JP2021128345A - Composition, cured film, color filter, light shield film, solid-state image capturing device, and image display device - Google Patents

Abstract

To provide a composition which allows for forming a light shield film with superior light-shielding performance, and to provide a cured film with superior light-shielding performance, color filter comprising the cured film, light shield film, solid-state image capturing device, and image display device.SOLUTION: A composition of the present invention contains an inorganic pigment and a black dye.SELECTED DRAWING: None

Description

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

The black light-shielding film is used for various purposes. For example, a light-shielding film is used in a solid-state image sensor. Usually, a solid-state image sensor is a solid-state imaging device such as a photographing lens and a CCD (Charge Coupled Device, charge-coupled device) and CMOS (Complementary Metal-Oxide Semiconductor) arranged behind the photographing lens. It includes an element (hereinafter, the solid-state image sensor is also referred to as an “image sensor”) and a circuit board on which the solid-state image sensor is mounted. In this solid-state image sensor, noise may be generated due to the reflection of visible light. Therefore, a predetermined light-shielding film may be provided in the solid-state image sensor for the purpose of suppressing the generation of noise.
Further, as another application of the light-shielding film, a so-called black matrix can also be mentioned.

Various compositions have been proposed as compositions for forming such a light-shielding film. For example, Patent Document 1 states, "A black resin composition for a resin black matrix containing at least a light-shielding material, a resin and a solvent, and containing at least titanium nitride particles as the light-shielding material, and using CuKα-ray as an X-ray source. The black resin composition for a resin black matrix in which the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride particles is 42.5 ° or more and 42.8 ° or less is disclosed (claim). 1).

Japanese Patent No. 5136139

The present inventor produced a light-shielding film of a color filter arranged in a solid-state imaging device, a liquid crystal image device, or the like using a black composition prepared based on Patent Document 1, and examined its various performances. It has been found that the light-shielding performance in a specific wavelength region is low (in other words, the optical density is low).
Generally, when a pigment such as titanium nitride-containing particles is 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, and as a result, the light-shielding performance of the obtained light-shielding film is improved. May decrease.
Therefore, it is desired to improve the light-shielding performance of the light-shielding film by means other than increasing the pigment concentration.

An object of the present invention is to provide a composition capable of forming a light-shielding film having excellent light-shielding performance in view of the above circumstances.
Another object of the present invention is to provide a cured film having excellent light-shielding performance, a color filter provided with the cured film, a light-shielding film, a solid-state image sensor, and an image display device.

As a result of diligent studies to achieve the above problems, the present inventors have found an inorganic pigment (preferably a black inorganic pigment described later, more preferably a pigment containing a nitride or an oxynitride) and a black dye. The present invention has been completed by finding that the above-mentioned problems can be solved by using a composition containing.
That is, it was found that the above object can be achieved by the following configuration.

(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 acryloyl group or a methacryloyl group.
(5) The composition according to any one of (1) to (4), wherein the black dye is a xanthene dye or an azo 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 at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, methyl polyacrylate and polymethyl methacrylate. thing.
(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 containing an organic solvent.
(12) The composition according to any one of (1) to (11), further containing an alkali-soluble resin.
(13) The composition according to any one of (1) to (12), wherein the content of the black dye is 0.3 or less by mass ratio with respect to the content of the inorganic pigment.
(14) The composition according to any one of (1) to (13), wherein the solid content is 10 to 40% by mass with respect to the total mass of the composition.
(15) The composition according to any one of (1) to (14), wherein the content of the inorganic pigment is 30 to 70% by mass with respect to the solid content.
(16) A cured film obtained by 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 image sensor having the cured film according to (16).
(20) An image display device having the cured film according to (16).

According to the present invention, it is possible to provide a composition capable of forming a light-shielding film having excellent light-shielding performance.
Further, according to the present invention, it is possible to provide a cured film having excellent light-shielding performance, a color filter provided with the cured film, a light-shielding film, a solid-state image sensor, and an image display device.

The present invention will be described below.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "active light" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. .. Further, in the present invention, light means active light rays or radiation. Unless otherwise specified, the term "exposure" as used herein refers to not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, and EUV light, but also particle beams such as electron beams and ion beams. Drawing by is also included in the exposure.
In the present specification, "(meth) acrylate" represents acrylate and methacrylate, "(meth) acrylic" represents acrylic and methacrylic, and "(meth) acryloyl" represents acryloyl and methacryloyl. Further, in the present specification, "monomer" and "monomer" are synonymous. The monomer in the present invention is distinguished 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 means a compound having a polymerizable group, and may be a monomer or a polymer. A polymerizable group is a group involved in a polymerization reaction.

〔Composition〕
The composition of the present invention contains an inorganic pigment (preferably a black inorganic pigment described later, more preferably a pigment containing a nitride or an acid nitride) and a black dye.
According to the composition of the present invention, a light-shielding film having excellent light-shielding performance can be formed. That is, according to the composition of the present invention, there is no deterioration in light-shielding performance in a specific wavelength region, and the minimum optical density (hereinafter, also referred to as "minimum OD value") is set in a predetermined region (for example, visible light region to 1200 nm). It is possible to form a light-shielding film within a range that can provide sufficient light-shielding ability.
A feature of the composition of the present invention is that it contains a black dye. When the concentration of the inorganic pigment is increased in order to improve the minimum optical density, the content of the dispersant used for the purpose of improving the dispersibility of the inorganic pigment in the composition becomes relatively large, which is caused by this. As a result, the light-shielding performance of the obtained light-shielding film may deteriorate. However, since the composition of the present invention contains a black dye that does not require a dispersant and has absorption over substantially the entire wavelength region of visible light, the minimum amount of the light-shielding film is obtained without increasing other components such as the dispersant. It is possible to improve the optical density.
In particular, it has been found that when a xanthene dye or an azo dye as described later is used, a light-shielding film having excellent light-shielding performance and excellent resolution can be formed.

Now, the present inventor has found that it is particularly preferable that the above-mentioned black dye has a polymerizable group. When a light-shielding film is formed using the composition of the present invention, if the black dye has a polymerizable group, the dye is incorporated into the matrix constituting the film via the polymerizable group. It is generally known that dyes are inferior in heat resistance to pigments, and when a dye is used as a constituent component of a light-shielding film, the light-shielding film may be inferior in heat resistance due to the dye. On the other hand, as described above, it has been confirmed that the matrix constituting the film and the black dye are chemically bonded by a polymerizable group to obtain better heat resistance.
Further, in recent years, after forming a light-shielding film on a predetermined substrate, it may be required to peel off the light-shielding film from the substrate due to a shift in the formation position of the light-shielding film or the like. So-called reworkability is required.
As described above, the present inventor has also found that the matrix constituting the film and the black dye are chemically bonded by a polymerizable group to improve the reworkability. That is, for example, a color filter (cured film) prepared by using a composition containing an inorganic pigment, a black dye having a polymerizable group, an alkali-soluble resin, or the like is used, for example, TMAH (tetramethylammonium hydroxide) or the like. When removing with an alkaline aqueous solution, the black dye is chemically bonded to a film composed of an alkali-soluble resin, so that the dye can be removed (peeled) together with the matrix. On the other hand, when the black dye does not have a polymerizable group, that is, when the black dye is not chemically bonded to the matrix, the dye is generally insoluble in an alkaline aqueous solution, so that it remains alone on the solid-state image sensor. It adheres to the surface and is difficult to remove. That is, it is inferior in reworkability.

Further, when the black dye has an acryloyl group or a methacryloyl group as a polymerizable group, the patterning property (hereinafter, also referred to as “resolution”) of the coating film formed by the composition of the present invention is further improved. I have also confirmed that.

Further, the black dye is preferably a dye multimer. Since the black dye is a dye multimer, the heat resistance is further improved. The black dye is preferably 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 inorganic pigments include carbon black, silica, zinc white, lead white, lithopon, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead tan, iron oxide red, chrome yellow, and zinc yellow (zinc yellow). Zinc yellow 1 type, Zinc yellow 2 types), Ultramarine blue, Prussian blue (ferrous iron potassium) Zircon gray, placeodium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, Prussian blue (unrelated to Prussian blue) , Vanadium zirconium blue, chrome tin pink, ceramic red, and salmon pink. Further, it is preferably a black inorganic pigment, and as the inorganic pigment, carbon black, titanium black, and carbon black, titanium black, and carbon black, titanium black, and the like can be obtained in that a composition capable of forming a cured film having at least a high optical density can be obtained. Metal pigments and the like are preferable. Examples of the metal pigment include metal oxidation containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Examples include materials, metal nitrogen products, and metal oxynitrides.
Inorganic pigments include titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, chromium oxide, chromium nitride, chromium oxynitride, iron oxide, iron oxynitride, and metal pigments containing silver. It is preferably at least one selected from the group consisting of a metal pigment containing tin and a metal pigment containing silver and tin.
Among them, the inorganic pigment is more preferably at least one selected from the nitrides or pigments containing 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 with respect to the total solid content of the composition. When the content of the inorganic pigment is 30% by mass or more with respect 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 with respect to the solid content, the reworkability and the patterning property are further improved. The content of the inorganic pigment is more preferably 35 to 70% by mass and further preferably 40 to 70% by mass with respect to the total solid content of the composition.

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

The average primary particle size 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.
Maximum length (Dmax: maximum length at two points on the contour of the particle image) and maximum length vertical length (DV-max: two straight lines parallel to the maximum length) of the particle image obtained using a transmission electron microscope. When the image was sandwiched between the two straight lines, the length was measured (the shortest length connecting the two straight lines vertically), and the synergistic average value (Dmax × DV-max) ^1/2 was taken as the particle size. The particle size of 100 particles is measured by this method, and the arithmetic mean value thereof is used as the average particle size to obtain the average primary particle size of the pigment.

(Pigment containing nitride or oxynitride)
As described above, the inorganic pigment is preferably a pigment containing a nitride or an oxynitride.
Examples of the nitride or the pigment containing the oxynitride include pigments such as titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, iron oxynitride, and tungsten oxynitride. Be done. Of these, those having absorption in the wavelength region of 400 to 1200 nm are preferable. 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) or the like.
From the viewpoint of achieving a high optical density with 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, but the titanium nitride described in International Publication No. 2008/123097, International Publication No. 2010/147098, and Japanese Patent No. 5577659 can be used.
Further, in the pigment containing a nitride or oxynitride, the content of the nitride or oxynitride (for example, when the pigment contains titanium nitride, the content of titanium nitride) is the total mass of the pigment. On the other hand, it is preferably 10 to 100% by mass, and more preferably 20 to 100% by mass.

-Titanium Black The titanium black particles, which are titanium oxynitride pigments, will be described below.
The surface of the titanium black particles can be modified as necessary for the purpose of improving dispersibility or suppressing cohesion. It is possible to coat titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, a surface treatment of titanium black is also possible with a water-repellent substance as shown in JP-A-2007-302836.
Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of the individual particles are small.
Specifically, those having an average primary particle size in the range of 10 nm to 80 nm are preferable. The average primary particle size can be measured by, for example, the above method.

The specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmet, Teller) method is used because the water repellency after surface treatment of titanium black with a water repellent agent has a predetermined performance. It is preferably 5 m ² / g or more and 150 m ² / g or less, and ^{more preferably 20 m 2} / g or more and 120 m ² / g or less.
Examples of commercially available titanium black products include titanium black 10S, 12S, 13M, 13M-C, 13R, 13RN, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), and Tilak. ) D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

Further, it is also preferable to contain titanium black as a dispersant containing titanium black and Si atoms.
In this form, titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is further preferable.
Here, the dispersant includes both those in which titanium black is in the state of primary particles and those in which titanium black is in the state of aggregates (secondary particles).
In order to change the Si / Ti of the dispersant (for example, to set it to 0.05 or more), the following means can be used.
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is reduced at a high temperature (for example, 850 to 1000 ° C.) to mainly produce titanium black particles. A dispersant containing Si and Ti as components can be obtained. The reduction treatment is performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo Co., Ltd.). Titanium oxide is not limited to this, but has a primary particle size of 5 nm or more and 70 nm or less, more preferably 7 nm or more and 50 nm or less, and any of rutile and anatase can be preferably used as the crystal system. These mixed crystals may be used.
Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade name: manufactured by Evonik).
A dispersant may be used to disperse the titanium oxide and the silica particles. Examples of the dispersant include those described in the column of dispersants described later.
The above dispersion may be carried out in a solvent. Examples of the solvent include water and organic solvents. Examples thereof will be described in the column of organic solvent described later.
Titanium black in which Si / Ti is adjusted to, for example, 0.05 or more is prepared by, for example, the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of JP-A-2008-266405. can do.

By adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersant containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), the composition containing the disperse is included. When a light-shielding film is formed using a material, the residue derived from the composition outside the light-shielding film formation region is reduced. The residue contains titanium black particles and components derived from the composition such as a resin component.
The reason why the residue is reduced is unknown, but the dispersant as described above tends to have a small particle size (for example, the particle size is 30 nm or less), and further, a component containing Si atoms of the dispersant. It is speculated that the increase in the amount of the coating film reduces the adhesiveness of the entire film to the substrate, which contributes to the improvement of the developability of the uncured composition (particularly titanium black) in the formation of the light-shielding film.
Further, since titanium black is excellent in light shielding property against light in a wide wavelength range from ultraviolet light to infrared light, the above-mentioned dispersant containing titanium black and Si atom (preferably Si / Ti is mass-converted). The light-shielding film formed by using (with a value of 0.05 or more) exhibits excellent light-shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is determined by, for example, the method (1-1) or method (1-2) described in paragraph 0033 of JP2013-249417A. ) Can be used for measurement.
Further, with respect to the dispersant contained in the light-shielding film obtained by curing the composition, whether or not the content ratio (Si / Ti) of Si atoms and Ti atoms in the disperse is 0.05 or more. In order to determine, the method (2) described in paragraph 0035 of JP2013-249417A is used.

In the dispersant containing titanium black and Si atom, the above-mentioned titanium black can be used.
In this case, it is preferable that the dispersant made of titanium black occupies 50% by mass or more of the total dispersoid.
Further, in this dispersion, for the purpose of adjusting the light-shielding property, other colorants (organic pigments, dyes, etc.) may be used in combination with titanium black as long as the effects of the present invention are not impaired. good.
Hereinafter, the materials used when introducing Si atoms into the dispersion to be dispersed will be described. When introducing a Si atom into the dispersion, a Si-containing substance such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, synthetic silica and the like, and these may be appropriately selected and used.
Further, when the particle size of the silica 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 fine particle type silica as the silica particles. Examples of the fine particle type silica include the silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.

-Titanium Nitride-Containing Particles Further, as the pigment containing a nitride or an oxynitride, for example, titanium nitride-containing particles can also be used.
The vapor phase reaction method is usually used for producing the titanium nitride-containing particles, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because of the fact that impurities are less mixed, the particle size is easily uniform, and the productivity is high.
Examples of the method for generating thermal plasma include DC arc discharge, multi-phase arc discharge, high frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less contamination of impurities from the electrodes is preferable. As a specific method for producing titanium nitride-containing particles by the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and the titanium powder is nitrided in the cooling process. , A method of synthesizing titanium nitride-containing particles and the like. The thermal plasma method is not limited to the above.
Further, the titanium nitride-containing particles are obtained by using the thermal plasma method, so that the diffraction angle 2θ (details will be described later) of the peak derived from the (200) plane when CuKα ray is used as an X-ray source. It becomes easy to adjust to the range of 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, and preferably 55 to 85% by mass, based on the total mass of the titanium nitride-containing particles. More preferably, it is more preferably 55 to 80% by mass. The content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP (radio frequency inductively coupled plasma) emission spectroscopy.
The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 15 to 50% by mass, preferably 15 to 45% by mass, based on the total mass of the titanium nitride-containing particles. More preferably, it is 20 to 40% by mass. The content of nitrogen atoms can be analyzed by the melting-thermal conductivity method of inert gas.

The titanium nitride-containing particles have a peak diffraction angle 2θ of more than 42.8 ° and 43.5 ° or less when the X-ray diffraction spectrum is measured using CuKα ray as an X-ray source. preferable. A light-shielding film obtained by using a composition containing titanium nitride-containing particles having such characteristics has an appropriate OD value and is excellent in patterning property (resolution).

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 43.5 ° or less as described above, and is 42.85 to 43.3 °. Is more preferable, and 42.9 to 43.2 ° is even more preferable.
Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and are usually noticeable when oxygen is mixed during their synthesis or when the particle size is small, but due to oxidation of the particle surface or the like, It may contain some oxygen atoms.
However, it is preferable that the amount of oxygen contained in the titanium nitride-containing particles is small because a higher OD value (optical concentration) can be obtained. Further, it is preferable that the titanium nitride-containing particles _{do not contain TiO 2 as an auxiliary component.} When titanium nitride-containing particles contain titanium _{oxide TiO 2} as a sub-component, _{the peak derived from anatase-type TiO 2} (101) as the strongest peak is in the vicinity of 2θ = 25.3 °, and rutile-type TiO ₂ ( A peak derived from 110) can be seen in the vicinity of 2θ = 27.4 °. However, since TiO ₂ is white and causes a factor of lowering the light-shielding property of the black matrix, it is preferable that it is reduced to such an extent that it is not observed as a peak.

The crystallite size constituting the titanium nitride-containing particles can be obtained from the half width of the X-ray diffraction peak, and is calculated using Scherrer's equation.

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

The specific surface area of the titanium nitride-containing particles can be determined by the BET method, is preferably of 40 to 60 ² / g, more preferably 40~58m ² / g, it is 42~55m ² / g Is even more preferable. By setting the specific surface area of the titanium nitride-containing particles to 40 to 60 m ² / g, the obtained light-shielding film has an OD (optical density) value in an appropriate range and is excellent in patterning property (resolution).

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

(Other pigments)
The composition of the present invention may also contain an inorganic pigment other than those listed above as the inorganic pigment. Other pigments include, for example, tungsten compounds and metal borides.
Tungsten compounds and metal borides are characterized by high absorption of infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light-shielding property (shielding property) with respect to infrared rays). It should be noted that the tungsten compound and the metal boride absorb less in visible light than in the light-shielding property against infrared rays. Further, the tungsten compound and the metal boride absorb less light in a shorter wave than the visible region used for exposure of a high-pressure mercury lamp, KrF, ArF, etc. used for image formation.

Examples of the tungsten compound include a tungsten oxide-based compound, a tungsten booxide-based compound, and a tungsten sulfide-based compound, and the tungsten oxide-based compound represented by the following general formula (composition formula) (I) is preferable.
M _x W _{y Oz} ... (I)
M stands for metal, W stands for tungsten, and O stands for 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, Cd, and the like. Examples thereof include Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os and Bi, but alkali metals are preferable. The metal of M may be one kind or two or more kinds.

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

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, the formation of an impurity phase in the tungsten compound can be more reliably avoided. can.
When z / y is 2.2 or more, the chemical stability as a 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 compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , and Ba _0.33 WO _3. Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

The tungsten compound is preferably fine particles. The average particle size of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. The average particle size of the tungsten fine particles is usually 1 nm or more for reasons such as ease of handling during production.

Moreover, it is possible to use two or more kinds of tungsten compounds.

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

Examples of metal borides include lanthanum boride (LaB ₆ ), _{placeodium boride (PrB 6} ), neodium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium borides (YB ₆ ), and boride. Titanium (TiB ₂ ), Zirconium borides (ZrB ₂ ), Hafnium borides (HfB ₂ ), Vanadium borides (VB ₂ ), Tantal borides (TaB ₂ ), Chromium borides (CrB, CrB ₂ ), Borides One or more of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten borides (W ₂ B ₅ ) and the like can be mentioned, and lanthanum boride (LaB ₆ ) is preferable. ..

The metal boride is preferably fine particles. The average particle size of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. The average particle size of the metal boride fine particles is usually 1 nm or more for reasons such as ease of handling during production.

Moreover, it is possible to use two or more kinds of metal borides.

The metal boride is available as a commercially available product, and is also available as a dispersion of fine metal boride particles such as KHF-07AH manufactured by Sumitomo Metal Mining Co., Ltd.

The inorganic pigment may be an extender pigment. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite.
When an extender pigment is used as the inorganic pigment, it is preferable to use the extender pigment in combination with a coloring pigment (for example, a black inorganic pigment). These extender pigments can be used alone or in admixture of two or more. The amount of the extender pigment used is usually 0 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the colorant. Colorants and extender pigments can optionally be used by modifying their surfaces with a polymer.

<Black dye>
The composition of the present invention contains a black dye.
The black dye preferably has absorption over the entire wavelength region of visible light (380 nm or more and 780 nm).
Examples of the black dye include C.I. I. Direct Black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like, as well as known dyes exhibiting a black color can be mentioned. Further, examples of the black dye include xanthene dyes, azo dyes, and aniline dyes.
The black dye preferably has an optical density of 2 or more, more preferably 4 or more, particularly in the entire wavelength region 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 applying energy, and examples thereof include a radical polymerizable group and a cationically polymerizable group. Of these, a radically polymerizable group is preferable because it has more excellent reactivity. Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, an acrylic acid ester group (acryloyloxy group), a methacrylate ester group (methacryloyloxy group), an itaconic acid ester group, a crotonic acid ester group, and an isocrotonic acid ester group. In addition to unsaturated carboxylic acid ester groups such as maleic acid ester groups, styryl groups, vinyl groups, acrylamide groups, methacrylic acid groups and the like can be mentioned. Of these, a methacryloyl group or an acryloyl group is more preferable from the viewpoint of further improving the resolution of the coating film.
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 may be one or two or more.

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

[In the general formula (1), ^{RA to RC} 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 a dye residue obtained by removing one arbitrary hydrogen atom from a black dye. ]

^{RA to RC} 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 preferable.
L represents a single bond or a divalent linking group.
The divalent linking group may be, for example, -O-, -S-, -NR ^1- , -CO-, vinylene group, ethynylene group, alkylene group (cyclic, branched or linear). A divalent group consisting of an arylene group, a heteroarylene group, or a combination thereof can be mentioned.
R ¹ is, for example, a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably an F atom, a Cl atom, a Br atom, or an I atom). ), An aryl group (preferably an aryl group having 6 to 20 carbon atoms). Among these, a hydrogen atom or an alkyl group is preferable.

Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from a black dye.
The black dye is not particularly limited, and examples thereof include the above-mentioned black dye. Of these, xanthene dyes or azo dyes are preferable from the viewpoint of being able to form a light-shielding film having better light-shielding performance.
When the dye multimer having the 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 having a polymerizable group. The fact that Dye has a polymerizable group means that the dye residue represented by Dye from which one arbitrary hydrogen atom has been removed from the black dye has a polymerizable group.

When the black dye is a dye multimer, the content of the structural unit represented by the above general formula (1) in the dye multimer is preferably 80% by mass or more, preferably 80% by mass or more, based on the total structural unit. By mass% or more is more preferable, 90% by mass or more is further preferable, and 95% by mass or more is particularly preferable.
The dye multimer having the 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, but it is preferable that the weight average molecular weight (Mw) is 1000 or more and 20000 or less as a polystyrene conversion value by the GPC (gel permeation chromatography) method. , 2000 or more and 15,000 or less, and more preferably 2000 or more and 10000 or less.
In the GPC method, HLC-8020GPC (manufactured by Tosoh Corporation) was used, TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) were used as columns, and THF (tetrahydrofuran, manufactured by Tosoh Corporation) was used as an eluent. ) Is used.

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

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

In the composition of the present invention, the content of the black dye is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, and 1 to 8% with respect to the total solid content of the composition. It is more preferably mass%.
In the composition of the present invention, one type of black dye may be used alone, or two or more types may be used in combination.

<Dispersant>
The composition of the present invention preferably contains a dispersant. The dispersant contributes to improving the dispersibility of the pigment component such as the above-mentioned inorganic pigment. In the present invention, the dispersant and the binder resin described later are different components.
As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Dispersants include polymer dispersants [eg, polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylics. Copolymers, naphthalene sulfonic acid formarin condensates, etc.], polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, pigment derivatives, etc. may be mentioned.
Polymer compounds can be further classified into linear polymers, end-modified polymers, graft-type polymers, and block-type polymers based on their structures.

The polymer compound is adsorbed on the surface of the object to be dispersed, such as an inorganic pigment and a pigment to be used in combination if desired, and acts to prevent reaggregation of the object to be dispersed. Therefore, terminal-modified polymers, graft-type polymers, and block-type polymers having an anchor site on the pigment surface are preferable.
On the other hand, by modifying the surface of the inorganic pigment, the adsorptivity of the polymer compound to the inorganic pigment can be promoted.

The polymer compound preferably has a structural unit having a graft chain. In addition, in this specification, "structural unit" is synonymous with "repeating unit".
Since the polymer compound having a structural unit having such a graft chain has an affinity with a solvent due to the graft chain, the dispersibility of the coloring pigment such as the above-mentioned inorganic pigment and the dispersion stability after aging are improved. It is excellent. Further, due to the presence of the graft chain, the polymer compound having a structural unit having the graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to generate a residue in alkaline development.
The longer the graft chain, the higher the steric repulsion effect and the better the dispersibility of pigments and the like. On the other hand, if the graft chain is too long, the adsorptive power to the coloring pigment such as the above-mentioned inorganic pigment is lowered, and the dispersibility of the pigment or the like tends to be lowered. Therefore, the graft chain preferably has an atomic number of 40 to 10000 excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and an atomic number excluding hydrogen atoms. It is more preferably 60 to 500.
Here, the graft chain indicates from the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably has a polymer structure, and examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. , And a polyether structure and the like.
In order to improve the interoperability between the graft chain and the solvent, thereby increasing the dispersibility, the graft chain shall be at least one selected from the group consisting of polyester structure, polyether structure and poly (meth) acrylate structure. A graft chain having at least one of a polyester structure and a polyether structure is preferable, and a 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, but a macromonomer having a reactive double bond group can be preferably used.

