural units selected from structural units derived from a singular body represented by the following general formula (vii) to general formula (ix).

[Chemical Formula 8]

In the general formulae (vii) to (ix), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like) or a carbon number of 1 to 6 alkyl (eg, methyl, ethyl, propyl, etc.). In the general formulae (vii) to (ix), R ²¹ , R ^22, and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each is independently a hydrogen atom or a methyl group. good. In the general formula (vii), it is particularly preferred that R ²¹ and R ²³ are each a hydrogen atom.

X ₂ in the general formula (vii) represents an oxygen atom (-O-) or an imine group (-NH-), and an oxygen atom is preferred. In addition, Y in the general formula (viii) represents a methine group or a nitrogen atom.

In addition, L ₂ in the general formulae (vii) to (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, an alkylene group and a substituted alkylene group); Valence aromatic group (for example, arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), Substituted imine bond (-NR ⁴¹ '-, wherein R ⁴¹ ' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 10. As for the aliphatic group, a saturated aliphatic group is more preferable than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15 and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. One or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed on the heterocyclic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ⁴²⁾ . ⁴² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

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

In the general formulae (vii) to (ix), Z ₂ is an acid group, and a carboxylic acid group is preferred.

In the general formula (ix), R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), and an alkyl group having 1 to 6 carbon atoms (for example, , methyl, ethyl, propyl, etc.), - Z ₂ or L ₂ -Z _2. Wherein, L _2, and the meaning is the same as Z ₂ in the above-described L ₂ and Z _2, preferred examples are also the same. R ²⁴ , R ^25, and R ²⁶ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as a singular body represented by the general formula (vii), R ²¹ , R ^22, and R ²³ are each independently a hydrogen atom or a methyl group, and L ₂ is an alkylene group or a divalent compound containing an alkylene oxide structure. A compound in which the linking group, X ₂ is an oxygen atom or an imine group, and Z ₂ is a carboxylic acid group is preferred. In addition, as a single body represented by the general formula (vii), a compound in which R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is a methine group is preferable. Further, as the singular body represented by the general formula (ix), compounds in which R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom or a methyl group, and Z ₂ is a carboxylic acid group are preferred.

The above-mentioned adhesive resin can be synthesized by the same method as the above-mentioned dispersant containing a structural unit having a graft chain, and its preferred acid value and weight average molecular weight are also the same.

The adhesive resin may have one or more structural units having an acid group. The content of the structural unit having an acid group is, in terms of mass conversion, preferably 5 to 95% relative to the total mass of the above-mentioned adhesive resin. From the viewpoint of suppressing damage to the image strength by alkali development, 10 to 90% is Better.

The content of the binder resin in the composition of the present invention is preferably 0.1 to 30% by mass, and more preferably 0.3 to 25% by mass relative to the total solid content of the composition. The adhesive resin can be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

<Polymerizable Compound> The composition of the present invention preferably contains a polymerizable compound. The polymerizable compound is preferably a compound containing one or more groups having an ethylenically unsaturated bond, more preferably two or more compounds, more preferably three or more, and particularly preferably five or more . The upper limit is, for example, 15 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acrylfluorenyl group.

The polymerizable compound may be, for example, any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture of these, and a polymer of these. A monomer is preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000, and more preferably 250 to 1500. The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and more preferably a 3 to 6-functional (meth) acrylate compound. Examples of the monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amines thereof. And these polymers, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amidines of unsaturated carboxylic acids and aliphatic polyamine compounds, and these polymers are preferred. Further, an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or the above may be appropriately used. Dehydration condensation reactants of unsaturated carboxylic acid esters or amidoamines with monofunctional or polyfunctional carboxylic acids, and the like. In addition, unsaturated carboxylic acid esters having an electrophilic substituent such as isocyanate group and epoxy group, or reactants of amidoamines with monofunctional or polyfunctional alcohols, amines, thiols, halogen groups or toluene Unsaturated carboxylic acid esters such as sulfonyl groups and the like or reactants of amidoamines with monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Further, instead of the unsaturated carboxylic acid, a styrene derivative such as an unsaturated phosphonic acid or styrene, or a compound group substituted with a vinyl ether, an allyl ether, or the like can be used. As these specific compounds, the compounds described in paragraphs [0095] to [0108] of Japanese Patent Application Laid-Open No. 2009-288705 can also be suitably used in the present invention.

In the present invention, as the polymerizable compound, a compound containing one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure is also preferable. As examples thereof, the compounds described in paragraphs 0227 of Japanese Patent Application Laid-Open No. 2013-29760 and paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 can be referred to, and the contents are incorporated into the specification of the present application.

As the polymerizable compound, 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) can also be used. 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) Sale product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these (meth) acrylfluorenyl groups are passed through ethylene glycol residues and propylene glycol residues The basic structure (for example, SR454, SR499 marketed by 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 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used. The following is a description of the state of a preferable polymerizable compound.

The polymerizable compound may have acid groups such as a carboxyl group, a sulfonic acid group, and a phosphate group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a non-aromatic carboxylic anhydride and an unreacted hydroxyl group of the aliphatic polyhydroxy compound are reacted to have an acid group. The polymerizable compound is more preferable. 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 TOAGOSEI CO., LTD.

The preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing and dissolving characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in terms of production or operation. In addition, the photopolymerization performance is good and the curability is excellent.

As for the polymerizable compound, a compound having a caprolactone structure is also preferable. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, and trihydroxymethyl. Polyols such as methylpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerin, and trimethylol melamine are obtained by esterification with (meth) acrylic acid and ε-caprolactone Ε-caprolactone modified polyfunctional (meth) acrylate. Among them, a compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.

[Chemical Formula 9]

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

[Chemical Formula 10]

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

[Chemical Formula 11]

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

The polymerizable compound having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and DPCA-20 (in the above formulae (Z-1) to (Z-3), m = 1. The number of groups represented by formula (Z-2) = 2, compounds in which R ^{1 is} all a hydrogen atom), DPCA-30 (same formula, m = 1, groups represented by formula (Z-2) Number = 3, compound where R ^{1 is} all hydrogen atom), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, compound where all R ¹ is hydrogen atom ), DPCA-120 (in the same formula, m = 2, the number of groups represented by formula (Z-2) = 6, all compounds where R ¹ is a hydrogen atom), etc.

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

[Chemical Formula 12]

In the general formulae (Z-4) and (Z-5), E each independently represents-((CH ₂ ) _y CH ₂ O)-, or-((CH ₂ ) _y CH (CH ₃ ) O)-, y each independently represents an integer of 0 to 10, and X each independently represents a (meth) acrylfluorenyl group, a hydrogen atom, or a carboxyl group. In the general formula (Z-4), the total number of (meth) acrylfluorenyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In the general formula (Z-5), the total number of (meth) acrylfluorenyl groups is five or six, n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In the general formula (Z-4), an integer of 0 to 6 is preferable, and an integer of 0 to 4 is more preferable. In addition, an integer of 2 to 40 in total for each m is preferable, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is even more preferable. In the general formula (Z-5), an integer of 0 to 6 is more preferable, and an integer of 0 to 4 is more preferable. In addition, an integer of 3 to 60 in total for each n is preferable, an integer of 3 to 24 is more preferable, and an integer of 6 to 12 is even more preferable. And-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-in the general formula (Z-4) or (Z-5) is an oxygen atom The form of the side end and the X bond is more preferable.

The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used singly or in combination of two or more kinds. In particular, at least one of the six X's in the general formula (Z-5) is a propylene fluorenyl group, and the six X's in the general formula (Z-5) are all acryl fluorinyl groups. The state of a mixture of compounds which are hydrogen atoms is preferred. With such a structure, developability can be further improved.

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

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be synthesized by a process known as a conventionally known process: through ring-opening addition reaction, ethylene oxide or propylene oxide is mixed with pentaerythritol Or a process of dipentaerythritol bonding; and, for example, a process of introducing a (meth) acrylfluorenyl group by reacting (meth) acrylfluorene chloride with a terminal hydroxyl group of a ring-opening skeleton. Each process is a well-known process, and those skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable. Specific examples include compounds represented by the following formulae (a) to (f) (hereinafter, also referred to as "exemplary compounds (a) to (f)"). Among them, the exemplary compounds (a) and (b) ), (E), (f) are preferred.

[Chemical Formula 13]

[Chemical Formula 14]

Examples of commercially available polymerizable compounds represented by the general formulae (Z-4) and (Z-5) include SR-, which is a four-functional acrylic ester having four ethylene oxide chains manufactured by Sartomer company Inc. 494. DPCA-60, a 6-functional acrylate with 6 pentyleneoxy chains, which is manufactured by Nippon Kayaku Co., Ltd., and TPA-330, a 3-functional acrylate with 3 isobutylene oxide chains, etc. .

