JPWO2017208771A1 - Composition, cured film, color filter, light shielding film, solid-state imaging device and image display device - Google Patents

Abstract

An object of the present invention is to provide a composition capable of forming a light shielding film excellent in light shielding performance. Another object of the present invention is to provide a cured film excellent in light blocking performance, a color filter provided with the cured film, a light blocking film, a solid-state imaging device, and an image display device. The composition of the present invention contains an inorganic pigment and a black dye.

Description

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

Black light shielding films are used in various applications. For example, a light shielding film is used in a solid-state imaging device. In general, a solid-state imaging device includes an imaging lens, and solid-state imaging such as a CCD (Charge Coupled Device) disposed behind the imaging lens and a Complementary Metal-Oxide Semiconductor (CMOS). A device (hereinafter, a solid-state imaging device is also referred to as an "image sensor") and a circuit board on which the solid-state imaging device is mounted. In this solid-state imaging device, noise may occur due to reflection of visible light. Therefore, in order to suppress the generation of noise, a predetermined light shielding film may be provided in the solid-state imaging device.
Further, as another application of the light shielding film, a so-called black matrix can also be mentioned.

  Various compositions have been proposed as compositions for forming such a light shielding film. For example, in Patent Document 1, “When the black resin composition for resin black matrix containing at least a light shielding material, a resin and a solvent and containing at least titanium nitride particles as a light shielding material, CuKα ray is used as an X-ray source A black resin composition for a resin black matrix, wherein 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. 1).

Patent No. 5136139 gazette

The inventors of the present invention manufactured a light shielding film of a color filter disposed in a solid-state imaging device, a liquid crystal imaging device, etc. using a black composition prepared based on Patent Document 1, and examined various performances thereof 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 to improve the light shielding performance, the content of the dispersant in the composition becomes relatively large, and the light shielding performance of the obtained light shielding film is attributed to this. It may decrease.
Therefore, it is desirable to improve the light shielding performance of the light shielding film by means other than increasing the pigment concentration.

An object of this invention is to provide the composition which can form the light shielding film excellent in light shielding performance in view of the said situation.
Another object of the present invention is to provide a cured film excellent in light blocking performance, a color filter provided with the cured film, a light blocking film, a solid-state imaging device, and an image display device.

As a result of intensive studies to achieve the above problems, the present inventors found that inorganic pigments (preferably black inorganic pigments described later, more preferably pigments containing nitride or oxynitride), black dyes, and the like It has been found that the above-mentioned problems can be solved by using a composition containing the present invention, and the present invention has been completed.
That is, it discovered that the said objective could be achieved by the following structures.

(1) A composition comprising 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 as described in (1) or (2) in which the said black dye has a polymeric 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 in any one of (1)-(5) whose said black dye is a dye multimer.
(7) The composition according to any one of (1) to (6), further comprising a dispersant.
(8) The composition as described in (7) whose acid value of the said dispersing agent 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 poly methyl methacrylate object.
(10) The composition according to any one of (1) to (9), further comprising a polymerizable compound and a polymerization initiator.
(11) The composition according to any one of (1) to (10), further comprising an organic solvent.
(12) The composition according to any one of (1) to (11), further comprising an alkali-soluble resin.
(13) The composition according to any one of (1) to (12), wherein the content of the black dye is 0.3 or less by mass ratio to the content of the inorganic pigment.
(14) The composition according to any one of (1) to (13), which has a solid content of 10 to 40% by mass based on the total mass of the composition.
(15) The composition in any one of (1)-(14) whose content of the said inorganic pigment is 30-70 mass% with respect to solid content.
(16) A cured film obtained using the composition according to any one of (1) to (15).
(17) A color filter having the cured film according to (16).
The light shielding film which has a cured film as described in (18) and (16).
The solid-state imaging device which has a cured film as described in (19) and (16).
The image display apparatus which has a cured film as described in (20) and (16).

ADVANTAGE OF THE INVENTION According to this invention, the composition which can form the light shielding film excellent in light shielding performance can be provided.
Further, according to the present invention, it is possible to provide a cured film excellent in light blocking performance, a color filter provided with the cured film, a light blocking film, a solid-state imaging device, and an image display device.