Commercially available macromonomers that correspond to the structural unit having the graft chain of the polymer compound and are preferably used for the synthesis of the polymer compound include AA-6 (trade name, Toagosei Co., Ltd.) and AA-10 (trade name, Toagosei Co., Ltd.). Product name, Toagosei Co., Ltd., AB-6 (Product name, Toagosei Co., Ltd.), AS-6 (Product name, Toagosei Co., Ltd.), AN-6 (Product name, Toagosei Co., Ltd.) (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 (commodity name) Name, Toagosei Co., Ltd., Blemmer PP-100 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PP-500 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PP-800 (trade name, manufactured by Nichiyu Co., Ltd.) Blemmer PP-1000 (trade name, manufactured by Nissui Co., Ltd.), Blemmer 55-PET-800 (trade name, manufactured by Nissui Co., Ltd.), Blemmer PME-4000 (trade name, manufactured by Nichiyu Co., Ltd.) Blemmer PSE-400 (trade name, manufactured by Nissui Co., Ltd.), Blemmer PSE-1300 (trade name, manufactured by Nissui Co., Ltd.), Blemmer 43PAPE-600B (trade name, manufactured by Nichiyu Co., Ltd.) (Manufactured by Co., Ltd.), etc. are used. Among these, preferably AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.). , AS-6 (trade name, Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), and Blemmer PME-4000 (trade name, manufactured by Nichiyu Co., Ltd.), etc. Be done.

The dispersant preferably has at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and cyclic or chain polyester. Among them, it is preferable to have at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and chain polyester, and polycaprolactone, polyvalerolactone, methyl polyacrylate and polymethacrylic acid. It is more preferable to have at least one structure selected from the group consisting of methyl. The dispersant may have the above-mentioned structures alone in one dispersant, or may have a plurality of these structures in one dispersant.
Here, the polycaprolactone structure refers to a structure having a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure having a ring-opened structure 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 5. 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 4.
Specific examples of the dispersant having a polymethyl acrylate structure, X ⁵ in formula (4) is a hydrogen atom, and R ⁴ is a methyl group. Specific examples of the dispersant having a polymethyl methacrylate structure, X ⁵ in formula (4) is a methyl group, and R ⁴ is a methyl group.

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

In formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ independently represent an oxygen atom or NH, respectively. W ¹ , W ² , W ³ and W ⁴ are preferably oxygen atoms.
In formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthetic constraints, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are preferably hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, respectively, and are independent of each other. In addition, it is more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly structurally restricted. 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 mean the binding sites with the left-terminal group and the right-terminal group in the formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable because of the ease of synthesis.

In formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, but specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group and the like. Can be mentioned. Among these, ^{as the organic group represented by Z 1} , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are preferable from the viewpoint of improving dispersibility, and each of them independently starts from 5 carbon atoms. Twenty-four alkyl groups or alkoxy groups are preferable, and among them, a branched chain alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms, respectively, are preferable. Is preferable. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

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

In the formula (3), R ³ represents a branched chain or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. when p is 2 to 500, R ³ existing in plural numbers may be different from one another the same.
In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly structurally limited. Preferred as R ^4, a hydrogen atom, an alkyl group, an aryl group, and include heteroaryl groups, more preferably a hydrogen atom, or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. , A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is further preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

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

The structural unit represented by the formula (1) is more preferably the structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability of the composition.
Further, the structural unit represented by the formula (2) is more preferably the structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability of the composition.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same. Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

Further, the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoint of dispersion stability and developability of the composition. ..

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

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

In the polymer compound, the structural unit having a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferably contained in the range, more preferably in the range of 5 to 30%. When a structural unit having a graft chain is included in this range, the above-mentioned inorganic pigment has high dispersibility and developability when forming a light-shielding film is good.

Moreover, it is preferable that the polymer compound has a hydrophobic structural unit different from the structural unit having a graft chain (that is, it does not correspond to the structural unit having a graft chain). However, in the present invention, the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

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

The ClogP value is determined by Daylight Chemical Information System, Inc. It is a value calculated by the program "CLOGP" available from. This program provides the value of "calculated logP" calculated by Hansch, Leo's fragment approach (see literature below). The fragment approach is based on the chemical structure of a compound, and the logP value of the compound is estimated by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.M. G. Sammenens, J. et al. B. Taylor and C.I. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev. , 93, 1281-1306, 1993.

logP means the common logarithm of the partition coefficient P (Partition Cofficient), and quantitatively describes how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is expressed by the following formula.
logP = log (Coil / Water)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Water represents the molar concentration of the compound in the aqueous phase.
When the logP value increases positively across 0, it means that oil solubility increases, and when it becomes negative and the absolute value increases, it means that water solubility increases. It is widely used as a parameter for estimating water content.

The polymer compound preferably has at least one structural unit selected from the structural units derived from the monomers represented by the following general formulas (i) to (iii) as the hydrophobic structural unit.

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1. Represents an alkyl group of ~ 6 (eg, methyl group, ethyl group, propyl group, 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. It is more preferable that R ² and R ^{3 are hydrogen atoms.}
X represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

L is a single bond or divalent linking group. The divalent linking group includes a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) and a divalent aromatic group (for example, an arylene group). , substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} Examples include an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and a combination thereof.

The divalent aliphatic group may have a cyclic structure or a branched chain 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 preferable. In addition, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, a heterocyclic group and the like.

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

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is fat. Group group, aromatic group or heterocyclic group), aliphatic group, aromatic group or heterocyclic group.

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

As Z, an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group) , A heterocyclic group, or a combination thereof. These groups an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} is an aliphatic group, an aromatic A group or heterocyclic group) or a carbonyl group (-CO-) may be contained.

The aliphatic group may have a cyclic structure or a branched chain 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 further includes a ring-assembled hydrocarbon group and a crosslinked ring-type hydrocarbon group. Examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -Includes cyclohexylphenyl group and the like. Examples of the crosslinked cyclic hydrocarbon ring include 2 such as pinan, bornan, norpinan, norbornane, and bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane rings, and , Tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodecane and 4-cyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene rings can be mentioned. In addition, the crosslinked cyclic hydrocarbon ring includes fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and the like. A fused ring in which a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenanthrene ring are condensed is also included.
As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, the aliphatic group does not have an acid group as a substituent.

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

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups can be mentioned. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are independently hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), and alkyl groups having 1 to 6 carbon atoms. Represents (eg, methyl group, ethyl group, propyl group, etc.), Z, or LZ. Here, L and Z are synonymous with those in the above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

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

Examples of typical compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes and the like.
As examples of the representative compounds represented by the formulas (i) to (iii), the compounds described in paragraphs 089 to 093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated in.

In the polymer compound, the hydrophobic structural unit is preferably contained in the range of 10 to 90%, more preferably 20 to 80%, based on the total mass of the polymer compound in terms of mass. Sufficient pattern formation can be obtained when the content is in the above range.

The polymer compound can introduce a functional group capable of forming an interaction with a coloring pigment such as the above-mentioned inorganic pigment. Here, it is preferable that the polymer compound further has a structural unit having a functional group capable of forming an interaction with a coloring pigment such as the above-mentioned inorganic pigment.
Examples of the functional group capable of forming an interaction with the coloring pigment such as the above-mentioned inorganic pigment include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound has an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit having an acid group, a structural unit having a basic group, and a coordinating group, respectively. It is preferable to have a structural unit having the above, or a structural unit having reactivity.
In particular, when the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be imparted with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, in the composition of the present invention, the polymer compound as a dispersant that contributes to the dispersion of the coloring pigment such as the above-mentioned inorganic pigment has alkali solubility. .. The composition containing such a polymer compound has excellent light-shielding properties in the exposed portion and improves the alkali developability of the unexposed portion.
Further, since the polymer compound has a structural unit having an acid group, the polymer compound tends to be easily compatible with the solvent and the coatability tends to be improved.
This is because the acid group in the structural unit having an acid group easily interacts with the coloring pigment such as the above-mentioned inorganic pigment, the polymer compound stably disperses the coloring pigment such as the above-mentioned inorganic pigment, and the above-mentioned inorganic pigment. It is presumed that this is because the viscosity of the polymer compound that disperses the coloring pigment such as the pigment is low, and the polymer compound itself is likely to be stably dispersed.

However, 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 a different structural unit, but the alkali-soluble group as an acid group The structural unit having is a structural unit different from the above-mentioned hydrophobic structural unit (that is, does not correspond to the above-mentioned hydrophobic structural unit).

Examples of the acid group which is a functional group capable of forming an interaction with the coloring pigment such as the above-mentioned inorganic pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group and the like, and preferably. At least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, more preferably one having good adsorption power to a coloring pigment such as the above-mentioned inorganic pigment, and dispersibility of the coloring pigment. At a high point, it is a carboxylic acid group.

When the polymer compound has an acid group, it preferably further has 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 more structural units having an acid group.
The polymer compound may or may not contain a structural unit having an acid group, but when it is contained, the content of the structural unit having an acid group is based on the total mass of the polymer compound in terms of mass. It is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage to the image intensity due to alkaline development.

Examples of the basic group which is a functional group capable of forming an interaction with a coloring pigment such as the above-mentioned inorganic pigment include a primary amino group, a secondary amino group, a tertiary amino group, and a hetero containing an N atom. There are a ring, an amide group, and the like, and the preferred one is a tertiary amino group in that it has good adsorption power to a coloring pigment such as the above-mentioned inorganic pigment and has high dispersibility of the coloring pigment. The polymer compound can have one or more of these basic groups.
The polymer compound may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is the total mass of the polymer compound in terms of mass. On the other hand, it is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppressing developmental inhibition.

Examples of the coordinating group which is a functional group capable of forming an interaction with the coloring pigment such as the above-mentioned inorganic pigment and the functional group having reactivity include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group and an acid anhydride. Things, acidified products and the like can be mentioned. Acetylacetoxy groups are preferable because they have good adsorption power to coloring pigments such as the above-mentioned inorganic pigments and have high dispersibility of coloring pigments. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, but when it is contained, the content of these structural units is determined. In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of suppressing developmental inhibition, with respect to the total mass of the polymer compound.

When the polymer compound in the present invention has a functional group capable of forming an interaction with a coloring pigment such as the above-mentioned inorganic pigment in addition to the graft chain, it can be used with various coloring pigments such as the above-mentioned inorganic pigment as described above. It suffices to contain functional groups capable of forming an interaction, and how these functional groups are introduced is not particularly limited, but the polymer compound has the following general formulas (iv) to (vi). It is preferable to have one or more structural units selected from the structural units derived from the monomer represented by.

In the general formula (iv) to the general formula (vi), R ¹¹ , R ¹² , and R ¹³ independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of carbon atoms. Represents 1 to 6 alkyl groups (eg, methyl group, ethyl group, propyl group, etc.).
In the general formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms independently of each other, and more preferably. Each is an independent hydrogen atom or methyl group. In the general formula (iv), ^{it is particularly preferable that R 12} and R ¹³ are hydrogen atoms, respectively.

_{X 1} in the general formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.
Further, Y in the general formula (v) represents a methine group or a nitrogen atom.

_{Further, L 1} in the general formula (iv) to the general formula (v) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), and divalent aromatic group (eg, substituted alkynylene group). , an arylene group, and a substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), substituted imino bond ^{(-NR 31} '- , wherein R ^{31 'is} an aliphatic group, an aromatic group or a heterocyclic group), carbonyl bond (-CO-), and, combinations thereof and the like.

The divalent aliphatic group may have a cyclic structure or a branched chain 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 the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups and heterocyclic groups.

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

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocycle. One or more of other heterocycles, aliphatic rings or aromatic rings may be condensed on the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups can be mentioned.

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

In the general formula (iv) to the general formula (vi), Z ₁ represents a functional group capable of forming an interaction with a coloring pigment such as the above-mentioned inorganic pigment other than the graft chain, and represents a carboxylic acid group and a tertiary. It is preferably an amino group, more preferably a carboxylic acid group.