Examples of the polymerizable compound include amine ester acrylates described in Japanese Patent Application Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Application No. 2-32293, and Japanese Patent Application No. 2-16765. Or amine esters having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, or Japanese Patent Publication No. 62-39418. Compounds are also preferred. In addition, it is also possible to use an amine structure or a thioether structure in the molecule by using those described in JP-A-63-277653, JP-A-63-260909, and JP-A-105238. The addition of a polymerizable compound results in a composition having a very high speed of light. Examples of commercially available products include amine ester oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd), and DPHA-40H (Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by KYOEISHA CHEMICAL Co., LTD), and the like.

In addition, the SP (solubility parameter) value of the polymerizable compound used in the present invention is preferably 9.50 or more, more preferably 10.40 or more, and even more preferably 10.60 or more. In this specification, the SP value is obtained by the Hoy method unless otherwise specified (HLHoy Journal of Painting, 1970, Vol. 42, 76-118). In addition, the SP value is shown by omitting the unit, but the unit is cal ^1/2 cm ^-3/2 .

Further, from the viewpoint of improving the development residue, it is also preferable that the composition contains a polymerizable compound having a Cardo skeleton. As the polymerizable compound having a Cardo skeleton, a polymerizable compound having a 9,9-diarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

Formula (Q3) [Chemical Formula 15]

In the general formula (Q3), Ar ¹¹ to Ar ¹⁴ each independently represent an aryl group including a benzene ring surrounded by a dotted line. X ¹ to X ⁴ each independently represent a substituent having a polymerizable group, and a carbon atom in the substituent may be substituted with a hetero atom. a and b each independently represent an integer of 1 to 5, and c and d each independently represent an integer of 0 to 4. R ¹ to R ⁴ each independently represent a substituent, e, f, g, and h each independently represent an integer of 0 or more, and the upper limits of e, f, g, and h are respectively from Ar ¹¹ to Ar ¹⁴ The number of substituents minus the value of a, b, c or d. Here, when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, X ¹ to X ⁴ and R ¹ to R ⁴ may be independently substituted with The benzene ring surrounded by a dotted line may be replaced by a ring other than the benzene ring surrounded by a dotted line.

In the general formula (Q3), the aryl group represented by Ar ¹¹ to Ar ¹⁴ containing a benzene ring surrounded by a dotted line is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms ( For example, phenyl, naphthyl) is more preferred, and phenyl (limited to a benzene ring surrounded by a dotted line) is more preferred.

In the general formula (Q3), X ¹ to X ⁴ each independently represent a substituent having a polymerizable group, and a carbon atom in the substituent may be substituted with a hetero atom. The substituent having a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but an aliphatic group having a polymerizable group is preferred. The aliphatic group having a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but an alkylene group having 1 to 12 carbon atoms other than the polymerizable group is preferred, and the number of carbon atoms is 2 An alkylene group of -10 is more preferable, and an alkylene group of 2 to 5 carbons is more preferable. In the aliphatic group having a polymerizable group represented by X ¹ to X ⁴ , when the aliphatic group is substituted with a hetero atom, it is substituted with -NR- (R is a substituent), an oxygen atom, and a sulfur atom. Jia, the aliphatic group of non-adjacent -CH ₂ - is substituted with an oxygen atom or a sulfur atom is more preferably the aliphatic group of non-adjacent -CH ₂ - is substituted with an oxygen atom is further preferred. With X ¹ ~ X ⁴ represents an aliphatic group of the polymerizable group at the 1 to 2 hetero atoms is substituted are preferred, substituted heteroatom is more preferably 1, and Ar ¹¹ ~ Ar ¹⁴ is represented to include It is further preferred that the aryl group of the benzene ring surrounded by a dashed line is substituted with a hetero atom next to it. As the polymerizable group contained in the aliphatic group having a polymerizable group represented by X ¹ to X ⁴ , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter, also referred to as a radical polymerizable property, respectively) And a cationic polymerizable group) are preferred. As the radically polymerizable group, a generally known radically polymerizable group can be used, and a preferable one includes a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization, and specifically, Examples include vinyl, (meth) acryloxy, and the like. Among them, (meth) acrylic fluorenyloxy is more preferable, and propylene fluorenyloxy is more preferable. As the cationically polymerizable group, generally known cationically polymerizable groups can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, and a spiro Cyclic orthoester groups and vinyloxy groups. Among them, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable. It is preferable that the polymerizable group included in the substituents included in Ar ¹ to Ar ⁴ is a radical polymerizable group. Two or more of Ar ¹ to Ar ⁴ include a substituent having a polymerizable group, two to four of Ar ¹ to Ar ⁴ include a substituent having a polymerizable group, and Ar ¹ to Ar ⁴ More preferably, 2 or 3 of the substituents having a polymerizable group are included, and 2 of Ar ¹ to Ar ⁴ further include a substituent of a polymerizable group. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, X ¹ to X ⁴ may be independently replaced by a benzene ring surrounded by a dotted line, or may be substituted. It is a ring other than a benzene ring surrounded by a dotted line.

In the above general formula (Q3), a and b each independently represent an integer of 1 to 5, 1 or 2 is more preferred, and a and b are both more preferably 1. In the above general formula (Q3), c and d each independently represent an integer of 0 to 5, 0 or 1 is more preferable, and both c and d are more preferably 0.

In the general formula (Q3), R ¹ to R ⁴ each independently represent a substituent. The substituents represented by R ¹ to R ⁴ are not particularly limited, and examples thereof include a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, a fluorenyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, and an aromatic group. Group, heteroaryl group and alicyclic group. The substituent represented by R ¹ to R ⁴ is preferably an alkyl group, an alkoxy group, or an aryl group, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group is more preferable. Of these, methyl, methoxy or phenyl is further preferred. In the general formula (Q3), when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, R ¹ to R ⁴ may be independently substituted by dotted lines. The surrounding benzene ring may be replaced by a ring other than the benzene ring surrounded by a dotted line.

In the general formula (Q3), e, f, g, and h each independently represent an integer of 0 or more, and the upper limits of e, f, g, and h are the numbers of substituents that can be included from Ar ¹¹ to Ar ¹⁴ respectively. Subtract the value of a, b, c, or d. e, f, g, and h are each independently 0 to 8 is preferable, 0 to 2 is more preferable, and 0 is further preferable. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, e, f, g, and h are preferably 0 or 1, and 0 is more preferable.

Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-propenyloxyethoxy) phenyl] fluorene and the like. As the polymerizable compound having a 9,9-diarylfluorene skeleton, the compounds described in Japanese Patent Application Laid-Open No. 2010-254732 can also be preferably used.

The polymerizable compound having a Cardo skeleton is not limited, and examples thereof include On court EX series (manufactured by NAGASE & CO., LTD.) And OGSOL (manufactured by Osaka Gas Chemicals Co., Ltd.).

When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably from 0.1 to 40% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 30% by mass or less, and more preferably 20% by mass or less. The polymerizable compound may be used singly or in combination of two or more kinds. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

<Polymerization initiator> The composition of the present invention preferably has a polymerization initiator. The polymerization initiator is not particularly limited, and can be appropriately selected from known polymerization initiators. For example, those having a photosensitivity (so-called photopolymerization initiator) are preferred. When the composition of the present invention contains a photopolymerization initiator and the polymerizable compound in addition to the inorganic pigment and the black dye, it is hardened by irradiation with actinic rays or radiation, so it is sometimes called "photosensitive composition" Thing. " The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have sensitivity from the ultraviolet region to visible light. In addition, the polymerization initiator may be an active agent that has some effect with a photo-excited photosensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of monomer. In addition, the photopolymerization initiator preferably contains at least one compound having a light absorption coefficient of at least about 50 moles in a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm.).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), fluorenylphosphine compounds such as fluorenylphosphine oxide, hexaarylbisimidazole, Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1384492, and Japanese special Compounds described in Japanese Patent Publication No. 53-133428, compounds described in German Patent No. 3337024, compounds based on J. Org. Chem. Of FC Schaefer, etc .; compounds described in 29, 1527 (1964), Japanese Patent Application Laid-Open No. 62-58241 Compounds described in the gazette, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, compounds described in the specification of US Patent No. 4212976, and the like.

From the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a fluorenylphosphine compound, a phosphine oxide compound, Metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes, and Compounds in the group consisting of a salt, a halomethyloxadiazole compound, and a 3-aryl substituted coumarin compound are preferred.

Further preferred examples include trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, and benzophenone compounds. The acetophenone compound is further preferred, and is selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound. 1 compound.