The present invention will be described below.
The numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
In the notation of groups (atomic groups) in the present specification, notations not describing substitution and non-substitution include 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).
In the present specification, the term "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like. . In the present invention, light means actinic rays or radiation. Unless otherwise specified, the "exposure" in the present specification means not only exposure by far ultraviolet rays represented by a mercury lamp or excimer laser, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. The 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. 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. The polymerizable group refers to a group involved in the 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 oxynitride), and a black dye.
According to the composition of the present invention, a light shielding film excellent in light shielding performance can be formed. That is, according to the composition of the present invention, there is no decrease in light shielding performance in a specific wavelength region, and the lowest optical density (hereinafter also referred to as "minimum OD value") in a predetermined region (for example, visible light region-1200 nm). It is possible to form a light shielding film in 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 inorganic pigment concentration is increased 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 is relatively large, which is attributed to this. As a result, the light shielding performance of the obtained light shielding film may be lowered. However, since the composition of the present invention does not require a dispersant and contains a black dye having absorption over substantially the entire wavelength range of visible light, the composition of the present invention does not increase other components such as a dispersant. It is possible to improve the optical density.
In particular, it has been found that when a xanthene-based dye or an azo-based dye as described later is used, it is possible to form a light-shielding film which is excellent in light-shielding performance and excellent in resolution.

The present inventors have now 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, when the black dye has a polymerizable group, the dye is incorporated into the matrix constituting the film via the polymerizable group. Dyes are generally known to be inferior in heat resistance to pigments, and when a dye is used as a 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 to each other by the polymerizable group, whereby the heat resistance is improved.
In recent years, after the light shielding film is formed 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. So-called reworkability is required.
The inventor also found that the reworkability is also improved by chemically bonding the matrix constituting the membrane and the black dye through the polymerizable group as described above. That is, for example, a color filter (cured film) produced using a composition containing an inorganic pigment, a black dye having a polymerizable group, an alkali-soluble resin, etc. is, for example, TMAH (tetramethylammonium hydroxide) etc. In the case of removal with an alkaline aqueous solution, the black dye is chemically bonded to the film comprising the alkali-soluble resin, so that the dye can be removed (stripped) 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 aqueous alkaline solution, and therefore, the residue alone on the solid-state imaging device As it adheres, removal becomes difficult. That is, it is inferior to rework property.

  In addition, 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 also confirmed that.

  Also, the black dye is preferably a dye multimer. The heat resistance is further improved by the black dye being a dye multimer. Among them, the black dye is desirably a dye multimer having a polymerizable group.

  Hereinafter, the components contained in the composition and the components that may 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 known inorganic pigments can be used.
As inorganic pigments, for example, carbon black, silica, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow ( Zinc yellow 1 species, zinc yellow 2 species), ultramarine blue, Prussia blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chromium titanium yellow, chromium green, peacock, Victoria green, bitumen (irrespective of Prussian blue) And vanadium zirconium blue, chromium tin pink, porcelain enamel, salmon pink and the like. In addition, black inorganic pigments are preferable, and as the inorganic pigments, carbon black, titanium black, and the like in that a composition capable of forming a cured film having a high optical density at least at a content can be obtained. Metal pigments and the like are preferred. The metal pigment includes, for example, metal oxides 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. And metal nitrides and metal oxynitrides.
As inorganic pigments, titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium oxynitride, vanadium oxynitride, chromium oxide, chromium nitride, chromium oxynitride, iron oxide, iron oxynitride, metal pigments containing silver, It is preferable that it is at least 1 sort (s) selected from the group which consists 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 pigments containing nitride or oxynitride described later.
The inorganic pigments 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 further improved. On the other hand, when the content of the inorganic pigment is 70% by mass or less with respect to the solid content, reworkability and patternability are further improved. The content of the inorganic pigment is more preferably 35 to 70% by mass, 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, for example, by the following method.

The average primary particle size of the inorganic pigment can be measured using a transmission electron microscope (TEM). As a transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
Maximum length of particle image obtained using transmission electron microscope (Dmax: maximum length at two points on the contour of particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length When sandwiching the image, the shortest length connecting two straight lines vertically was measured, and the geometric mean value (Dmax × DV-max) ^1/2 was defined as the particle diameter. The particle diameter of 100 particles is measured by this method, and the arithmetic mean value is taken as an average particle diameter to obtain an average primary particle diameter of the pigment.