In the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms, halogen atoms (for example, fluorine, chlorine, bromine, etc.) and alkyl groups having 1 to 6 carbon atoms (for example, for example). methyl group, ethyl group, propyl group, etc.), - _{Z 1,} or an _L 1 -Z _1. Wherein _{L 1} and _{Z 1} are the same meaning as _{L 1} and _{Z 1} in the above, it is the preferable examples. As R ¹⁴ , R ¹⁵ and R ¹⁶ , each independently has a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the general formula (iv), R ¹¹ , R ¹² and R ¹³ are independently hydrogen atoms or methyl groups, and L ₁ is an alkylene group or an oxyalkylene group. A compound having a divalent linking group containing the above, in which X ₁ is an oxygen atom or an imino group and Z ₁ is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine. The base compound is preferred.
Further, as the monomers represented by the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms or methyl groups, and L ₁ is a single bond or an alkylene group. A compound in which Z ₁ is a carboxylic acid group is preferable.

Representative examples of the monomers (compounds) represented by the general formulas (iv) to the general formulas (vi) are shown below.
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and phthalic anhydride, and a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic anhydride. , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Examples thereof include acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenylmethacrylate and the like.

The content of the structural unit having a functional group capable of forming an interaction with the coloring pigment such as the above-mentioned inorganic pigment is the interaction with the coloring pigment such as the above-mentioned inorganic pigment, the dispersion stability, and the permeability to the developing solution. From the above viewpoint, 0.05 to 90% by mass is preferable, 1.0 to 80% by mass is more preferable, and 10 to 70% by mass is further preferable with respect to the total mass of the polymer compound.

Further, the polymer compound is used for coloring structural units having a graft chain, hydrophobic structural units, and the above-mentioned inorganic pigments, etc., for the purpose of improving various performances such as image intensity, as long as the effects of the present invention are not impaired. A structural unit having a functional group having an affinity with a dispersion medium used for a dispersion (for example, a structural unit having an affinity with a dispersion medium used for a dispersion), which is different from a structural unit having a functional group capable of forming an interaction with a pigment. ) May be further provided.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
As the polymer compound, one or more of these other structural units can be used, and the content thereof is preferably 0% or more and 80% or less with respect to the total mass of the polymer compound in terms of mass. It is particularly preferable that it is 10% or more and 60% or less. Sufficient pattern formation is maintained when the content is in the above range.

The acid value of the polymer compound is preferably in the range of 0 mgKOH / g or more and 160 mgKOH / g or less. From the viewpoint of improving the alkali developability, the lower limit is more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. When the acid value of the polymer compound is 50 mgKOH / g or more, the precipitation of coloring pigments such as the above-mentioned inorganic pigments can be further suppressed, and the number of coarse particles can be reduced (in other words, the amount of particles in the liquid can be reduced). And the stability of the composition over time can be further improved.
Further, from the viewpoint of more effectively suppressing pattern peeling during development when forming a light-shielding film, the upper limit thereof is preferably 140 mgKOH / g or less, and more 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. Further, a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group which is a constituent component of the polymer compound.

The weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene-equivalent value by the GPC (gel permeation chromatography) method from the viewpoint of suppressing pattern peeling during development and developability when forming a light-shielding film. It is preferably 300,000 or more, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferable to have.
In the GPC method, HLC-8020GPC (manufactured by Tosoh Corporation) was used, TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) were used as columns, and THF (tetrahydrofuran, manufactured by Tosoh Corporation) was used as an eluent. ) Is used.

The polymer compound can be synthesized based on a known method, and examples of the solvent used in synthesizing the polymer compound include ethylene dichloride, 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-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, Examples thereof include ethyl acetate, methyl lactate, and ethyl lactate. 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 Kusunoki Kasei Co., Ltd., "Disperbyk-101 (polypolyamine phosphate), 107 (carboxylic acid ester)" and 110 (acid group) manufactured by BYK Chemie. , 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ", EFKA" EFKA4047, 4050-4010-4165 (polyurethane type), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester) Amid), 5765 (high molecular weight polycarboxylate), 6220 (fatty polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fine Techno Co., Ltd." Azispar PB821, PB822, PB880, PB881 ", Kyoeisha "Floren TG-710 (urethane oligomer)" manufactured by Kagaku Co., Ltd., "Polyflow No. 50E, No. 300 (acrylic copolymer)", "Disparon KS-860, 873SN, 874, # 2150 (fat) manufactured by Kusumoto Kasei Co., Ltd." Group polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", Kao" Demor RN, N (naphthalene sulfonate formalin polycondensate), MS, C, SN-B (aromatic sulfonate formalin polycondensate) "," homogenol L-18 (polymer polycarboxylic acid) "," emalgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ", "Acetamine 86 (stearylamine acetate)", manufactured by Nippon Lubrizol Co., Ltd. "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (terminal part) (Polymer having a functional part), 24000, 28000, 32000, 38500 (graft copolymer) ”, Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemical Co., Ltd. ) ”, Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, etc., Shinetsu Chemical Industry Co., Ltd., Organoshiro Xanpolymer KP341, "W001: Cationic Surfactant" manufactured by Yusho Co., Ltd., Polyoxyethylene lauryl ether, Polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, Polyoxyethylene octylphenyl ether, Polyoxyethylene nonylphenyl Nonionic surfactants such as ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA" manufactured by Morishita Sangyo Co., Ltd. -47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 ", Sannopco Co., Ltd." Dispers Aid 6, Dispers Aid 8, Dispers Aid 15, Dispers Aid 9100 " Such as polymer dispersant, manufactured by ADEKA Co., Ltd. "Adecapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P. -123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like. Further, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-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, DISPERBYK-2001 and DISPER, manufactured by Big Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajinomoto Fine Techno Co., Ltd. Ajispar PB821, Ajispar PB822, Ajispar PB881 and the like can be mentioned.
These polymer compounds may be used alone or in combination of two or more.

As a specific example of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.

Further, as the dispersant, in addition to the above-mentioned polymer compound, the graft copolymers of paragraphs 0037 to 0115 of JP-A-2010-106268 (paragraphs 0075 to 0133 of the corresponding US2011 / 0124824) can be used, and these can be used. The contents of are hereby incorporated into this specification.
In addition to the above, it has a side chain structure in which acidic groups of paragraphs 0028 to 0084 of JP2011-153283 (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group. High molecular weight compounds containing the constituents can be used, the contents of which can be incorporated and incorporated herein by reference.

When the composition contains a dispersant, the content of the dispersant is preferably in the range of 0.1 to 1 by mass ratio with respect to the above-mentioned inorganic pigment, and is 0.1 to 0.4. More preferably, it is in the range. By setting the content of the dispersant in the range of 0.1 to 0.4 by mass ratio with respect to the above-mentioned inorganic pigment, the amount of coarse particles in the composition can be further reduced, and the obtained light-shielding film can be obtained. It also has excellent light-shielding performance.

When the composition contains a dispersant, the content of the dispersant is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and 0, based on the total solid content of the composition. .5 to 10% by mass is more preferable.
The dispersant may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range.

<Binder resin>
The composition of the present invention preferably contains a binder resin.
As the binder resin, it is preferable to use a linear organic polymer. As such a linear organic polymer, known ones can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weakly alkaline water is selected to allow water or weakly alkaline water development. Among them, as the binder resin, an alkali-soluble resin (a resin having a group that promotes alkali solubility) is particularly preferable.
The binder resin is a linear organic polymer that promotes at least one alkali solubility in the molecule (preferably a (meth) acrylic copolymer or a molecule having a styrene copolymer as a main chain). It can be appropriately selected from the alkali-soluble resins having a group to be used. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, (meth) acrylic / (meth) acrylamide copolymer resin are preferable, and developability is preferable. From the viewpoint of control, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic / (meth) acrylamide copolymer resin are preferable.
Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid 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 weak alkaline aqueous solution are preferable, and alkali-soluble resins having a structural unit derived from (meth) acrylic acid are more preferable. These acid groups may be only one kind or two or more kinds.

Examples of the binder resin include radical polymers having a carboxylic acid group in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Application Laid-Open No. 54-34327, Japanese Patent Publication No. 58-125777, Japanese Patent Publication No. 54-25957, and Special Publication No. Those described in Kaisho 54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins and acid anhydrides obtained by singly or copolymerizing a monomer having a carboxyl group. Resins obtained by hydrolyzing, half-esterifying, or half-amidizing an acid anhydride unit by singly or copolymerizing a monomer having the above, and epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride. Can be mentioned. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like, and examples of the monomer having an acid anhydride include. Maleic anhydride and the like can be mentioned. Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain is also mentioned as an example. In addition to this, a polymer having a hydroxyl group to which a cyclic acid anhydride is added is useful.
Further, the acetal-modified polyvinyl alcohol-based binder resin having an acid group described in each of the publications such as European Patent No. 9993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318436 has a film strength and developability. It has an excellent balance and is suitable.
Further, as the water-soluble linear organic polymer, polyvinylpyrrolidone, polyethylene oxide and the like are useful. Further, 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 vinyl monomer if necessary] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / necessary Other addition-polymerizable vinyl monomers] The copolymer is suitable because it has an excellent balance of film strength, sensitivity, and developability.
Commercially available products include, for example, Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai Co., Ltd.), and Cyclomer P (ACA) manufactured by Daicel Ornex Co., Ltd. 230AA and the like can be mentioned.

For the production of the binder resin, for example, a known method by a radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent when producing an alkali-soluble resin by a radical polymerization method can be easily set by those skilled in the art.

Further, as the binder resin, it is also preferable to use a polymer having 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 synonymous with the structural unit having a graft chain of 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 phosphoric acid group, a phenolic hydroxyl group, and the like, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Yes, more preferred are carboxylic acid groups.

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

In the general formula (vii) to the general formula (ix), R ²¹ , R ²² , and R ²³ independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of carbon atoms. Represents 1 to 6 alkyl groups (eg, methyl group, ethyl group, propyl group, etc.).
In the general formula (vii) to the general formula (ix), R ²¹ , R ²² , and R ²³ are preferably independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and more preferably. Each is independently a hydrogen atom or a methyl group. In the general formula (vii), ^{it is particularly preferable that R 21} and R ²³ are hydrogen atoms, respectively.

_{X 2} in the general formula (vii) represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.
Further, Y in the general formula (viii) represents a methine group or a nitrogen atom.

_{Further, L 2} in the general formula (vii) to the general formula (ix) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), and divalent aromatic group (eg, substituted alkynylene group). , an arylene group, and a substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), substituted imino bond ^{(-NR 41} '- , Here, R ^41'is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and a combination thereof.

The divalent aliphatic group may have a cyclic structure or a branched chain 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 the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups and heterocyclic groups.

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

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocycle. One or more of other heterocycles, aliphatic rings or aromatic rings may be condensed on the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ⁴² , where R ⁴² is fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups can be mentioned.

L ₂ is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. Further, L ₂ may include a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is _{represented by − (OCH 2} CH ₂ ) n−, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In the general formula (vii) to the general formula (ix), Z ₂ is an acid group, preferably a carboxylic acid group.

In the general formula (ix), R ²⁴ , R ²⁵ , and R ²⁶ are independently hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), and alkyl groups having 1 to 6 carbon atoms. (e.g., methyl group, ethyl group, propyl group, etc.), - represents a _{Z 2,} or _L 2 -Z _2. Here _{L 2} and _{Z 2} has the same meaning as _{L 2} and _{Z 2} in the above, and preferred examples are also the same. As R ²⁴ , R ²⁵ , and R ²⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the general formula (vii), R ²¹ , R ²² , and R ²³ are independently hydrogen atoms or methyl groups, and L ₂ is an alkylene group or an oxyalkylene group. A compound having a divalent linking group containing the above, in which X ₂ is an oxygen atom or an imino group and Z ₂ is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (vii), 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. The base compound is preferred.
Further, as the monomer represented by the general formula (ix), a compound in which R ²⁴ , R ²⁵ , and R ²⁶ are independently hydrogen atoms or methyl groups and Z ₂ is a carboxylic acid group is preferable.

The binder resin can be synthesized by the same method as the dispersant having a structural unit having a graft chain described above, and has the same preferable acid value and weight average molecular weight.

The binder resin may have one or more structural units having an acid group.
The content of the structural unit having an acid group is preferably 5 to 95% with respect to the total mass of the binder resin in terms of mass, and more preferably from the viewpoint of suppressing damage to the image intensity due to alkaline development. It is 10 to 90%.

The content of the binder resin in the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.3 to 25% by mass, based on the total solid content of the composition.
The binder resin may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range.

<Polymerizable compound>
The composition of the present invention preferably contains a polymerizable compound.
The polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably two or more, further 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) acryloyl group.

The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer, and a mixture thereof, and a multimer thereof. Monomers are preferred.
The molecular weight of the polymerizable compound is preferably 100 to 3000, more preferably 250 to 1500.
The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters, amides, and multimers thereof. These are preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or the above-mentioned unsaturated product. A dehydration condensation reaction product of a carboxylic acid ester or amide and a monofunctional or polyfunctional carboxylic acid is also preferably used. Further, a reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, a halogen group or a tosyloxy group. Reactants of unsaturated carboxylic acid esters or amides having a releasable substituent such as, etc. with monofunctional or polyfunctional alcohols, amines, thiols, etc. are also suitable. Further, instead of the above-mentioned unsaturated carboxylic acid, it is also possible to use a compound group in which a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like is replaced.
As these specific compounds, the compounds described in paragraphs [0905] to [0108] of JP-A-2009-288705 can also be preferably used in the present invention.