In particular, when a light-shielding film of a solid-state imaging element is produced using the composition of the present invention, it is necessary to form a fine pattern in a sharp shape, and therefore it is important to develop it without residue in an unexposed portion together with hardenability. From such a viewpoint, it is preferable to use an oxime compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging element, step exposure is used for hardening exposure. However, the exposure machine may be damaged by halogen, and the addition amount of the photopolymerization initiator needs to be kept low. Taking these points into consideration, it is preferable to use an oxime compound as a photopolymerization initiator when forming a fine pattern such as a solid-state imaging element. In addition, by using an oxime compound, color transfer properties can be optimized. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and the contents are incorporated into the specification of the present application.

As a photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be used suitably. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and a fluorenylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names, all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 can be used in which the absorption wavelength matches a long-wave light source such as 365 nm or 405 nm. As a fluorenylphosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: both manufactured by BASF) can be used as commercially available products.

Examples of the photopolymerization initiator include an oxime compound (oxime-based initiator). In particular, the oxime compound has high sensitivity and high polymerization efficiency, and can be hardened irrespective of the color material concentration, and it is easy to design the color material concentration to be high, so it is preferable. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, and a compound described in JP 2006-342166 can be used. As the oxime compound that can be preferably used in the present invention, for example, 3-benzyloxyiminobutane-2-one and 3-ethoxyiminobutane-2-one can be mentioned. Ketone, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane- 1-keto, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Carbonyloxyimino-1-phenylpropane-1-one and the like. In addition, JCSPerkin II (1979) pp.1653-1660), JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japan Compounds described in JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166. Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), Adeka Arkls NCI-831 and Adeka Arkls NCI-930 (manufactured by ADEKA CORPORATION), N-1919 (containing carbazole and oxime ester skeleton light) Starter (manufactured by ADEKA CORPORATION)).

In addition, as the oxime compound other than the above, U.S. Patent No. 7,626,957 may be used as described in Japanese Patent Publication No. 2009-519904, in which an oxime is linked to the N-position of carbazole, and a heterosubstituent is introduced into a diphenyl ketone. Compounds described in Japanese Patent Publication No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into a pigment, ketoxime compounds described in International Patent Publication No. 2009-131189, Compounds described in U.S. Patent No. 7,565,910, which contains a triazine skeleton and an oxime skeleton in the same molecule, compounds described in Japanese Patent Application Laid-Open No. 2009-221114, which have a maximum absorption at 405 nm and have good sensitivity to a g-ray light source. For example, paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760 can be preferably referred to, and the contents are incorporated into the specification of the present application. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. The N-O bond of the oxime may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[Chemical Formula 16]

In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. As the monovalent substituent represented by R in the general formula (OX-1), a monovalent non-metal atomic group is preferred. Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The 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, a fluorenyloxy group, a fluorenyl group, an alkyl group, and an aryl group. As the monovalent substituent represented by B in the general formula (OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents. As the divalent organic group represented by A in the general formula (OX-1), an alkylene group, a cycloalkylene group, or an alkynyl group having 1 to 12 carbon atoms is preferable. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents.

In the present invention, as the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds described in Japanese Patent Application No. 2014-500852, and Japanese Patent Application No. 2013-164471. Compound (C-3) and the like described in the Gazette. This content is incorporated into this manual.

In the present invention, as the photopolymerization initiator, a compound represented by the following general formula (1) or (2) can also be used.

[Chemical Formula 17]

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

^{(2), R 1, R 2, 1} , R 2, R ³ and the same formula the meanings of R ⁴ in the 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 group, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents direct A bond or a carbonyl group, a represents an integer of 0 to 4.

In the above formula (1) and formula (2), it is preferable that R ¹ and R ² are each independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. Specific examples of the compounds represented by the formulas (1) and (2) include, for example, compounds described in paragraphs 0076 to 079 of Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into this manual.

Specific examples of the oxime compound that can be preferably used in the present invention are shown below, but the present invention is not limited to these.

[Chemical Formula 18]

The oxime compound is preferably one having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably one having a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and one having a higher absorbance at 365 nm and 405 nm is more preferable. Among the oxime compounds, the Mohr absorption coefficient at 365 nm or 405 nm is more preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000 from the viewpoint of sensitivity. The Molar absorption coefficient of the compound can be measured by a known method, for example, using a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian Corporation) and an ethyl acetate solvent at a concentration of 0.01 g / L. The photopolymerization initiator used in the present invention can be used in combination of two or more kinds as necessary.

When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator relative to the total solid content in the composition is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and 1 to 10% by mass. % Is further preferred. The composition of the present invention may contain only one kind of polymerization initiator, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total measurement falls within the above range.

<Organic solvent> It is preferable that the composition of this invention contains an organic solvent. Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, dichloroethylene, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and propylene glycol monomethyl. Ether, propylene glycol monoethyl ether, acetone acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol Alcohol monobutyl ether acetate, 3-methoxypropanol, methoxyethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol Alcohol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamidine, dimethylsulfinium, γ -Butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and the like, but are not limited to these.

The composition of the present invention may contain one type of organic solvent, or may contain two or more types of organic solvents. However, from the viewpoint of suppressing the particle size change of the inorganic pigment when the composition of the present invention is adjusted, the composition contains two or more types of organic solvents. Solvent. When two or more organic solvents are contained, it is selected from the group consisting of the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol mono A mixed solution of two or more types of methyl ether and propylene glycol monomethyl ether acetate is particularly preferred.

When the composition of the present invention contains an organic solvent, the content of the organic solvent is preferably 10 to 90% by mass, and more preferably 60 to 90% by mass relative to the total mass of the composition. When two or more kinds of organic solvents are contained, the total amount thereof is preferably in the above range.

<Water> The composition of the present invention may contain water. Water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention. The content of water with respect to 100% by mass of the composition is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.8% by mass, and still more preferably 0.1 to 0.7% by mass. When the content of water is within the above range, pinholes can be suppressed when the light-shielding film is produced, or the moisture resistance of the light-shielding film can be improved.

<Other components> The composition of this invention may contain other components other than the above-mentioned components. Hereinafter, each component is demonstrated in detail.

(Silane coupling agent) A silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. 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 through a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, a fluorenyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. An alkoxy group having 4 or less carbon atoms or an alkenyl group having 4 or less carbon atoms is particularly preferred. In addition, in order to improve the adhesion between the substrate and the light-shielding film, it is preferable that the silane coupling agent does not include fluorine atoms and silicon atoms (except for silicon atoms bonded by hydrolyzable groups), and does not include fluorine atoms and silicon Atoms (except silicon atoms bonded to hydrolyzable groups), alkylene groups substituted with silicon atoms, linear alkyl groups with 8 or more carbon atoms, and branched alkyl groups with 3 or more carbon atoms good.

The silane coupling agent preferably has a group represented by the following formula (Z). * Indicates the bonding position. Formula (Z) *-Si- (R _Z1 ) _{3 In} formula (Z), R _Z1 represents a hydrolyzable group, and its definition is as described above.

The silane coupling agent preferably has one or more hardenable functional groups selected from the group consisting of (meth) acrylic fluorenyloxy, epoxy, and oxetanyl. The hardening functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom through a linking group. Moreover, as a preferable aspect of the curable functional group contained in the said silane coupling agent, a radical polymerizable group is mentioned.

The molecular weight of the silane coupling agent is not particularly limited. From the viewpoint of operability, there are many cases of 100 to 1,000. From the viewpoint of more excellent effects of the present invention, 270 or more is preferable, and 270 to 1,000 is more preferable.

One of the preferable aspects of the silane coupling agent includes a silane coupling agent X represented by the formula (W). The formula (W) R _Z2 -Lz-Si- (R _Z1 ) ₃ R _z1 represents a hydrolyzable group, and is defined as described above. R _z2 represents a hardenable functional group, as defined above, and the preferred range is also as described above. Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include a halogen atom-substituted alkylene group, a halogen atom-substituted alkylene group, -NR ^12- , -CONR ^12- , -CO- , -CO _2- , SO ₂ NR ^12- , -O-, -S-, -SO ₂ -or a combination of these. Among them, at least one selected from the group consisting of an alkylene group which can be substituted with a halogen atom having 2 to 10 carbon atoms and an alkylene group which can be substituted with a halogen atom having 6 to 12 carbon atoms, or including these groups and A combination of at least one group selected from the group consisting of -NR ^12- , -CONR ^12- , -CO-, -CO _2- , SO ₂ NR ^12- , -O-, -S-, and SO _2- The group is preferably a group including a substituted alkylene group having 2 to 10 carbon atoms, a -CO _2- , -O-, -CO-, -CONR ¹² -or a combination of these groups. For the better. Here, the above R ¹² represents a hydrogen atom or a methyl group.