(Pigment containing nitride or oxynitride)
As mentioned above, the inorganic pigment is preferably a pigment containing a nitride or an oxynitride.
Examples of pigments containing nitride or oxynitride include pigments such as titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium oxynitride, vanadium oxynitride, iron oxynitride, and tungsten oxynitride. Be Among them, those having absorption in the wavelength range of 400 to 1200 nm are preferable. The absorption wavelength and the 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 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. Although it does not specifically limit as titanium nitride or titanium oxynitride, The titanium nitride as described in the international publication 2008/123097, the international publication 2010/147098, and the patent 5577659 can be used.
In addition, in pigments containing nitride or oxynitride, the content of nitride or oxynitride (for example, when the pigment contains titanium nitride, the content of titanium nitride) is the total mass of the pigment. The content is preferably 10 to 100% by mass, and more preferably 20 to 100% by mass.

-Titanium black Hereinafter, titanium black particles which are titanium oxynitride pigments will be described.
The surface of the titanium black particles can be modified as needed for the purpose of improving dispersibility or suppressing aggregation. It is possible to coat titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconium oxide. In addition, a surface treatment of titanium black is also possible with a water repellent material as disclosed 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 be 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, for example, by the method described above.

The specific surface area of titanium black is not particularly limited, but since the water repellency after surface treatment of titanium black with a water repellent becomes a predetermined performance, the value measured by the BET (Brunauer, Emmett, Teller) method is 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 products of titanium black include titanium black 10S, 12S, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), and Tilack (Tilack) D) (trade name: manufactured by Akaho Kasei Co., Ltd.) and the like.

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a substance to be dispersed in the composition, and the content ratio (Si / Ti) of Si atoms to Ti atoms in the substance to be dispersed is 0.05 or more in mass conversion. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is more preferable.
Here, the above-mentioned to-be-dispersed body includes both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In order to change the Si / Ti of the material to be dispersed (for example, 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 subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.) to obtain mainly titanium black particles. A dispersed material containing Si and Ti as components can be obtained. The reduction treatment is performed under an atmosphere of reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo). The titanium oxide is not limited to this, but the primary particle size is preferably 5 nm to 70 nm, more preferably 7 nm to 50 nm, and any crystal system such as rutile or anatase can be suitably used. These mixed crystals may be used.
Commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade name: manufactured by Evonik).
Dispersion of titanium oxide and silica particles may use a dispersant. As a dispersing agent, what is demonstrated by the column of the dispersing agent mentioned later is mentioned.
The above dispersion may be carried out in a solvent. The solvent may, for example, be water or an organic solvent. What is demonstrated by the column of the organic solvent mentioned later is mentioned.
For example, titanium black in which Si / Ti is adjusted to, for example, 0.05 or more is produced, for example, by the method described in paragraph No. [0005] and paragraph Nos. [0016] to [0021] of JP 2008-266045A. can do.

A composition containing the material to be dispersed by adjusting the content ratio (Si / Ti) of Si atom to Ti atom in the material to be dispersed containing titanium black and Si atoms to a suitable range (for example, 0.05 or more) When a light shielding film is formed using a material, the residue derived from the composition outside the formation region of the light shielding film is reduced. In addition, a residue contains the component derived from compositions, such as a titanium black particle | grain, and a resin component.
Although the reason why the residue is reduced is unclear, the above-mentioned material to be dispersed 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 this material to be dispersed In addition, it is presumed that the adsorptivity of the entire film to the substrate is reduced, which contributes to the improvement of the development removability of the uncured composition (particularly, titanium black) in the formation of the light-shielding film.
Moreover, since titanium black is excellent in the light shielding property to light in a wide wavelength range from ultraviolet light to infrared light, a dispersion containing the above-described titanium black and Si atoms (preferably, Si / Ti is mass converted The light shielding film formed by using the one having 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 material to be dispersed is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP-A-2013-249417. ) Can be used.
In addition, for the material to be dispersed contained in the light shielding film obtained by curing the composition, the content ratio (Si / Ti) of Si atom to Ti atom in the material to be dispersed is 0.05 or more In order to judge, the method (2) as described in Paragraph 0035 of JP, 2013-249417, A is used.