In the present invention, as the polymerizable compound, a compound having 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 an example thereof, the compounds described in paragraphs 0227 of JP2013-29760A and paragraphs 0254 to 0257 of JP2008-292970 can be referred to, and the contents thereof are incorporated in the present specification.

The polymerizable compounds are dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). , Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd., and structures in which these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues (for example, SR454, SR499 commercially available from Sartmer). ) Is preferable. These oligomer types can also be used. Further, 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 preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A polymerizable compound having a group is more preferable, and more preferably, in this ester, 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 properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

As the polymerizable compound, a compound having a caprolactone structure is also a preferable embodiment.
The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc. Ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Be done. Among them, a compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.

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 the following general formulas (Z). It is a group represented by -2), and the residue is a group represented by the following general formula (Z-3).

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

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

The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, formula Number of groups represented by (Z-2) = 2, ^{compound in which R 1} is all hydrogen atoms), DPCA-30 (same formula, m = 1, number of groups represented by formula (Z-2)) = 3, R ¹
Is a compound in which all are hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, ^{compound in which R 1} is all hydrogen atoms), DPCA-120 (In the same formula, m = 2, the number of groups represented by the formula (Z-2) = 6, and R ¹ is a compound in which all hydrogen atoms are present) and the like.

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

In the general formulas (Z-4) and (Z-5), E is independently − ((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) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each of m 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) acryloyl groups is 5 or 6, each of n 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), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
In the general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.
_{Further,-((CH 2} ) _y CH ₂ O)-or ((CH ₂ ) _y CH (CH ₃ ) O)-in the general formula (Z-4) or the general formula (Z-5) is an oxygen atom. A form in which the end on the side binds to X is preferable.

The compounds represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), all 6 Xs are acryloyl groups, in the general formula (Z-5), all 6 Xs are acryloyl groups, and 6 Xs. Of these, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a configuration, the 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, more preferably 50% by mass or more.

For the compound represented by the general formula (Z-4) or the general formula (Z-5), ethylene oxide or propylene oxide is ring-opened and added to pentaerythritol or dipentaerythritol, which is a conventionally known step. It can be synthesized from a step of binding a ring-opening skeleton by a reaction and a step of reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, 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.
Specifically, compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as “exemplified compounds (a) to (f)”) can be mentioned, and among them, the exemplary compounds (a), (B), (e), and (f) are preferable.

Commercially available products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and Nippon Kayaku. Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains, manufactured by Co., Ltd.

Examples of the polymerizable compound include urethane acrylates as described in JP-A-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. , Urethane compounds having an ethylene oxide-based 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 are also suitable. .. In addition, addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, are used. Therefore, a composition having a very excellent photosensitive speed can be obtained.
Commercially available products include urethane oligomer UA-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- Examples thereof include 306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoei Co., Ltd.).

Further, the polymerizable compound used in the present invention preferably has an SP (solubility parameter) value of 9.50 or more, more preferably 10.40 or more, and more preferably 10.60 or more. More preferred.
Unless otherwise specified, the SP value in the present specification is obtained by the Hoy method (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal ^1/2 cm ^-3/2 .

Further, the composition preferably has a polymerizable compound having a cardo skeleton from the viewpoint of improving the development residue.
As the polymerizable compound having a cardo skeleton, a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

General formula (Q3)

In the above general formula (Q3), Ar ^{11 to} Ar ¹⁴ each independently represent an aryl group containing a benzene ring surrounded by a broken line. X ^{1 to} X ⁴ each represent a substituent having a polymerizable group independently, and the 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 independently represent substituents, 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 Ar ^{11 to} Ar ^{14, respectively.} It is a value obtained by subtracting a, b, c or d from the number of substituents that can be possessed. However, when Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each containing a benzene ring surrounded by a broken line as one of the fused rings, X ^{1 to} X ⁴ and R ^{1 to} R ⁴ are respectively. It may be independently replaced with a benzene ring surrounded by a broken line, or may be replaced with a ring other than the benzene ring surrounded by a broken line.

In the above general formula (Q3), the ^{aryl group containing the benzene ring represented by Ar 11 to} Ar ¹⁴ is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms. (For example, a phenyl group or a naphthyl group) is more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is further preferable.

In the above general formula (Q3), X ^{1 to} X ⁴ each represent a substituent having a polymerizable group independently, and the 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 is preferably an aliphatic group having a polymerizable group.
The ^{aliphatic group having a polymerizable group represented by X 1 to} X ⁴ is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and has 2 to 10 carbon atoms. It is more preferably an alkylene group, and even more preferably an alkylene group having 2 to 5 carbon atoms.
Further, 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. it is preferable that the, -CH not adjacent in the aliphatic group 2 _- is more preferably is substituted with an oxygen atom or a sulfur atom, -CH 2 nonadjacent in the aliphatic group _- is It is more preferred that it is replaced with an oxygen atom. The ^{aliphatic group having a polymerizable group represented by X 1 to} X ⁴ is preferably substituted at 1 to 2 sites by a hetero atom, more preferably at 1 site by a hetero atom, and Ar ^{11 to} Ar. It is more preferable that one location adjacent to the aryl group containing the benzene ring surrounded by the broken line represented by ^{14 is substituted with a heteroatom.}
The ^{polymerizable group contained in the aliphatic group having a polymerizable group represented by X 1 to} X ⁴ is a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter, also referred to as a radical polymerizable group and a cationic polymerizable group, respectively). Is preferable.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and as a suitable one, a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned, and specifically, a polymerizable group having an ethylenically unsaturated bond can be mentioned. Examples include a vinyl group and a (meth) acryloyloxy group. Among them, the (meth) acryloyloxy group is preferable, and the acryloyloxy group is more preferable.
As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spirolethoester group, and vinyloxy. The group etc. can be mentioned. Of these, an alicyclic ether group and a vinyloxy group are preferable, and an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable.
The polymerizable group contained in the substituents contained in Ar ^{1 to} Ar ^{4 is preferably a radical polymerizable group.}
Two or more of Ar ¹ to Ar ⁴ include a substituent having a polymerizable ^group, preferably contains a substituent with 2-4 polymerizable group of Ar 1 ~Ar ^4, Ar 1 ~Ar ^{It is more preferable that 2 or 3 of 4} contain a substituent having a polymerizable group, and further preferably 2 of Ar ^{1 to} Ar ⁴ contain a substituent having a polymerizable group.
When Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each containing a benzene ring independently surrounded by a broken line as one of the fused rings, X ^{1 to} X ⁴ are benzenes independently surrounded by a broken line. It may be replaced with a ring or a ring other than the benzene ring surrounded by a broken line.

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

In the above general formula (Q3), R ^{1 to} R ⁴ each independently represent a substituent. The ^{substituent represented by R 1 to} R ⁴ is not particularly limited, and for example, a halogen atom, an alkyl halide group, an alkyl group, an alkenyl group, an acyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an aryl group and a hetero Examples thereof include an aryl group and an alicyclic group. The ^{substituent represented by R 1 to} R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group having 1 to 5 carbon atoms and an alkoxy group or a phenyl group having 1 to 5 carbon atoms. , Methyl group, methoxy group or phenyl group is more preferable.
In the above general formula (Q3), when Ars ^{11 to Ar 14} are polycyclic aromatic hydrocarbon groups each containing a benzene ring surrounded by a broken line as one of the fused rings, R ^{1 to} R ⁴ are respectively. It may be independently replaced with a benzene ring surrounded by a broken line, or may be replaced with a ring other than the benzene ring surrounded by a broken line.

In the above general formula (Q3), e, f, g and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g and h are substituents that ^{Ar 11 to} Ar ^{14 can have, respectively.} It is a value obtained by subtracting a, b, c or d from the number of.
e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and even more preferably 0.
When Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each containing a benzene ring independently surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1. , 0 is more preferable.

Examples of the compound represented by the above formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. As the polymerizable compound having a 9,9-bisarylfluorene skeleton, the compounds described in JP-A-2010-254732 can also be preferably used.

Examples of the polymerizable compound having such a cardo skeleton include, but are not limited to, Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).

When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, further preferably 20% by mass or less.
The polymerizable compound may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range.

<Polymerization initiator>
The composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited and may be appropriately selected from known polymerization initiators. For example, a photosensitive initiator (so-called photopolymerization initiator) is preferable.
When the composition of the present invention contains a photopolymerization initiator and the above-mentioned polymerizable compound in addition to the above-mentioned inorganic pigment and black dye, it is cured by irradiation with active light or radiation, and thus is "photosensitive". Sometimes referred to as a "composition".
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light rays visible from the ultraviolet region are preferable. Further, it may be an activator that causes some action with a photoexcited sensitizer to generate an active radical, or may be an initiator that initiates cationic polymerization depending on the type of monomer.
Further, the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the 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, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like can be mentioned. Examples of the halogenated hydrocarbon compound having a triazine skeleton include Wakabayashi et al., Bull. Chem. Soc. Japanese Patent No. 42, 2924 (1969), British Patent No. 1388492, Compound described in JP-A-53-133428, German Patent No. 3337024, F.I. C. J. by Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-58241, compound described in JP-A-5-281728, compound described in JP-A-5-341920, US Pat. No. 4,212,976. Examples include the compounds described in the book.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triallylimidazole dimer, onium A compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxaziazole compound, and a 3-aryl-substituted coumarin compound. preferable.

More preferably, it is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzophenone compound, an acetophenone compound, and a trihalomethyltriazine compound or an α-aminoketone. Examples thereof include at least one compound selected from the group consisting of a compound, an oxime compound, a triallyl imidazole dimer, and a benzophenone compound.

In particular, when the composition of the present invention is used for producing a light-shielding film for a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape. It is important to be done. From this point of view, it is preferable to use an oxime compound as the photopolymerization initiator. In particular, when forming a fine pattern in a solid-state image sensor, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in consideration of these points, it is preferable to use an oxime compound as the photopolymerization initiator in order to form a fine pattern such as a solid-state image sensor. Further, by using the oxime compound, the color transfer property can be further improved.
As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine-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) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm, can also be used.
As the acylphosphine-based initiator, a commercially available IRGACURE-819 or DAROCUR-TPO (trade name: both manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound (oxime-based initiator). In particular, an oxime compound is preferable because it has high sensitivity, high polymerization efficiency, can be cured regardless of the concentration of the coloring material, and has a high concentration of the coloring material and is easy to design.
As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used.
Examples of the oxime compound that can be preferably used in the present invention include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, and the like. 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane -2-one, 2-ethoxycarbonyloxyimine-1-phenylpropan-1-one and the like can be mentioned.
In addition, J. C. S. Perkin II (1979) pp. 1653-1660), J. Mol. C. S. Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A-2000-66385, compounds described in JP-A-2000-80068, JP-A-2004-534977, and JP-A-2006-342166 can also be mentioned.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. In addition, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCLUDS NCI-930 (manufactured by ADEKA), N-1919 (carbazole / oxime ester skeleton-containing photoinitiator). (Manufactured by ADEKA) can also be used.

Further, as an oxime compound other than the above, the compound described in JP-A-2009-5199004 in which an oxime is linked to the N-position of carbazole, and the compound described in US Pat. No. 7,626,957 in which a heterosubstituted group is introduced at a benzophenone moiety. Compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye moiety, keto-oxime compounds described in International Publication Patent No. 2009-131189, triazine skeleton and oxime skeleton having the same molecule. The compound described in JP-A-7556910, the compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source, and the like contained therein may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, the contents of which are incorporated herein by reference.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. The NO bond of the oxime may be an (E) -form oxime compound, a (Z) -form oxime compound, or a mixture of the (E) -form and the (Z) -form. ..

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

In the present invention, an oxime compound having a fluorine atom can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in JP-A-2014-500852, and the compounds described in JP-A-2013-164471. C-3) and the like can be mentioned. This content is incorporated herein by reference.

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

In the formula (1), R ¹ and R ² are independently 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 an aryl group having 6 to 30 carbon atoms. Represents an arylalkyl group having 7 to 30 carbon atoms, ^{and when R 1} and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are independent of each other. It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond or carbonyl. Indicates a group.

In the formula ^(2), R ^1, R 2, ^{R 3} and ^{R 4} have the same meanings as ^{R 1,} R 2, ^{R 3} and ^{R 4} in Formula (1), ^{R 5 is} -R 6, -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSO R ⁶ , -CN, Halogen Represents an atom or hydroxyl group, and R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. X represents a direct bond or a carbonyl group, and a represents an integer from 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably methyl group, ethyl group, n-propyl group, i-propyl, cyclohexyl group or phenyl group, respectively. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xsilyl group. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. Direct binding is preferable for X.
Specific examples of the compounds represented by the formulas (1) and (2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein by reference.