Examples of the silane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N -β-aminoethyl-γ-aminopropyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-tri Ethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-Aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. product name KBE-903), 3-Methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co. , Ltd. (trade name: KBM-503), Glycidoxyoctyltrimethoxysilane (trade name, KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

As another preferable aspect of the silane coupling agent, a silane coupling agent Y having at least a silicon atom, a nitrogen atom, a hardenable functional group in the molecule, and a hydrolyzable group bonded to a silicon atom is mentioned. . The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. These may be the same atom or substituent, or may be different. Examples of the bondable atom and substituent include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, and an amine group which may be substituted by an alkyl group and / or an aryl group. , Silyl, alkoxy, aryloxy having 1 to 20 carbon atoms, and the like. These substituents may be further substituted by silyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, amine groups which may be substituted with alkyl and / or aryl, halogen atoms, Sulfonamido, alkoxycarbonyl, amido, urea, ammonium, alkylammonium, carboxyl or its salt, sulfo or its salt, and the like. In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above. The silane coupling agent Y may contain a group represented by the above formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and it is preferable that the nitrogen atom exists in the form of a secondary amine group or a tertiary amine group, that is, the nitrogen atom has at least one organic group as a substituent. Mission is better. The structure of the amine group may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocyclic ring, or may exist as a substituted amine group such as aniline. Among them, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent, and examples of the substituent that can be introduced include silyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, amine, and halogen atoms. , Sulfonylamino, alkoxycarbonyl, carbonyloxy, fluorenylamino, urea, alkoxyammonium, alkylammonyl, carboxyl or its salt, sulfo, and the like. In addition, it is preferable that the nitrogen atom is bonded to the curable functional group via an arbitrary organic linking group. Preferred examples of the organic linking group include substituents which can be introduced into the nitrogen atom and an organic group bonded thereto.

The definition of the hardenable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above. The silane coupling agent Y may have at least one hardenable functional group in one molecule, but may take the form of two or more hardenable functional groups. From the viewpoint of sensitivity and stability, It is more preferable to have 2 to 20 hardenable functional groups, and it is more preferable to have 4 to 15 hardenable functional groups. It is best to have 6 to 10 hardenable functional groups in the molecule.

The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, and examples thereof include the above range (270 or more is preferred).

The content of the silane coupling agent in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 1.0 to 6% by mass, relative to the total solids in the composition. .

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

(Surfactant) The composition of the present invention may contain various surfactants from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

By containing a fluorine-based surfactant in the composition of the present invention, the liquid characteristics (especially, flowability) when preparing a coating liquid are further improved, and the uniformity of coating thickness and liquid saving can be further improved. That is, when a coating liquid containing a composition containing a fluorine-based surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is improved. The applicability to the surface to be coated is improved. Therefore, formation of a film having a uniform thickness with small thickness unevenness can be performed more preferably.

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

Examples of the fluorine-based surfactant include Megaface F171, Megaface F172, Megaface F173, Megaface F176, Megaface F177, Megaface F141, Megaface F142, Megaface F143, Megaface F144, Megaface R30, Megaface F437, Megaface F475, Megaface F479 , Megaface F482, Megaface F554, Megaface F780, RS-72-K (above, manufactured by DIC Corporation), Fluorado FC430, Fluorado FC431, Fluorado FC171 (above, manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTIONS INC.), Etc. As the fluorine-based surfactant, a compound described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used. As the fluorine-based surfactant, a block polymer can also be used. As a specific example, for example, a compound described in Japanese Patent Application Laid-Open No. 2011-89090 can be mentioned. The fluorine-based surfactant can also preferably be used as a fluorine-containing polymer compound including a repeating unit derived from a (meth) acrylate compound having a fluorine atom and derived from a compound having 2 or more (5 or more is preferred) ) Repeating units of (meth) acrylate compounds of alkoxy (vinyloxy and propyleneoxy are preferred). The following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Chemical Formula 19]

The weight average molecular weight of the compound is preferably 3,000 to 50,000, and is, for example, 14,000. In addition, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, such as Megaface RS-101, RS-102, RS-718K, or RS-72 manufactured by DIC Corporation. -K and so on.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, glycerol propoxylate) , Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylen Glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901, 904, 150R1, SOLSPERSE 20000 (manufactured by The Lubrizol Corporatin), etc. In addition, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), And an organosiloxane polymer KP341 (Shin-Etsu Chemical Co. , Ltd.), (meth) acrylic (co) polymer Polyflow No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD), W001 (manufactured by Yusho Co Ltd), and the like.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co Ltd), Sandetto BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

Examples of the silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (above, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by BYK Additives & Instruments), etc.

The surfactant may be used singly or in combination of two or more kinds. The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass based on the total solid content of the composition of the present invention.

<Polymerization inhibitor> It is preferable that the said composition contains a polymerization inhibitor. If a polymerization inhibitor is contained, the said composition will have more excellent time-dependent stability. The content of the polymerization inhibitor is relative to the total solid content of the composition. 0.00055 to 0.055 mass% is more preferable, and 0.0015 to 0.01 mass% is more preferable.

The polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used. Examples of the compound used as a polymerization inhibitor include phenol-based compounds, anthraquinone-based compounds, hindered amine-based compounds, phenothiazine-based compounds, and nitrobenzene-based compounds. These compounds may be used individually by 1 type, and may use 2 or more types together.

Examples of the phenol-based compound include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, resorcinol, 4-tert-butylbenzenediol, and 2,6-dihydroquinone. -Third-butylphenol, 2,6-di-third-butyl-4-methylphenol, 2,6-di-third-butyl-4-ethylphenol, 4-hydroxymethyl-2,6 -Di-tert-butylphenol, pentaerythritol tetra (3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) ester, 4-methoxy-1-naphthol and 1,4-dihydroxynaphthalene Wait.

As the phenolic compound, a phenolic compound represented by the formula (IH-1) is preferable.

[Chemical Formula 20]

In the formula (IH-1), R ₁ to R ₅ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group, an amine group, an aryl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a fluorenyl group. R ₁ to R ₅ may be connected to each other to form a ring.

As R ₁ to R ₅ in the formula (IH-1), a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, methyl and ethyl), and an alkoxy group having 1 to 5 carbon atoms (for example, (Methoxy, ethoxy, etc.), alkenyl (for example, vinyl, etc.) having 2 to 4 carbon atoms, or phenyl is preferred. Among them, R ₁ and R ₅ are each preferably a hydrogen atom or a third butyl group, R ₂ and R ₄ are more preferably a hydrogen atom, R ₃ is a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms or An alkoxy group having 1 to 5 carbon atoms is more preferred.

Examples of the anthraquinone-based compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.

Examples of the hindered amine-based compound include a polymerization inhibitor represented by the following formula (IH-2).

[Chemical Formula 21]

R ₆ in formula (IH-2) represents a hydrogen atom, a hydroxyl group, an amine group, an alkoxy group, an alkoxycarbonyl group, or a fluorenyl group. Among them, a hydrogen atom or a hydroxyl group is preferable, and a hydroxyl group is more preferable. In addition, R ₇ to R ₁₀ in the formula (IH-2) each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R ₇ to R ₁₀ is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.

As the polymerization inhibitor, each of the above compounds may be used alone, two kinds may be used, and three or more kinds may be used. The polymerization inhibitor preferably contains a phenolic compound. Among these, from the viewpoint of stability over time, it is more preferable that the polymerization inhibitor contains two or more phenol-based compounds. From the standpoint of stability over time, the polymerization inhibitor preferably contains a phenol-based compound and a hindered amine-based compound.

<Ultraviolet absorbent> The said composition may contain an ultraviolet absorber. Thereby, the pattern shape of a cured film can be made more excellent (fine). As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorber can be used. As specific examples of these, compounds of paragraphs 0137 to 0142 of Japanese Patent Application Laid-Open No. 2012-068418 (corresponding paragraphs 0251 to 0254 of US2012 / 0068292) can be used, and those contents can be incorporated into this specification by reference. . In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., Trade name: UV-503) and the like can also be preferably used. Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of Japanese Patent Application Laid-Open No. 2012-32556. The content of the ultraviolet absorber is more preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass with respect to the total solid content of the composition. As the ultraviolet absorber, each of the above-mentioned compounds may be used alone, or two or more of them may be used alone.

(Organic Pigment) The composition may contain an organic pigment. Examples of the organic pigment include the following: Dye 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, 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, etc .; CI Pigment Green 7, 10, 36, 37, 58, 59, etc .; CI Pigment Violet 1, 19, 23, 27, 32, 37, etc. 42 etc .; CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. The pigment may be used singly or in combination of two or more kinds.