In the dispersion containing titanium black and Si atoms, titanium black can be used as described above.
In this case, it is preferable that the to-be-dispersed body which consists of titanium black occupies 50 mass% or more in all to-be-dispersed bodies.
Further, in this material to be dispersed, other colorants (organic pigments, dyes, etc.) may be optionally used together with titanium black, as long as the effects of the present invention are not impaired, for the purpose of adjusting light shielding properties etc. Good.
Hereinafter, materials to be used when introducing Si atoms into the material to be dispersed will be described. When introducing Si atoms into the material to be dispersed, a Si-containing substance such as silica may be used.
Examples of the 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.
Furthermore, 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, so it is preferable to use fine particle type silica as the silica particles. In addition, as an example of silica of a fine particle type, the silica of Unexamined-Japanese-Patent No. 2013-249417, Paragraph is mentioned, for example, and these content is integrated in this specification.

-Titanium nitride containing particle Moreover, as a pigment containing nitride or oxynitride, titanium nitride containing particle can also be used, for example.
For the production of titanium nitride-containing particles, a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable from the viewpoints of low contamination with impurities, easy uniformity of particle diameter, high productivity, and the like.
As a method of generating thermal plasma, direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, etc. may be mentioned, and radio frequency plasma with less contamination of impurities from the electrode is preferable. As a specific production method of titanium nitride-containing particles by thermal plasma method, for example, titanium powder is evaporated by high frequency thermal plasma, nitrogen is introduced as a carrier gas into the apparatus, and titanium powder is nitrided in the cooling process. , Methods of synthesizing titanium nitride-containing particles, and the like. The thermal plasma method is not limited to the above.
In addition, the titanium nitride-containing particles are obtained by using a thermal plasma method, and the diffraction angle 2θ (details will be described later) of the peak derived from the (200) plane when the CuKα ray is used as the X-ray source is It becomes easy to adjust in the range of 42.8 ° or more and 43.5 ° or less.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 50 to 85% by mass, and 55 to 85% by mass, based on the total mass of the titanium nitride-containing particles. More preferably, the content is 55 to 80% by mass. The content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP (high 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, and 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 inert gas melting-thermal conductivity method.

  In the titanium nitride-containing particles, the diffraction angle 2θ of the peak derived from the (200) plane when the X-ray diffraction spectrum is measured using the CuKα ray as the X-ray source is more than 42.8 ° and 43.5 ° or less preferable. A light shielding film obtained using a composition containing titanium nitride-containing particles having such characteristics has an OD value that is an appropriate numerical value, and is excellent in patterning property (resolution).

As described above, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particle is preferably more than 42.8 ° and not more than 43.5 °, and is 42.85 to 43.3 °. Is more preferable, and 42.9 to 43.2 ° is more preferable.
The titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become prominent when oxygen is mixed in during their synthesis, or when the particle diameter is small, but due to oxidation of the particle surface, etc. Some oxygen atoms may be contained.
However, a smaller amount of oxygen contained in the titanium nitride-containing particles is preferable because a higher OD value (optical density) can be obtained. Further, the titanium nitride-containing particles, preferably contains no TiO ₂ as an auxiliary component. When titanium nitride-containing particles contain titanium oxide TiO ₂ as an accessory component, a peak derived from anatase-type TiO ₂ (101) has a peak at 2θ = 25.3 ° as the strongest peak and is rutile TiO ₂ ( A peak derived from 110) is observed in the vicinity of 2θ = 27.4 °. However, since TiO ₂ is white and causes a reduction in the light shielding properties of the black matrix, it is preferable that it be reduced to such an extent that it is not observed as a peak.

  The crystallite size constituting the titanium nitride-containing particles can be determined from the half-width of the X-ray diffraction peak, and is calculated using Scheller'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, is 42~55m ² / g Is more preferred. By setting the specific surface area of the titanium nitride-containing particles to 40 to 60 m ² / g, the light shielding film obtained has an appropriate range of an OD (optical density) value, and is excellent in patterning property (resolution).