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and further preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, from the viewpoint of sensitivity, 5,000 to 200. It is more preferably 000.
A known method can be used for the molar extinction coefficient of the compound. For example, an ultraviolet-visible spectrophotometer (Varian Cary-5 spctrophotometer) is used with an ethyl acetate solvent at a concentration of 0.01 g / L. It is preferable to measure.
The photopolymerization initiator used in the present invention may be used in combination of two or more, if necessary.

When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30% by mass, preferably 1 to 25% by mass, based on the total solid content in the composition. It is more preferably%, and further preferably 1 to 10% by mass. The composition of the present invention may contain only one type of polymerization initiator, or may contain two or more types of polymerization initiators. When two or more types are included, the total amount is preferably in the above range.

<Organic solvent>
The composition of the present invention preferably contains an organic solvent.
Examples of organic solvents include acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, etc. Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate , And ethyl lactate, etc., but are not limited thereto.

The composition of the present invention may contain one kind of organic solvent or two or more kinds of organic solvents, but when the composition of the present invention is prepared, the particles of the above-mentioned inorganic pigment may be contained. It is preferable to contain two or more kinds of organic solvents from the viewpoint that the diameter fluctuation can be suppressed.
When two or more kinds of organic solvents are contained, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -It is preferably composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

When the composition of the present invention contains an organic solvent, the content of the organic solvent is preferably 10 to 90% by mass, more preferably 60 to 90% by mass, based on the total mass of the composition. preferable. 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 water content is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.8% by mass, and 0.1 to 0% by mass with respect to 100% by mass of the composition. It is more preferably 7% by mass. When the water content is within the above range, the occurrence of pinholes when the light-shielding film is produced can be suppressed, and the moisture resistance of the light-shielding film can be improved.

<Other ingredients>
The composition of the present invention may contain components other than those described above.
Hereinafter, each component will be described 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 linked to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms thereof is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
Further, in order to improve the adhesion between the substrate and the light-shielding film, the silane coupling agent preferably does not contain fluorine atoms and silicon atoms (excluding silicon atoms to which a hydrolyzable group is bonded). A silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and a branched alkyl group having 3 or more carbon atoms It is desirable not to include it.

The silane coupling agent preferably has a group represented by the following formula (Z). * Represents the bond position.
Formula (Z) * -Si- (R _Z1 ) ₃
In formula (Z), R _Z1 represents a hydrolyzable group, the definition of which is as described above.

The silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group. The curable functional group may be directly bonded to the silicon atom or may be bonded to the silicon atom via the linking group.
A radically polymerizable group is also mentioned as a preferable embodiment of the curable functional group contained in the silane coupling agent.

The molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1000 from the viewpoint of handleability, and 270 or more is preferable, and 270 to 1000 is more preferable, from the viewpoint of more excellent effect of the present invention.

One of the preferred embodiments of the silane coupling agent is the silane coupling agent X represented by the formula (W).
Equation (W) R _Z2- Lz-Si- (R _Z1 ) ₃
R _z1 represents a hydrolyzable group, the definition of which is as described above.
R _z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. If Lz represents a divalent linking group, the divalent As the linking group, an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 ^{-, -} CONR _{^{12 -, - CO -, -}} CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof. Among them, at least one selected from the group consisting of an alkylene group optionally substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group optionally substituted with a halogen atom having 6 to 12 carbon atoms, or at least one selected from the group. these groups and ^{-NR 12 -, - CONR 12 -} , - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S-, and SO ₂ -, at least selected from the group consisting of group is preferred, which consist of a combination of one group, an alkylene group optionally substituted with a halogen atom having 2 to 10 carbon _{atoms, -CO 2 -, - O -} , - CO -, - CONR 12 -, or , A group consisting of a combination of these groups is more preferable. Here, 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.) and N-β-aminoethyl-γ-aminopropyl-trimethoxy. Silane (Shin-Etsu Chemical Co., Ltd. trade name KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBE-602), γ-aminopropyl-trimethoxysilane (Shin-Etsu Chemical Co., Ltd. product name KBM-903), γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. product name KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. product name) KBM-503), glycidoxyoctyltrimethoxysilane (trade name: KBM-4803 manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

Another preferred embodiment of the silane coupling agent is a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom. Can be mentioned.
The silane coupling agent Y may have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different. The atoms and substituents that can be bonded are hydrogen atom, halogen atom, hydroxyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group, alkynyl group, aryl group, alkyl group and / or amino group substitutable with aryl group, silyl. Examples thereof include a group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group. These substituents further include an amino group, a halogen atom, a sulfonamide group, which can be substituted with a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group. It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, or a salt thereof, a sulfo group, a salt thereof or the like.
At least one hydrolyzable group is bonded to the silicon atom. The definition of hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by the formula (Z).

The silane coupling agent Y preferably has at least one nitrogen atom in the molecule, and the nitrogen atom preferably exists in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group. The structure of the amino group may be present in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may be present as a substituted amino group such as aniline.
Here, 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 the substituents that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom and a sulfonamide. Examples thereof include a group, an alkoxycarbonyl group, a carbonyloxy group, an amide group, a urea group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxyl group, or a salt thereof, a sulfo group and the like.
Further, the nitrogen atom is preferably bonded to a curable functional group via an arbitrary organic linking group. Preferred organic linking groups include the above-mentioned nitrogen atom and substituents that can be introduced into the organic group bonded thereto.

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

The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but the above range (preferably 270 or more) can be mentioned.

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, based on the total solid content in the composition. 0 to 6% by mass is more preferable.

The composition of the present invention may contain one type of silane coupling agent alone, or may contain two or more types. When the composition contains two or more kinds of silane coupling agents, the total 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 nonionic 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 (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness or the liquid saving property is further improved. be able to. That is, when a film is formed using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. It is improved and the applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

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 uniformity in the thickness of the coating film or liquid saving, and has good solubility in the composition.

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, F780, RS-72-K (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC -101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, Examples thereof include PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used. A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The fluorosurfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compounds is preferably 3,000 to 50,000, for example 14,000.
Further, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as a fluorine-based surfactant. As a specific example, the compounds described in JP-A-2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, for example, Megafuck RS-101, RS-102, RS-718K, or RS-, manufactured by DIC Corporation. 72-K and the like can be mentioned.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, and polyoxyethylene. Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF Pluronic L10, L31, L61, L62, Examples thereof include 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), and NCW-101, manufactured by Wako Pure Chemical Industries, Ltd. NCW-1001 and NCW-1002 can also be used.

Specifically, as cationic surfactants, phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (meth) acrylic acid-based (meth) Co) Polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.

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

Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Co., Ltd.), KP341, KF6001, KF6002 (manufactured by Shinetsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (all manufactured by Big Chemie) and the like.

Only one type of surfactant may be used, or two or more types may be combined. The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition of the present invention.

<Polymerization inhibitor>
The composition preferably contains a polymerization inhibitor. The composition has better stability over time when it contains a polymerization inhibitor.
The content of the polymerization inhibitor is preferably 0.00055 to 0.055% by mass, more preferably 0.0015 to 0.01% by mass, based on the total solid content of the composition.

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 the polymerization inhibitor include phenol-based compounds, quinone-based compounds, hindered amine-based compounds, phenothiazine-based compounds, and nitrobenzene-based compounds. The above compounds may be used alone or in combination of two or more.

Examples of the phenolic compound include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, and 2,6-di. -Tert-Butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, pentaerythritol tetrakis (3,5-di- tert-Butyl-4-hydroxyhydrosinname), 4-methoxy-1-naphthol, 1,4-dihydroxynaphthalene and the like.

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

In the formula (IH-1), R _{1 to} R ₅ are independently hydrogen atoms, alkyl groups, alkenyl groups, hydroxy groups, amino groups, aryl groups, alkoxy groups, carboxyl groups, alkoxycarbonyl groups, or acyls. Represents a group. R _{1 to} R ₅ may be connected to each other to form a ring.

_{Examples of R 1 to} R ₅ in the formula (IH-1) include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group and an ethyl group), and an alkoxy group having 1 to 5 carbon atoms (for example, methoxy). Groups and ethoxy groups, etc.), alkenyl groups having 2 to 4 carbon atoms (for example, vinyl groups, etc.), or phenyl groups are preferable.
Among them, R ₁ and R ₅ are independent of each other, and a hydrogen atom or a tert-butyl group is more preferable, R ₂ and R ₄ are more preferably a _{hydrogen atom, R 3} is a hydrogen atom and an alkyl having 1 to 5 carbon atoms. A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.

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

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

_{R 6} in the formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Among them, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.
_{Further, R 7 to} R ₁₀ in the formula (IH-2) independently represent a hydrogen atom or an alkyl group. As the _{alkyl group represented by R 7 to} R ₁₀ , an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

As the polymerization inhibitor, each of the above compounds may be used alone, in combination of two, or in combination of three or more.
The polymerization inhibitor preferably contains a phenolic compound. Among them, from the viewpoint of stability over time, the polymerization inhibitor preferably contains two or more kinds of phenolic compounds.
Further, the polymerization inhibitor preferably contains a phenol-based compound and a hindered amine-based compound from the viewpoint of stability over time.

<UV absorber>
The composition may contain an ultraviolet absorber. As a result, the shape of the pattern of the cured film can be made more excellent (fine).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples thereof, compounds of paragraphs 0137 to 0142 of JP2012-068418 (corresponding paragraphs 027 to 0254 of US2012 / 0068292) can be used, and these contents can be incorporated and incorporated in the present specification. ..
In addition, a diethylamino-phenylsulfonyl UV absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.1 to 5% by mass, based on the total solid content of the composition. As the ultraviolet absorber, each of the above compounds may be used alone or in combination of two or more.

(Organic pigment)
The composition may contain an organic pigment.
Examples of organic pigments include Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24. , 31, 32, 34, 35, 35: 1,36, 36: 1,37, 37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77 , 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 , 126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171 , 172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc .;
C. I. 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. ;
C. I. 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.;
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment Violet 1,19,23,27,32,37,42, etc .;
C. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,60,64,66,79,80, etc .;
Can be mentioned. The pigment may be used alone or in combination of two or more.

<Colored dye>
Examples of the dye include Japanese Patent Application Laid-Open No. 64-9043, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent Application Laid-Open No. 2592207, and US Pat. No. 4,808.501. , U.S. Pat. No. 5,667,920, U.S. Patent No. 505950, U.S. Patent No. 566,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6- Dyes disclosed in Japanese Patent Application Laid-Open No. 194828 can be used. When classified as a chemical structure, pyrazole azo compound, pyromethene compound, anilino azo compound, triphenylmethane compound, anthraquinone compound, benzylidene compound, oxonor compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyropyrazole azomethine compound, etc. Can be used. Moreover, you may use a dye multimer as a dye. Examples of the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097. Further, a chromatic dye polymerizable dye having a polymerizable property in the molecule may be used, and examples of commercially available products include the RDW series manufactured by Wako Pure Chemical Industries, Ltd.

<Infrared absorber>
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in a wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm). Preferably, the infrared absorber is a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm.
Examples of the colorant having such spectral characteristics include a pyrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an iminium compound, a thiol complex compound, a transition metal oxide compound, a squarylium compound, a naphthalocyanine compound, and a quaterylene. Examples thereof include compounds, dithiol metal complex compounds, and croconium compounds.
As the phthalocyanine compound, the naphthalocyanine compound, the iminium compound, the cyanine compound, the squalium compound, and the croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750 may be used, and the contents thereof are described herein. Incorporated in. As the cyanine compound, for example, "functional dye, Shin Ogawara / Ken Matsuoka / Eijiro Kitao / Tsuneaki Hirashima, Kodansha Scientific" can be referred to, and this content is incorporated in the present specification.

Examples of the colorant having the above spectral characteristics include the compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or the compounds disclosed in paragraphs 0027-0062 of JP-A-2002-146254, JP-A-2011-164583. Near-infrared absorbing particles having a number average agglomerated particle diameter of 5 to 200 nm, which are composed of crystallites of an oxide containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication, can also be used.
The infrared absorber may be used alone or in combination of two or more.

When the composition of the present invention contains a colorant other than the above-mentioned inorganic pigment, the content of the colorant is preferably 1 to 10% by mass with respect to the total solid content of the composition. ~ 7% by mass is more preferable.