<Color dyes> As the dye, for example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, and Tedden can be used. No. 2592207, U.S. Patent No. 4,850,001, U.S. Patent No. 5,667,920, U.S. Patent No. 505950, U.S. Patent No. 5,667,920, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application No. 6-35183, Japanese Patent Application No. 6-35183 Pigments disclosed in Japanese Patent Publication No. 51115 and Japanese Patent Application Laid-Open No. 6-194828. When distinguished as a chemical structure, a pyrazole azo compound, a pyrrole methylene compound, an aniline azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxonol compound, and pyridine can be used. Zolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazomethine compounds, and the like. As the dye, a pigment multimer can be used. Examples of the pigment multimer include compounds described in Japanese Patent Application Laid-Open No. 2011-213925 and Japanese Patent Application Laid-Open No. 2013-041097. In addition, as a commercially available product, a color dye polymerizable dye having polymerizability in a molecule can be used. For example, RDW series manufactured by Wako Pure Chemical Industries, Ltd. can be used.

<Infrared absorbing agent> The coloring agent may further contain an infrared absorbing agent. The infrared absorber means a compound having absorption in a wavelength region of an infrared region (wavelength of 650 to 1300 nm is preferable). The infrared absorber is preferably a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm. Examples of the coloring agent having such a spectroscopic property include a pyrrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an imine compound, a thiol complex compound, a transition metal oxide compound, Squaric acid cyanine compounds, naphthalocyanine compounds, quartrenene compounds, dithiol metal complex compounds, ketonium compounds, and the like. As the phthalocyanine compound, naphthalocyanine compound, imine compound, cyanine compound, squaraine compound, and ketonium compound, the compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Application Laid-Open No. 2010-111750 can be used, and the contents are incorporated herein In the manual. The cyanine compounds can be referred to, for example, "functional pigments, Ogawara Nobuyoshi / Matsuoka Ken / Hiro Kitahiro / Hiroshi Hirano, Kodansha Scientific Ltd.", and the contents are incorporated into this specification.

As the coloring agent having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Laid-Open No. 07-164729 and / or compounds disclosed in paragraphs 0027 to 0061 of Japanese Patent Application Laid-Open No. 2002-146254, Near-infrared absorbing particles containing microcrystals of Cu and / or P-containing oxides and having a number-average agglomerated particle diameter of 5 to 200 nm, which are disclosed in paragraphs 0034 to 0066 of Japanese Patent Application Laid-Open No. 2011-164583. In addition, the infrared absorber may be used singly or in combination of two or more kinds.

When the composition of the present invention contains a colorant other than the inorganic pigment, the content of the colorant is preferably 1 to 10% by mass, and more preferably 2 to 7% by mass relative to the total solid content of the composition.

In addition to the above components, the following components may be added to the composition of the present invention. For example, sensitizers, pigment dispersants, co-sensitizers, cross-linking agents, hardening accelerators, fillers, heat hardening accelerators, plasticizers, diluents, and fat sensitizers other than those described above. Add adhesion promoters and other additives (such as conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, and surface tension modifiers) to the substrate surface as needed And chain transfer agents). These components can be referred to, for example, Japanese Patent Application Publication No. 2012-003225, paragraph numbers 0183 to 0228 (corresponding to [0237] to [0309] of US Patent Application Publication No. 2013/0034812), Japanese Patent Application Laid-Open No. 2008-250074 The descriptions of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of Japanese Patent Application Laid-Open No. 2013-195480 are incorporated in this specification.

The solid content of the composition of the present invention is preferably 10 to 40% by mass. When the solid content of the composition is 10% by mass or more, the light-shielding property of the light-shielding film is further improved. In addition, when the solid content of the composition is 40% by mass or less, the amount of particles in the composition can be further reduced, and stability over time can be improved. From the viewpoint of further improving the light-shielding performance of the light-shielding film, the solid content is preferably 12% by mass or more.

<Manufacturing method of a composition> The composition of this invention can be manufactured by mixing the said various components by a well-known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser). When manufacturing the composition, various components constituting the composition may be compounded at one time, or the various components may be dissolved or dispersed in an organic solvent and then compounded sequentially. In addition, the input sequence and working conditions at the time of cooperation are not particularly limited. In addition, in the process of dispersing the pigment, examples of the mechanical force for dispersing the pigment include compression, pressing, impact, cutting, and pitting. Specific examples of these processes include bead milling, sand mixing, roll milling, high-speed impeller, sand milling, jet flow mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, it is possible to appropriately use "Encyclopedia of Dispersion Technology, Issued by Information Corporation, July 15, 2005" and "Actually Comprehensive Information on Dispersion Technology and Industrial Applications Focusing on Suspension (Solid / Liquid Dispersion System)" Collected, issued by the Publishing Department of the Business Development Center, October 10, 1978 ". In addition, in the process of dispersing the pigment, the pigment can be refined by a salt milling process. The raw materials, equipment, and processing conditions used in the salt milling process can be, for example, those described in Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application No. 2012-046629. In order to remove foreign matter or reduce defects, it is preferable to filter the composition of the present invention with a filter. The filter can be used without particular limitation as long as it has been used for filtering applications and the like. Examples include filters based on fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), and the like. . Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is preferably about 0.1 to 7.0 μm, more preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and even more preferably 0.3 to 0.7 μm. By setting it as this range, it is possible to suppress filtration clogging of the pigment, and to reliably remove fine foreign matters such as impurities or aggregates contained in the pigment. When using filters, different filters can be combined. In this case, the filtration by the first filter may be performed only once, or may be performed twice or more. When two or more filtrations are performed by combining different filters, the pore diameter after the second filtration is preferably the same as or larger than the pore diameter of the first filtration. In addition, the first filters having different pore diameters within the above range may be combined. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, various filters provided by NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon squirrel co., Ltd.) or KITZ MICROFILTER CORPORATION can be selected. The second filter can be formed using the same material as that of the first filter. The pore diameter of the second filter is preferably about 0.2 to 10.0 μm, more preferably about 0.2 to 7.0 μm, and even more preferably about 0.3 to 6.0 μm.

[Curable Film (Light-shielding Film)] The cured film of the present invention is obtained using the above composition. The cured film of the present invention mainly includes the above-mentioned inorganic pigment (preferably a black inorganic pigment, and more preferably a pigment containing a nitride or an oxynitride) and a black dye. The cured film of the present invention is suitably used as a light-shielding film, and specifically, it is suitable as a light-shielding film (frame light-shielding film) around an image sensor such as a CCD image sensor or a CMOS image sensor. The light shielding film surrounding the image sensor obtained by using the composition of the present invention has excellent light shielding performance. That is, the light-shielding performance does not decrease in a specific wavelength region, and the minimum optical density is in a range that can provide sufficient light-shielding performance in a predetermined region (for example, visible light region to 1200 nm).

The film thickness of the cured film of the present invention can be appropriately selected depending on the application, and is not particularly limited. When the cured film of the present invention is used as, for example, a light-shielding film around an image sensor, the thickness of the light-shielding film is not particularly limited. The film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and 0.2 μm. It is more preferable that it is more than 30 μm, and it is more preferable that it is 0.2 μm or more and 25 μm or less. 0.2 μm or more and 20 μm or less is particularly preferable, and 0.2 μm or more and 10 μm or less is most preferable. The size (length of one side) of the light shielding film is preferably 0.001 mm or more and 5 mm or less, more preferably 0.05 mm or more and 4 mm or less, and more preferably 0.1 mm or more and 3.5 mm or less.

<The manufacturing method of a cured film (light-shielding film)> Next, the manufacturing method of the cured film (light-shielding film) of this invention is not specifically limited, A well-known method can be employ | adopted. Hereinafter, as a representative example, a method for producing a patterned cured film will be described in detail.

The method for producing a patterned cured film according to the present invention includes a process of applying a composition of the present invention on a substrate to form a composition layer (coating film) (hereinafter, referred to as “composition layer formation as appropriate”). Process ".); A process of exposing the above-mentioned composition layer through a mask (hereinafter, appropriately referred to as" exposure process "); and a process of developing the composition layer after exposure to form a patterned cured film ( Hereinafter, it is appropriately referred to as "developing process.")

Specifically, the composition of the present invention is coated on a substrate directly or via another layer to form a composition layer (composition layer forming process), and exposure is performed through a predetermined mask pattern, so that only the composition irradiated with light The layer is partially cured (exposure process), and a patterned cured film including pixels is formed by developing with a developing solution (development process). Hereinafter, each process will be described.

(Composition Layer Formation Process) In the composition layer formation process, the composition of the present invention is applied on a substrate to form a composition layer (coating film).

Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, and photoelectric conversion element substrates used for solid-state imaging elements such as those with a transparent conductive film attached thereto ( For example, silicone substrates, etc.), CCD substrates, and CMOS substrates. In addition, in order to improve adhesion to the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate, an undercoat layer may be provided on these substrates as needed.

As a coating method for applying the composition of the present invention to a substrate, various coatings such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, or a screen printing method can be applied. method.

When manufacturing a peripheral light-shielding film for an image sensor, as a coating film thickness of the composition, from the viewpoint of resolution and developability, 0.35 μm or more and 1.5 μm or less is preferable, and 0.40 μm or more and 1.0 μm or less is more preferable. good.