In addition to the above components, the following components may be further added to the composition of the present invention. Examples thereof include sensitizers, pigment dispersants other than those described above, co-sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, fat sensitizers, and the like. , Adhesion promoters to substrate surfaces and other auxiliaries (eg conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, and , Chain transfer agent, etc.) and other known additives may be added as needed.
These components are, for example, paragraph numbers 0183 to 0228 of JP2012-003225A ([0237] to [0309] of the corresponding US Patent Application Publication No. 2013/0034812), JP2008-250074. The descriptions of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 of JP2013-195480, etc. can be taken into consideration, and these contents are incorporated in the present 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 performance of the light-shielding film is further improved. Further, 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 the stability over time becomes good. 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 composition>
The composition of the present invention can be produced by mixing the above-mentioned various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
In the production of the composition, various components constituting the composition may be collectively blended, or the various components may be dissolved or dispersed in an organic solvent and then sequentially blended. Further, the charging order and working conditions at the time of blending are not particularly limited.
Further, in the process of dispersing the pigment, examples of the mechanical force used for dispersing the pigment include compression, squeezing, impact, shearing and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization and ultrasonic dispersion. In addition, "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and practical comprehensive data collection of industrial applications, published by Management Development Center" The processes and dispersers described in "Published by the Department, October 10, 1978" can be preferably used.
Further, in the process of dispersing the pigment, the pigment may be miniaturized by a salt milling step. As the materials, equipment, processing conditions, etc. used in the salt milling step, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used, for example.
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. The filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like. Examples thereof include a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and further preferably about 0.3 to 0. It is 7 μm. Within this range, it is possible to reliably remove fine foreign substances such as impurities or agglomerates contained in the pigment while suppressing the filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the pore diameters of the second and subsequent filters are the same or larger than the pore diameter of the first filtering. Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., and the like. ..
As the second filter, one formed of the same material as the first filter described above can be used. The pore size of the second filter is preferably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

[Curing film (light-shielding film)]
The cured film of the present invention can be obtained by using the above-mentioned composition. The cured film of the present invention mainly contains the above-mentioned inorganic pigment (preferably a black inorganic pigment, more preferably a pigment containing a nitride or an oxynitride) and a black dye.
The cured film of the present invention is preferably used as a light-shielding film, and specifically, is preferably used 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 around the image sensor obtained by using the composition of the present invention has excellent light-shielding performance. That is, there is no deterioration in the light-shielding performance in a specific wavelength region, and the minimum optical density is in a range in which sufficient light-shielding ability can be provided 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 intended use, and is not particularly limited.
When the cured film of the present invention is, for example, a light-shielding film around an image sensor, the film thickness of the light-shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, preferably 0.2 μm. More than 30 μm is more preferable, 0.2 μm or more and 25 μm or less is further preferable, 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 further preferably 0.1 mm or more and 3.5 mm or less.

<Manufacturing method of cured film (light-shielding film)>
Next, the method for producing the cured film (light-shielding film) of the present invention is not particularly limited, and a known method can be adopted. Hereinafter, as a typical example, a method for producing a patterned cured film will be described in detail.

The method for producing a patterned cured film of the present invention is a step of applying the composition of the present invention on a substrate to form a composition layer (coating film) (hereinafter, appropriately abbreviated as "composition layer forming step"). ), The step of exposing the composition layer through a mask (hereinafter, appropriately abbreviated as "exposure step"), and the development of the composition layer after exposure to form a patterned cured film. It is characterized by including a step of performing (hereinafter, appropriately abbreviated as "development step").

Specifically, the composition of the present invention is applied directly or via another layer onto a substrate to form a composition layer (composition layer forming step), and the composition is exposed through a predetermined mask pattern. By curing only the light-irradiated composition layer portion (exposure step) and developing with a developing solution (development step), a patterned cured film composed of pixels can be formed.
Hereinafter, each step will be described.

(Composition layer forming step)
In the composition layer forming step, the composition of the present invention is applied onto a substrate to form a composition layer (coating film).

As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, etc., those having a transparent conductive film attached thereto, photoelectric used for a solid-state image sensor, etc. Examples thereof include a conversion element substrate (for example, a silicon substrate), a CCD substrate, and a CMOS substrate.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface of the substrate.

As a method for applying the composition of the present invention on a substrate, various coating methods such as slit coating, inkjet method, rotary coating, cast coating, roll coating, and screen printing method can be applied.

When producing a light-shielding film around an image sensor, the coating film thickness of the composition is preferably 0.35 μm or more and 1.5 μm or less, more preferably 0.40 μm or more and 1.0 μm or less, from the viewpoint of resolution and developability. preferable.

The composition applied on the substrate is usually dried at 70 ° C. or higher and 110 ° C. or lower under the conditions of about 2 minutes or more and 4 minutes or less. Thereby, the composition layer can be formed.

(Exposure process)
In the exposure step, the composition layer (coating film) formed in the composition layer forming step is exposed through a mask, and only the light-irradiated coating film portion is cured.
The exposure is preferably carried out by irradiation with active light rays or radiation, and in particular, ultraviolet rays such as g-line, h-line, or i-line are more preferable. The irradiation intensity is preferably ^{5~1500mJ / cm 2, 10~1000mJ / cm} 2 is more preferable.

(Development process)
Following the exposure step, an alkaline development process (development step) is performed to elute the unirradiated portion of the light in the exposure step into an alkaline aqueous solution. As a result, only the photocured portion (light-irradiated coating film portion) remains.
As the developing solution, an organic alkaline developing solution that does not cause damage to the underlying circuit or the like is desirable. The developing temperature is usually 20 to 30 ° C., and the developing time is 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. As the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, or sodium metaphosphate is used at a concentration of 0.001 to 10% by mass, preferably 0.01 to. An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned. Examples of the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline, pyrrol, piperidine, or 1,8-diazabicyclo- [5.4. .0] Examples thereof include an alkaline aqueous solution in which an alkaline compound such as -7-undecene is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the alkaline aqueous solution. When a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

As the developing method, for example, a paddle developing method, a shower developing method, or the like can be used.

In the method for producing a cured film of the present invention, after performing the composition layer forming step, the exposure step, and the developing step described above, the formed cured film is cured by heating and / or exposure, if necessary. It may include a curing step.

[Color filter, light-shielding film]
The cured film formed by using the composition of the present invention can be preferably used as a pixel black matrix of a color filter or a light-shielding film applied to various members in an image display device or a sensor module described later.

(Color filter)
The color filter can be suitably used for a solid-state image sensor such as a CCD or CMOS, and is particularly suitable for a high-resolution CCD or CMOS having more than 1 million pixels. The color filter can be used, for example, by arranging it between a light receiving portion of each pixel constituting the CCD or CMOS and a microlens for condensing light. Further, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include the devices described in JP-A-2012-227478 and JP-A-2014-179757.
The form 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 suitably used as, for example, a pixel black matrix of a color filter.

(Shading film)
The light-shielding film is formed on various members (for example, an infrared light cut filter, an outer peripheral portion of a solid-state image sensor, a wafer-level lens outer peripheral portion, a back surface of a solid-state image sensor, etc.) in an image display device or a sensor module. Can be used.
Further, a light-shielding film may be formed on at least a part of the surface of the infrared light cut filter to form an 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, more preferably 0.2 to 10 μm. The above-mentioned thickness is an average thickness, which is a value obtained by measuring the thickness of any five or more points of the light-shielding film and arithmetically averaging them.
The reflectance of the light-shielding film is preferably 10% or less, more preferably 8% or less, further preferably 6% or less, and particularly preferably 4% or less. The reflectance of the light-shielding film is a value obtained by incident light of 400 to 700 nm into the light-shielding film at an incident angle of 5 ° and measuring the reflectance with a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. ..

[Solid image sensor]
The solid-state image sensor of the present invention includes the solid-state image sensor as described above, and includes the cured film (color filter, light-shielding film, etc.) on the outer peripheral portion or the back surface of the solid-state image sensor. The configuration of the solid-state image sensor of the present invention is not particularly limited as long as it has the cured film and the solid-state image sensor, and examples thereof include the following configurations.

A transfer electrode made of a plurality of photodiodes, polyvinyl, etc. constituting a light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) is provided on a substrate, and the photodiode receives light on the photodiode and the transfer electrode. It has a light-shielding film with only a portion open, a device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part on the light-shielding film, and a color filter is placed on the device protective film. It is a configuration to have.
Further, there is a configuration in which a condensing means (for example, a microlens or the like; the same applies hereinafter) is provided on the device protective layer and below the color filter (on the side closer to the substrate), a configuration having a condensing means on the color filter, and the like. You may.

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

For details on the definition of display devices or the details of each display device, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", "Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd.)" (Issued in the first year) ”etc. The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-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, aspects of applying the color filter of the present invention to a liquid crystal display device will be described in detail.
The color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. A color TFT liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Shuppan Co., Ltd. in 1996)". Further, the color filter of the present invention is a liquid crystal display device having an enlarged viewing angle such as a transverse electric field drive method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domine Vertical Element), or STN (STN). Super-Twisted Nematic, TN (Twisted Nematic), VA (Vertical Element), OCS (on-chip spacer), FFS (Fringe field switching), or R-OCB (Reflect) Applicable to Remote.
Further, the color filter of the present invention can also be used in a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter are required to have the required characteristics for the interlayer insulating film, that is, low dielectric constant and resistance to the stripping liquid, in addition to the usual required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA type liquid crystal display device having high resolution and excellent long-term durability. In addition, in order to satisfy the required characteristics of low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD Display-Latest Trends in Technology and Market- (Toray Research Center Research Division, 2001)".

In addition to the color filter of the present invention, the liquid crystal display device of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these materials, for example, "'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima Co., Ltd., published in 1994)", "2003 Liquid Crystal Related Market Current Status and Future Prospects (Volume 2)" (Omote Yoshikichi (Omote Yoshikichi) Fuji Chimera Research Institute, Inc., published in 2003) ”.
Regarding backlight, SID meeting Digest 1380 (2005) (A.Konno et.al) or Monthly Display December 2005 issue, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. It is described in.

Further, the cured film of the present invention is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone or a digital camera; an OA (Office Automation) device such as a printer compound machine or a scanner; a surveillance camera, a bar code reader, an automatic cash deposit. Payers (ATMs) or industrial equipment such as personal authentication using high-speed cameras or face image authentication; in-vehicle camera equipment; medical camera equipment such as endoscopes, capsule endoscopes or catheters; biosensors Optical filters used in space equipment such as biosensors, military reconnaissance cameras, stereoscopic map cameras, meteorological or oceanographic observation cameras, land resource exploration cameras, or exploration cameras for space astronomical or deep space targets. Alternatively, it can be used as a light-shielding member or a light-shielding layer of a module, and further as an antireflection member or an antireflection layer.

Further, the cured film of the present invention can also be used for applications such as micro LED (Light Emitting Diode) or micro OLED (Organic Light Emitting Diode). Although not particularly limited, it is preferably used for an optical filter or an optical film used for a micro LED or a micro OLED, as well as a member for which a light-shielding function or an antireflection function is imparted.
Examples of the micro LED or the micro OLED include those described in the special table 2015-500562 and the special table 2014-533890.

Further, the cured film obtained by curing the composition of the present invention can also be used for applications such as quantum dot displays. Although not particularly limited, it is suitably used for an optical or optical film used for a quantum dot display, as well as a member for which a light-shielding function or an antireflection function is imparted.
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. The ones described are mentioned.

Hereinafter, the present invention will be described in more detail based on Examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
Unless otherwise specified, "parts" and "%" are based on mass.

〔Composition〕
Hereinafter, in preparing the compositions of Examples and Comparative Examples, first, each component contained in the composition will be described.

<Inorganic pigment (pigment containing nitride or oxynitride)>
(TiN-1) Manufactured by Nisshin Engineering Co., Ltd. (Titanium nitride-containing particles, BET specific surface area 55 m ² / g, average primary particle size 24.2 nm)
(TiN-2) Made by Hefei, trade name "TiN 20 nm" (titanium nitride-containing particles, average primary particle diameter 41.7 nm)
(TiN-3) Made by Mitsubishi Materials Corporation, trade name "13MT" (titanium nitride-containing particles, average primary particle size 75 nm)

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

47 g of the intermediate (C) described in paragraph [0340] of JP-A-2016-69656 was dissolved in 500 ml of N, N-dimethylacetamide, and the internal temperature was cooled to 0 ° C. 5.5 g of a methacrylate chloride (manufactured by Tokyo Kasei) was added dropwise thereto while maintaining an internal temperature of 5 ° C. or lower, and then the reaction was carried out at room temperature for 90 minutes. The obtained reaction solution was poured into a large excess of ethyl acetate and filtered off. This was dissolved in chloroform, purified by column chromatography, concentrated to dryness by a rotary evaporator, and the following polymerizable group-containing compound was taken out (yield 12%).

Next, 5 g of the above-mentioned polymerizable group-containing compound was dissolved in 45 g of N, N-dimethylacetamide in a flask and heated to 70 ° C. Under a nitrogen atmosphere, a solution of 0.5 g of a thermal polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) in 45 g of N, N-dimethylacetamide was added dropwise over 30 minutes. After the dropping, the 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 obtained oligomer was analyzed by GPC, and it was confirmed that the average value of the repeating unit n was 6.3.

5 g of the oligomer obtained above was dissolved in 500 ml of N, N-dimethylacetamide, and the internal temperature was cooled to 0 ° C. Here, 5 g of a methacrylate chloride (manufactured by Tokyo Kasei) was added dropwise while maintaining an internal temperature of 5 ° C. or lower, and then the reaction was carried out at room temperature for 90 minutes. The obtained reaction solution was poured into a large excess of ethyl acetate, filtered off, and the following polymerizable group-containing xanthene oligomer was taken out (yield 98%).

(Dye B)
A xanthene skeleton compound having no polymerizable group represented by the following structure was obtained according to Japanese Patent Application Laid-Open No. 2013-253170.

(Dye C)
According to Japanese Patent Application Laid-Open 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.

<Binder resin>
As the binder resin, the following resin A, which is an alkali-soluble resin, was used.
-Resin A (Acrycure RD-F8 manufactured by Nippon Shokubai, see the formula below)

<Dispersant>
As the dispersant, dispersants A to E having the following structures were used. In the dispersants A, B, and D, the numerical value described in each structural unit is intended to be the mass% of each structural unit with respect to all the structural units. Further, in the dispersant C, the numerical values (a to e) described in each structural unit are intended to be the molar ratio of each structural unit to all the structural units, and x and y are intended to be the number of linkages. Further, in the dispersant E, the numerical value described in the linking group linked to Z means the number of linked groups linked to Z.

<Polymerizable compound>
The following polymerizable compound M1 was used as the polymerizable compound.
-Polymerizable compound M1
(Manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA", see the formula below)

<Polymerization initiator>
The following oxime-based initiators were used as the polymerization initiators.
-OXE-02: Irgacare OXE02 (trade name, manufactured by BASF Japan Ltd.)

<Organic solvent>
The following organic solvents were used as the organic solvents.
-PGMEA: Propylene glycol monomethyl ether acetate-Cyclopentanone

<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)

The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the various resins 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 with a stirrer (Eurostar manufactured by IKA) for 15 minutes to obtain a dispersion. Next, the obtained dispersion was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Symmal Enterprises Co., Ltd. to obtain a pigment dispersion. The ratio (mass ratio) of the dispersant to the pigment containing nitride or oxynitride (hereinafter, also referred to as “D / P”) shall be the ratio shown in each Example and Comparative Example in Table 1. Was added to.
(Dispersion condition)
-Bead diameter: φ0.05 mm, (Nikkato zirconia beads, YTZ)
-Bead filling rate: 65% by volume
・ Mill peripheral speed: 10 m / sec
・ Separator peripheral speed: 13 m / s
-Amount of mixed liquid to be dispersed: 15 kg
・ Circulation flow rate (pump supply amount): 90 kg / hour
-Treatment liquid temperature: 19 to 21 ° C
・ Cooling water: Water ・ Treatment time: About 22 hours

<Preparation of composition>
Next, the pigment dispersion, the black dye, the binder resin, the polymerizable compound, the polymerization initiator, the surfactant and the organic solvent are mixed and stirred, and the compositions of Examples and Comparative Examples shown in Table 1 below are mixed and stirred. Got As for the black dye, a composition in which the “carry-on agent” described in the table and the black dye were mixed was prepared in advance, and this was mixed with other components such as a pigment dispersion.
The content (mass%) of each component contained in each composition of Examples and Comparative Examples is shown in Table 1.

<Measurement of water content in composition>
The water content of each composition of Examples and Comparative Examples was measured by MKV-710 (trade name, manufactured by Kyoto Denshi Kogyo Co., Ltd.) using the Karl Fischer method as a measurement principle. The results are shown in Table 1.
The water content in the composition is derived from various raw materials.

[Evaluation test]
The following evaluation tests were carried out for each of the compositions of Examples and Comparative Examples.

<Number of particles>
Each composition of Example and Comparative Example was placed in a 100 mL bloom bottle and allowed 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 this evaluation liquid was counted by a flow-type particle image analyzer (trade name “FPIA”, manufactured by Malvern).

<Spectroscopic (light-shielding)>
The composition is applied by spin coating on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) at a rotation speed of 1.0 μm to form a coating film, which is then placed on a hot plate. A dry film was obtained by heat-treating the coating film at 100 ° C. for 2 minutes. The OD (optical density) of the obtained dried film was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the minimum OD at a wavelength of 400 to 1200 nm, the spectroscopy (light-shielding property) was evaluated according to the following criteria. At this time, by preparing the composition of the composition, 50% by mass in the solid content of the coating liquid was used as the 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>
The compositions of Examples and Comparative Examples were stored at 23 ° C. for 10 days and then at 7 ° C. for 90 days. 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 type viscometer") under the conditions of a rotation speed of 10 rpm and 23 ° C. Then, the value (%) of [{(viscosity after aging-viscosity immediately after liquid preparation) / viscosity immediately after liquid preparation} × 100] was calculated. The evaluation criteria are as follows.
"A": within ± 3% "B": over ± 3%, within ± 5% "C": over ± 5%, within ± 10% "D": over ± 10%

<Reworkability>
Using each of the compositions of Examples and Comparative Examples, the electrode pattern (copper) was formed on the surface of the electrode pattern of the silicon wafer so that the dry film thickness of the coating film of each composition was 0.7 μm. , Each composition was spin-coated. Then, the silicon wafer on which each composition was coated was heat-treated (prebaked) for 120 seconds using a hot plate at 100 ° C. to form a coating film.
Next, the coating film was exposed at an exposure amount of ^{500 mJ / cm 2} through an Island pattern mask having a pattern of 20 μm square at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.).
Each of the compositions of Examples and Comparative Examples is a negative type photosensitive resin composition in which the exposed portion is cured.
After that, the silicon wafer substrate on which the exposed coating film was formed was placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fujifilm Electronics Co., Ltd.) was placed. Paddle development was performed at 23 ° C. for 60 seconds using an organic alkaline developer (manufactured by Materials Co., Ltd.).
Next, the silicon wafer after paddle development is fixed to the horizontal rotary table by a vacuum chuck method, and while rotating the silicon wafer substrate at a rotation speed of 50 rpm by a rotating device, pure water is ejected from above the center of rotation in a shower shape. Was supplied to the wafer and rinsed, and then spray-dried to form a wafer having a frame-like pattern.

Next, the obtained wafer having a frame-like pattern is immersed in a 25% aqueous solution of TMAH (tetramethylammonium hydroxide) at 85 ° C. for 5 hours, and immersed in a 2 L DIW (pure water) tank at room temperature for 2 minutes. Rinse treatment was performed by doing so. The reworkability was evaluated by observing the state of removal of the frame-shaped pattern from the obtained washed wafer with an optical microscope (manufactured by Olympus Corporation, trade name "LEXT OLS4500"). The evaluation criteria are as follows.
"A": No pattern is observed "B": Particle-like removal residue is observed in 5% or less of the pattern-forming region "C": Particle-like removal residue is observed in more than 5% and 10% or less of the pattern-forming area. Observed "D": Particle-like removal residue is observed in more than 10% of the pattern formation area, or a pattern or a part of the pattern is observed.

<Heat resistance>
The composition is applied by spin coating on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) at a rotation speed of 1.0 μm to form a coating film, which is then placed on a hot plate. A dry film was obtained by heat-treating the coating film at 100 ° C. for 2 minutes. The OD (optical density) of the obtained dried film was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Spectroscopy (light-shielding property) was evaluated based on the minimum OD at a wavelength of 400 to 1200 nm, and the minimum OD before the heat resistance test was used. The dried film was heat-treated on a hot plate at 265 ° C. for 10 minutes, and spectroscopic evaluation was performed in the same manner as described above to obtain the minimum OD after the heat resistance test. The amount of spectral fluctuation in the heat resistance test was calculated by the following formula and evaluated.
"Variation amount = {(minimum OD after heat resistance test-minimum OD before heat resistance test) / minimum OD before heat resistance test} x 100"
"A": within ± 3% "B": over ± 3%, within ± 5% "C": over ± 5%, within ± 10% "D": over ± 10%

<Patterning property (resolution)>
Using the compositions of Examples and Comparative Examples, a coating film was formed on the image sensor device substrate by a spin coater. Next, the obtained coating film was prebaked at 100 ° C. for 2 minutes on a hot plate. Subsequently, the coating film that has undergone the prebaking treatment is exposed using an i-line exposure apparatus (FPA, manufactured by Canon), and further developed to cover the outer peripheral portion of the light receiving portion on the substrate except for the dicing line and the electrode portion. At the same time as forming the light-shielding film, 20 alignment marks having a line width of 20 μm were formed on the substrate.
The resolution was evaluated by observing the number of formed alignment marks using an optical microscope.
"A": 20 marks were formed.
"B": 19 marks were formed.
"C": 18 marks were formed.
"D": 17 or less marks could be formed.

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

From the results in Table 1, it was confirmed that the light-shielding film formed from the compositions 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.

Comparing Examples 1, 6, 7 and 8, the content of the black dye is 0.3 or less (preferably 0.25 or less, more preferably 0.25 or less) by mass ratio with respect to the nitride or the pigment containing the oxynitride. It was shown that the reworkability was further improved when the value was 0.2 or less.

Comparing Examples 1, 4 and 5, it was shown that the black dye having a polymerizable group further improved the reworkability, heat resistance and patterning property. Further, in Example 5 using the azo dye, it was confirmed that the heat resistance was excellent.

Comparing Examples 1 and 9 to 12, it was shown 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, in Example 1, it was shown that the amount of particles in the liquid was smaller and the patterning property was also excellent by using the dispersant A containing benzyl methacrylate, which is a hydrophobic component.

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

Comparing Examples 1, 20 and 21, it is shown that when the pigment content is 30% by mass or more with respect to the solid content, the light-shielding performance of the obtained light-shielding film is further improved, and the heat resistance is also improved. Was done. On the other hand, it was shown that when the content of the pigment was 70% by mass or less with respect to the solid content, the reworkability and the patterning property were further improved.

(Example 22)
A composition was prepared and evaluated in the same manner except that the polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the dye A in Example 1. It was found to have the same performance as in Example 1.

(Example 23)
The same applies except that the dye A and the polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) were used instead of the dye A in Example 1 and used at a mass ratio of 1: 1. When the composition was prepared and evaluated, it was found to have the same performance as that of Example 1.

(Example 24)
The same applies except that the dye B and the polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) were used instead of the dye B in Example 4, and the mass ratio was 1: 1. When the composition was prepared and evaluated, a better evaluation than that of Example 4 was obtained. Specifically, the reworkability evaluation, the heat resistance evaluation, and the patterning property evaluation were all "B". I understood.

(Example 25)
In Example 1, instead of using TiN-1, TiN-1 and carbon black (trade name "Color Black S170", manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m ² / g, gas black method) The composition was prepared and evaluated in the same manner except that it was used in a mass ratio of 7: 3, and it was found that the composition had the same performance as that of Example 1.

(Example 26)
In Example 1, instead of using 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 9: 1. When the composition was prepared and evaluated in the same manner except that it was used as in Example 1, it was found that the composition had the same performance as that of Example 1, and that a light-shielding film having a deeper black tint could be obtained. From this result, it is presumed that the desired effect of the present application can be obtained even when used in combination with other organic pigments or chromatic dyes.

Claims (20)

A composition containing an inorganic pigment and a black dye. The composition according to claim 1, wherein the inorganic pigment is a pigment containing a nitride or an oxynitride. The composition according to claim 1 or 2, wherein the black dye has a polymerizable group. The composition according to claim 3, wherein the polymerizable group is an acryloyl group or a methacryloyl group. The composition according to any one of claims 1 to 4, wherein the black dye is a xanthene dye or an azo dye. The composition according to any one of claims 1 to 5, wherein the black dye is a dye multimer. The composition according to any one of claims 1 to 6, further comprising a dispersant. The composition according to claim 7, wherein the acid value of the dispersant is 50 mgKOH / g or more. The composition according to claim 7 or 8, wherein the dispersant has at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, methyl polyacrylate and polymethyl methacrylate. The composition according to any one of claims 1 to 9, further comprising a polymerizable compound and a polymerization initiator. The composition according to any one of claims 1 to 10, further comprising an organic solvent. The composition according to any one of claims 1 to 11, further comprising an alkali-soluble resin. The composition according to any one of claims 1 to 12, wherein the content of the black dye is 0.3 or less by mass ratio with respect to the content of the inorganic pigment. The composition according to any one of claims 1 to 13, wherein the solid content is 10 to 40% by mass with respect to the total mass of the composition. The composition according to any one of claims 1 to 14, wherein the content of the inorganic pigment is 30 to 70% by mass with respect to the solid content. A cured film obtained by using the composition according to any one of claims 1 to 15. A color filter having the cured film according to claim 16. A light-shielding film having the cured film according to claim 16. A solid-state image sensor having the cured film according to claim 16. An image display device having the cured film according to claim 16.