The composition coated on the substrate is usually dried at a temperature of 70 ° C or higher and 110 ° C or lower, and is dried for about 2 minutes to 4 minutes. Thereby, a composition layer can be formed.

(Exposure Process) In the exposure process, the composition layer (coating film) formed in the composition layer forming process is exposed through a mask, and only a part of the coating film irradiated with light is hardened. It is preferable to perform exposure by actinic rays or radiation, and particularly, ultraviolet rays such as g rays, h rays, or i rays are more preferable. The irradiation intensity is preferably 5 to 1500 mJ / cm ^{2, and more} preferably 10 to 1000 mJ / cm ² .

(Development process) The exposure process is followed by an alkali development process (development process), and the light-irradiated part in an exposure process is melt | dissolved in alkaline aqueous solution. Thereby, only the light-hardened portion (the portion of the coating film irradiated with light) remains. As the developer, an organic alkali developer that does not cause damage to the circuit of the substrate or the like is preferred. The development temperature is usually 20 to 30 ° C, and the development time is 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. Examples of the inorganic developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, or sodium metasilicate, and the concentration thereof is 0.001 to 10% by mass, and preferably 0.01 to 1% by mass alkaline aqueous solution. Examples of the organic developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1 , 8-Diazabicyclo- [5.4.0] -7-undecene and other organic basic compounds are dissolved into an alkaline aqueous solution having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. To the alkaline aqueous solution, for example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added. In addition, when using a developing solution containing such an alkaline aqueous solution, it is usually preferable to wash (rinse) with pure water after development.

As a development method, a spin-on immersion development method, a shower development method, etc. can be used, for example.

In addition, in the method for manufacturing a cured film of the present invention, after the above-mentioned composition layer forming process, exposure process, and development process are performed, as required, the formed cured film may be cured by heating and / or exposure. Hardening process.

[Color filter and light-shielding film] The cured film formed using the composition of the present invention can be suitably used as a pixel black matrix of a color filter or various kinds in an image display device or a sensor module described later. Applicable light-shielding film in components.

(Color Filter) The color filter can be preferably used for a solid-state imaging element such as a CCD or CMOS, and is particularly suitable for a high-resolution CCD or CMOS with a resolution of more than 1 million pixels. The color filter can be used, for example, by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a micro lens for condensing light. In addition, the color filter may have a structure in which a hardened film of each color pixel is embedded in a space partitioned into a grid shape by a partition wall, for example. It is preferable that the partition wall has a low refractive index for each color pixel. Examples of the imaging element having such a structure include the devices described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Laid-Open No. 2014-179577. The shape of the color filter of the present invention is not particularly limited as long as it has the cured film. The cured film can be preferably used as a pixel black matrix of a color filter, for example.

(Light-shielding film) The light-shielding film can be formed in various components in an image display device or a sensor module (for example, an infrared light cut filter, a peripheral portion of a solid-state imaging element, a wafer-level lens peripheral portion, or a solid-state imaging element). Back, etc.) and so on. In addition, a light-shielding film may be formed on at least a part of the surface of the infrared-light-cut filter as the infrared-light-cut filter with a light-shielding film. The thickness of the light-shielding film is not particularly limited, but is preferably 0.2 to 25 μm, and more preferably 0.2 to 10 μm. The thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the light-shielding film and arithmetically averaging the thicknesses. The reflectance of the light-shielding film is preferably 10% or less, more preferably 8% or less, even more preferably 6% or less, and particularly preferably 4% or less. The reflectance of the light-shielding film is a value in which light of 400 to 700 nm is incident on the light-shielding film at an incident angle of 5 °, and the reflectance is measured by a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation.

[Solid-State Imaging Device] The solid-state imaging device of the present invention includes the solid-state imaging element described above, and the above-mentioned cured film (color filter, light-shielding film, etc.) is provided on the outer peripheral portion or the back surface of the solid-state imaging element. The structure of the solid-state imaging device according to the present invention is not particularly limited as long as it has the above-mentioned cured film and solid-state imaging element, and examples thereof include the following structures.

The structure is as follows: a plurality of transfer electrodes including a photodiode, polycrystalline silicon, and the like are provided on a substrate to constitute a light receiving region of a solid-state imaging element (a CCD image sensor or a CMOS image sensor, etc.); The body and the transfer electrode are provided with a light-shielding film opened only to the light-receiving part of the photodiode, and the light-shielding film is provided with a device protection including silicon nitride and the like formed to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. Film, which has a color filter on the device protection film. In addition, it is also possible to have a structure that has a light-concentrating mechanism (for example, a micro lens, etc. below) on the device protective layer and under the color filter (close to one side of the substrate), and that has light-concentrating on the color filter. Structure of institutions, etc.

[Image Display Device] The cured film (such as a color filter or a light-shielding film) of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device.

Definitions of display devices or details of each display device are described, for example, in "Electronic Display Devices (Asa Sasaki, Kogyo Chosakai Publishing Co., Ltd. 1990)", "Display Devices (Ibuki Shunshu, Industrial Books) Co., Ltd. issued in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display Technology (edited by Ryuu Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the liquid crystal display device can be applied to various types of liquid crystal display devices described in the "second generation liquid crystal display technology".

When the color filter of the present invention is applied to a liquid crystal display device, its form is not particularly limited. Hereinafter, a case where the color filter of the present invention is applied to a liquid crystal display device will be described in detail. The color filter of the present invention can be used for a liquid crystal display device of a color TFT (Thin Film Transistor) system. A color TFT-type liquid crystal display device is described in, for example, "color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD., 1996)". In addition, the color filter of the present invention can also be applied to a liquid crystal display device or a STN (Super-N) with an enlarged viewing angle such as a lateral electric field drive method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment) Twist Nematic, TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), or R-OCB (Reflective Optically Compensated Bend). In addition, the color filter of the present invention can also be used in a bright and high-definition COA (Color-filter On Array) method. As for the liquid crystal display device of the COA method, the required characteristics of the color filter may require the required characteristics of the interlayer insulation film in addition to the general required characteristics as described above, that is, low dielectric constant and resistance to the release liquid. . The color filter of the present invention is excellent in light resistance and the like, and therefore can provide a liquid crystal display device of the COA system with high resolution and excellent long-term durability. In addition, in order to meet the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer. These image display methods are described in, for example, page 43 of "EL, PDP, LCD Display-Latest Trends in Technology and Market-(TORAY Research Center, Inc. Survey and Research Division 2001)".

In addition to the color filter of the present invention, the liquid crystal display device of the present invention may be composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle protection film. The color filter of the present invention can be applied to a liquid crystal display device including these known members. These components are described in, for example, "'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Shimadaro CMC-Group. Released in 1994)", "Current Status and Future Prospects of the Liquid Crystal-Related Market in 2003 (Volume II) (Table Ryoji Fuji Chimera Research Institute, Inc., 2003) ". The backlight is described in SID meeting Digest 1380 (2005) (A.Konno et.al) or the monthly display of December 2005, pages 18 to 24 (Island Kangyu), and the monthly display of December 2005, pages 25 to 30. (Yaki Takaki) and so on.

In addition, the cured film of the present invention can be used in portable devices such as personal computers, tablet computers, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multifunction printers or scanners; surveillance cameras, and bar code readers And industrial equipment such as automatic teller machines (ATMs) or high-speed cameras or personal authentication using face image authentication; automotive camera equipment; medical camera equipment such as endoscopes, capsule endoscopes or catheters; living organisms Used in sensors, biosensors, military surveillance cameras, stereo map cameras, meteorological or ocean observation cameras, land resource surveillance cameras, or space astronomy or deep space target exploration cameras, etc. The light-shielding member or light-shielding layer of the optical filter or module can be used as an anti-reflection member or an anti-reflection layer.

The cured film of the present invention can also be used in applications such as micro LEDs (Light Emitting Diodes) or micro OLEDs (Organic Light Emitting Diodes). Although it is not particularly limited, in addition to an optical filter or an optical film used in a micro LED or a micro OLED, it can also be preferably used as a member that imparts a light-shielding function or an anti-reflection function. Examples of the micro LED or micro OLED include those described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.

The cured film obtained by curing the composition of the present invention can also be used in applications such as quantum dot displays. Although not particularly limited, in addition to an optical filter or an optical film used in a quantum dot display, it can also be preferably used as a member that imparts a light-shielding function or an anti-reflection function. Examples of quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960 Recorder. [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be interpreted restrictively by the examples shown below. In addition, unless otherwise specified, "parts" and "%" are quality standards.

[Composition] Hereinafter, the preparation of the compositions of the examples and comparative examples will first be described with respect to each component contained in the composition.

<Inorganic pigments (pigments containing nitrides or nitrogen oxides)> (TiN-1) Manufactured by NISSHIN ENGINEERING INC. (Containing titanium nitride particles, BET specific surface area 55m ² / g, average primary particle size 24.2nm) (TiN- 2) Product name "TiN20nm" (including titanium nitride particles, average primary particle diameter 41.7nm) manufactured by Hefei Company (TiN-3) Product name "13M-T" (nitrogen-containing titanium oxide particles, average Primary particle size: 75nm)

<Dye> (Dye A) Dye A was synthesized by the following procedure.

47 g of intermediate (C) described in paragraph [0340] of Japanese Patent Application Laid-Open No. 2016-69656 was dissolved in 500 ml of N, N-dimethylacetamide, and the internal temperature was cooled to 0 ° C. While keeping the internal temperature at 5 ° C. or lower, 5.5 g of osmium methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto, and the mixture was allowed to react at room temperature for 90 minutes. The obtained reaction solution was poured into a large amount of excess ethyl acetate and filtered off. This was dissolved in chloroform, purified by column chromatography, and concentrated and dried by a rotary evaporator, and the following polymerizable group-containing compound was taken out (yield: 12%).

[Chemical Formula 22]

Next, 5 g of the polymerizable group-containing compound was dissolved in 45 g of N, N-dimethylacetamide in the flask, and heated to 70 ° C. Under a nitrogen atmosphere, 0.5 g of 45-g of N, N-dimethylacetamide dissolved in a thermal polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After the dropwise addition, a heating reaction was further continued for 5 hours, and then the reaction solution was poured into a large amount of ethyl acetate, and the following oligomer was taken out as a precipitate (yield 95%). The oligomer obtained by GPC analysis confirmed that the average value of the repeating unit n was 6.3.

[Chemical Formula 23]

5 g of the oligomer obtained in the above was dissolved in 500 ml of N, N-dimethylacetamide, and the internal temperature was cooled to 0 ° C. While keeping the internal temperature at 5 ° C. or lower, 5 g of gadolinium methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto, and the mixture was allowed to react at room temperature for 90 minutes. The obtained reaction solution was poured into a large amount of excess ethyl acetate and filtered off, and the following polymerizable group-containing xanthene oligomer was taken out (yield: 98%).

[Chemical Formula 24]

(Dye B) According to Japanese Patent Application Laid-Open No. 2013-253170, a xanthene skeleton compound having no polymerizable group represented by the following structural formula was obtained.

[Chemical Formula 25]

(Dye C) According to Japanese Patent Application Publication No. 2004-534121, an azo compound having no polymerizable group represented by the following structural formula was obtained. In the following structural formula, M represents a hydrogen atom and / or a sodium atom depending on the pH.

[Chemical Formula 26]

<Binder resin> As the binder resin, the following resin A was used as the alkali-soluble resin.・ Resin A (manufactured by Akurikuya RD-F8 NIPPON SHOKUBAI CO., LTD., See formula below)

[Chemical Formula 27]

<Dispersant> As a dispersant, the following dispersants A to E were used. In the dispersants A, B, and D, the numerical value described in each structural unit represents the mass% of each structural unit with respect to all the structural units. In addition, in the dispersant C, the numerical values (a to e) described in each structural unit represent the molar ratio of each structural unit to all the structural units, and x and y represent the number of connections. In the dispersant E, the numerical value described in the linking group linked to Z indicates the number of links linked to Z.

[Chemical Formula 28]

<Polymerizable Compound> As the polymerizable compound, the following polymerizable compound M1 was used.・ Polymerizable compound M1 (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA", see formula below) [Chemical formula 29]

<Polymerization initiator> As the polymerization initiator, the following oxime-based initiators were used.・ OXE-02: Irgacure OXE02 (trade name, manufactured by BASF JAPAN LTD.)

<Organic solvent> As an organic solvent, the following organic solvents were used.・ PGMEA: Propylene glycol monomethyl ether acetate

<Surfactant> As the surfactant, the following surfactant 1 was used. (Surfactant 1) Mixture F-1 represented by the following structural formula (weight average molecular weight (Mw) = 14000)

[Chemical Formula 30]

In addition, the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of each resin used were calculated by GPC (Gel Permeation Chromatography) measurement.

<Preparation of Pigment Dispersion> First, a pigment containing a nitride or an oxynitride, a dispersant, and an organic solvent were mixed for 15 minutes with a blender (Eurostar, manufactured by IKA Company) to obtain a dispersion. Next, the obtained dispersion was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Corporation to obtain a pigment dispersion. In addition, the ratio (mass ratio) of the dispersant to the pigment containing nitride or oxynitride (hereinafter, also referred to as "D / P") is the ratio shown in each of the examples and comparative examples in Table 1. Way was added. (Dispersion conditions) ・ Bead diameter: φ0.05mm, (Zirconium oxide beads manufactured by NIKKATO CORPORATION, YTZ) ・ Bead filling rate: 65% by volume ・ Grinding peripheral speed: 10m / sec ・ Separator peripheral speed: 13m / s ・ Dispersion Amount of mixed liquid to be processed: 15kg • Circulating flow rate (supply amount of pump): 90kg / hour • Temperature of processing liquid: 19 to 21 ° C • Cooling water: water • Processing time: about 22 hours

<Preparation of composition> Next, the pigment dispersion liquid, black dye, binder resin, polymerizable compound, polymerization initiator, surfactant, and organic solvent were mixed and stirred to obtain Examples shown in the following Table 1. And each composition of the comparative example. In addition, regarding the black dye, a composition of the "carrying agent" and the black dye described in the mixing table is prepared in advance, and this is mixed with other components such as a pigment dispersion. The content (mass%) of each component contained in each composition of an Example and a comparative example is shown in Table 1.

<Measurement of Moisture Content in Compositions> With respect to the moisture content of each composition in the examples and comparative examples, MKV-710 (trade name, KYOTO ELECTRONICS MANUFACTURING) using the Karl Fischer method as a measuring principle CO., LTD.). The results are shown in Table 1. The moisture in the composition is derived from various raw materials.

[Evaluation Test] The following evaluation tests were performed on each composition of Examples and Comparative Examples.

<Number of Particles> Each composition of the Examples and Comparative Examples was put into a 100 mL Bloom bottle, and left to stand in an environment of 45 ° C. for 7 days. Then, 90 mL of the supernatant was removed, and the remaining 10 mL of the composition was diluted 500-fold with PGMEA (propylene glycol monomethyl ether acetate) to prepare an evaluation solution. The number of particles of 10 μm or more contained in 10 ml of the evaluation solution was counted by a flow-type particle image analysis device (trade name “FPIA”, manufactured by Malvern Instruments Ltd).

<Spectral (light-shielding)> A 0.7 mm, 10 cm square glass plate (EagleXG, Corning) was applied at a rotation speed of 1.0 μm with a film thickness to form a coating film by a spin coating method, and heated. The coated film was heat-treated at 100 ° C for 2 minutes to obtain a dried film. About the obtained dried film, OD (optical density) was measured with the spectrophotometer U-4100 (made by Hitachi High-Technologies Corporation.). Based on the lowest OD at a wavelength of 400 to 1200 nm, the spectral (light-shielding) evaluation was performed based on the following criteria. At this time, by adjusting the composition of the composition, 50% by mass of the solid content of the coating liquid became a pigment. "A": minimum OD> 2.5 "B": 2.5 ≥ minimum OD> 2.3 "C": 2.3 ≥ minimum OD> 2.1 "D": 2.1 ≥ minimum OD

<Viscosity stability over time> After the compositions of Examples and Comparative Examples were stored at 23 ° C for 10 days, the compositions were stored at 7 ° C for 90 days. In addition, the viscosity of each composition before and after storage was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., trade name "R85-shaped viscometer") under conditions of a rotation speed of 10 rpm and 23 ° C. Then, a value (%) of [｛(viscosity after time-viscosity immediately after liquid adjustment) / viscosity immediately after liquid adjustment｝ 100] was calculated. The evaluation criteria are as follows. "A": Within ± 3% "B": Within ± 3% and within ± 5% "C": Within ± 5% and within ± 10% "D": Within ± 10%

<Reworkability> Using each composition of Examples and Comparative Examples, each composition was spin-coated on an electrode pattern of a silicon wafer having an electrode pattern (copper) formed on the surface, and a dried film of a coating film of each composition The thickness is 0.7 μm. Thereafter, the silicon wafer coated with each composition was subjected to a heat treatment (pre-baking) for 120 minutes in this state by using a hot plate at 100 ° C for 120 seconds to form a coating film. Next, using an i-ray step exposure device FPA-3000i5 + (manufactured by Canon Inc.), at a wavelength of 365 nm, the pattern was passed through an Island pattern mask with 20 μm on four sides, and the coating film was exposed at an exposure of 500 mJ / cm ² . exposure. Moreover, each composition of an Example and a comparative example is a negative photosensitive resin composition which hardened an exposure part. Thereafter, the silicon wafer substrate on which the exposed coating film was formed was placed on a horizontal rotary table of a rotary shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Electronic alkaloid developer (manufactured by Electronic Materials Co., Ltd.), and subjected to spin-on immersion development at 23 ° C for 60 seconds. Next, the silicon wafer after the spin-over immersion development was fixed to the above-mentioned horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate was rotated at a rotation speed of 50 rpm by a rotating device, and sprayed from above the rotation center from a nozzle. Pure water was supplied for washing processing, and then spray-dried to form a wafer having a frame-like pattern.

Next, the obtained wafer having a frame pattern was immersed in a 25% aqueous solution of TMAH (tetramethylammonium hydroxide) at 85 ° C for 5 hours, and immersed in a 2L DIW (pure water) tank at room temperature. The rinse process was performed for 2 minutes. The removability was evaluated by observing the state where the frame pattern was removed from the obtained cleaned wafer with an optical microscope (manufactured by Olympus Corporation, trade name "LEXTLEXOLS4500"). The evaluation criteria are as follows. "A": No pattern is observed. "B": Residual particles are observed in a patterned area of 5% or less. "C": Particles are observed in a patterned area of more than 5% and less than 10%. Removal residue "D": particulate removal residue can be observed in more than 10% of the pattern formation area, or a pattern or a part of the pattern can be observed

<Heat resistance> A glass film (EagleXG, Corning) having a thickness of 0.7 mm and 10 cm square was coated with a composition at a rotation speed of 1.0 μm to form a coating film by a spin coating method. The coating film was heat-treated at 100 ° C. for 2 minutes to obtain a dry film. About the obtained dried film, OD (optical density) was measured with the spectrophotometer U-4100 (made by Hitachi High-Technologies Corporation.). Based on the lowest OD at a wavelength of 400 to 1200 nm, the spectroscopic (light-shielding) evaluation was performed as the lowest OD before the heat resistance test. The dried film was heat-treated on a hot plate at 265 ° C. for 10 minutes, and the spectroscopic evaluation was performed in the same manner as described above to obtain the lowest OD after the heat resistance test. The amount of spectroscopic variation in the heat resistance test was calculated by the following formula and evaluated. "Amount of change = ｛(lowest OD after heat resistance test-lowest OD before heat resistance test) / lowest OD before heat resistance test × 100" "A": within ± 3% "B": more than ± 3% and within ± 5% " "C": Within ± 5% and within ± 10% "D": Above ± 10%

<Pattern Formability (Resolution)> Using the compositions of Examples and Comparative Examples, a coating film was formed on a substrate of an image sensing device by a spin coater. Next, the obtained coating film was subjected to a pre-baking treatment at 100 ° C. for 2 minutes on a hot plate. Next, an i-ray exposure device (manufactured by FPA, Canon Inc.) was used to expose the coating film subjected to the pre-baking treatment and further develop it, thereby forming a covered cutting line and an electrode portion on the peripheral portion of the light receiving portion on the substrate. At the same time as the other light-shielding films, 20 alignment marks having a line width of 20 μm were formed on the substrate. The number of alignment marks formed was observed with an optical microscope to evaluate the resolution. "A": 20 marks were formed. "B": 19 marks were formed. "C": 18 marks were formed. "D": 17 or less marks are formed.

The evaluation results of the above evaluation tests are shown in Table 1. [Table 1]

From the results in Table 1, it was confirmed that the light-shielding film formed of the composition of Examples 1 to 21 exhibited high light-shielding performance. On the other hand, the light-shielding film formed from the composition of Comparative Example 1 did not satisfy the required light-shielding performance.

Comparative Examples 1, 6, 7, and 8 show that the content of the black dye relative to the pigment containing nitride or oxynitride is 0.3 or less in terms of mass ratio (0.25 or less is preferable, and 0.2 or less) For better), and further improve reworkability.

Comparing Examples 1, 4 and 5, it was shown that the black dye has a polymerizable group, so that reworkability, heat resistance, and pattern formation properties are further improved. In addition, in Example 5 using an azo dye, it was confirmed that heat resistance was excellent.

Comparison of Examples 1 and 9 to 12 shows that the amount of particles in the liquid can be further reduced by setting the acid value of the dispersant to 50 mgKOH / g or more. In particular, Example 1 shows that by using the dispersant A containing benzyl methacrylate as a hydrophobic component, the amount of particles in the liquid is smaller and the pattern formation property is also excellent.

Comparative Examples 1, 16, and 17 show that when the amount of solid content relative to the total mass of the composition is 10 to 40% by mass, the amount of particles is further reduced, and the stability over time is further improved. In addition, from the results of Examples 13, 14, and 15, it was shown that when the solid content of the total mass of the composition was 12% by mass or more, the light-shielding performance of the obtained light-shielding film was further improved.

Comparative Examples 1, 20, and 21 show that when the content of the pigment is 30% by mass or more relative to the solid content, the light-shielding performance of the obtained light-shielding film is further improved, and the heat resistance is also improved. On the other hand, when the content of the pigment is 70% by mass or less based on the solid content, it is shown that the reworkability and the pattern formability are further improved.

(Example 22) In Example 1, a polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of dye A, and a composition was prepared in the same manner as in Example 1. As a result of evaluation, it was found that the performance was equivalent to that of Example 1.

(Example 23) In Example 1, instead of dye A, dye A and a polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) were used and used in a ratio of 1: 1 by mass. In addition, the composition was prepared and evaluated by the same method. As a result, it was found that the composition had the same performance as that of Example 1.

(Example 24) In Example 4, instead of the dye B, the dye B and a polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) were used, and the mass ratio was 1: 1 and used. In addition, the composition was prepared and evaluated by the same method. As a result, an evaluation superior to that of Example 4 was obtained. Specifically, it was found that the reworkability evaluation, heat resistance evaluation, and pattern formation evaluation were all Become "B".

(Example 25) In Example 1, instead of TiN-1, TiN-1 and carbon black (trade name "Color Black S170", manufactured by Degussa-Hüls AG, average primary particle diameter of 17 nm, and BET specific surface area of 200 m ² / g were used. (Carbon black produced by gas black method) and set it to 7: 3 by mass ratio, except that the composition was prepared in the same way and evaluated. As a result, it was found that 1 equivalent performance.

(Example 26) In Example 1, instead of TiN-1, TiN-1 and Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN) were used and the mass ratio was set. A composition was prepared and evaluated in the same manner except that it was used in a ratio of 9: 1. As a result, it was found that the composition had the same performance as that of Example 1, and it was found that a light-shielding film having a thicker black color was obtained. From this result, it is inferred that the desired effect of the present application can be obtained even when used with other organic pigments or color dyes.

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Claims (20)

A composition comprising an inorganic pigment and a black dye. The composition according to item 1 of the patent application range, wherein the inorganic pigment is a pigment containing a nitride or an oxynitride. The composition according to claim 1 or claim 2, wherein the black dye has a polymerizable group. The composition according to claim 1 or claim 2, wherein the polymerizable group is an acrylfluorenyl group or a methacrylfluorenyl group. The composition according to item 1 or item 2 of the scope of patent application, wherein the black dye is a xanthene-based dye or an azo-based dye. The composition according to item 1 or item 2 of the scope of patent application, wherein the black dye is a dye multimer. The composition according to item 1 or item 2 of the scope of patent application, further comprising a dispersant. The composition according to item 7 of the scope of patent application, wherein the acid value of the dispersant is 50 mgKOH / g or more. The composition according to item 7 of the scope of patent application, wherein the dispersant has at least one selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate, and polymethyl methacrylate 1 structure. The composition according to item 1 or item 2 of the scope of patent application, further comprising a polymerizable compound and a polymerization initiator. The composition according to item 1 or item 2 of the scope of patent application, further comprising an organic solvent. The composition according to item 1 or item 2 of the scope of patent application, further comprising an alkali-soluble resin. The composition according to claim 1 or claim 2, wherein the content of the black dye relative to the content of the inorganic pigment is 0.3 or less by mass ratio. The composition according to item 1 or 2 of the scope of patent application, wherein the solid content relative to the total mass of the composition is 10 to 40% by mass. The composition according to item 1 or item 2 of the scope of patent application, wherein the content of the inorganic pigment is 30 to 70% by mass based on the amount of solid content. A hardened film obtained by using the composition described in any one of claims 1 to 15 of the scope of patent application. A color filter having a hardened film as described in item 16 of the scope of patent application. A light-shielding film having a hardened film according to item 16 of the scope of patent application. A solid-state imaging device includes a hardened film as described in item 16 of the scope of patent application. An image display device has a hardened film as described in item 16 of the scope of patent application.