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

(Other pigments)
The composition of the present invention may also contain inorganic pigments other than those listed above as inorganic pigments. Other pigments include, for example, tungsten compounds and metal borides.
Tungsten compounds and metal borides are characterized by having high absorption for infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light shielding properties (shielding properties for infrared rays)). Tungsten compounds and metal borides have low absorption to visible light as compared to the light shielding property to infrared light. Tungsten compounds and metal borides are also less absorbed to short-wave light than visible regions used for exposure, such as high-pressure mercury lamps, KrF and ArF used for image formation.

As a tungsten compound, a tungsten oxide type compound, a tungsten boride type compound, a tungsten sulfide type compound and the like can be mentioned, and a tungsten oxide type compound represented by the following general formula (composition formula) (I) is preferable.
M _x W _y O _z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0

  Examples of the metal of M include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi and the like can be mentioned, with preference given to alkali metals. 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 still more preferably Cs.

When x / y is 0.001 or more, infrared rays can be shielded sufficiently, and when 1.1 or less, generation of an impurity phase in the tungsten compound is more reliably avoided. it 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 compounds represented by the above general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , or Ba _0.33 WO _{3 and the} like. 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 in the form of fine particles. The average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and still more 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 at the time of production and the like.

  Moreover, it is possible to use 2 or more types of tungsten compounds.

Tungsten compounds are commercially available, 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).
In addition, a tungsten oxide-based compound can also be obtained, for example, as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Moreover, as metal borides, lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (N dB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), boride Titanium (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), borided One or more of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB) and tungsten boride (W ₂ B ₅ ) can be mentioned, and lanthanum boride (LaB ₆ ) is preferred. .

  The metal boride is preferably in the form of fine particles. The average particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and still more 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 at the time of production and the like.

  Moreover, it is possible to use 2 or more types of metal borides.

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

The inorganic pigment may be an extender pigment. Examples of such an extender pigment include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite.
When using an extender pigment 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 combination 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, 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 with their surfaces modified with polymers.

<Black dye>
The composition of the present invention comprises a black dye.
As the black dye, those having absorption over the entire wavelength range of visible light (380 nm to 780 nm) are preferable.
As a black dye, for example, C.I. I. In addition to direct blacks 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168 and 171, etc., known dyes exhibiting black color can be mentioned. In addition, as the black dye, xanthene dyes, azo dyes, and aniline dyes may also be mentioned.
The black dye preferably has an optical density of 2 or more, more preferably 4 or more, particularly in the entire wavelength range of 400 to 500 nm.

The black dye preferably has a polymerizable group. The heat resistance and reworkability can be improved by the black dye having a polymerizable group.
The polymerizable group is a functional group capable of forming a chemical bond by energy application, and examples thereof include a radically polymerizable group and a cationically polymerizable group. Among them, a radically polymerizable group is preferable from the viewpoint of more excellent reactivity. Examples of the radically polymerizable group include acryloyl group, methacryloyl group, acrylic acid ester group (acryloyloxy group), methacrylic acid ester group (methacryloyloxy group), itaconic acid ester group, crotonic acid ester group, isocrotonic acid ester group, In addition to unsaturated carboxylic acid ester groups such as a maleic acid ester group, styryl groups, vinyl groups, acrylamide groups, methacrylamide groups and the like can be mentioned. Among these, a methacryloyl group or an acryloyl group is more preferable from the viewpoint of further improving the resolution of the coating film.
In the black dye, two or more kinds of polymerizable groups may be contained. In addition, 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 any of a dye monomer and a dye multimer, but is preferably a dye multimer from the viewpoint of further improving heat resistance.
Among them, a dye polymer having a structural unit represented by the following general formula (1) is preferable, and a dye having a polymerizable group and having a structural unit represented by the following general formula (1) More preferably, it is a multimer.

[In general formula (1), R ^{A to} R ^C each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, L represents a single bond or a divalent linking group, and Dye Represents a dye residue obtained by removing one arbitrary hydrogen atom from the black dye. ]

Each of ^{RA to RC} independently represents 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.
Examples of the divalent linking group include, for example, -O-, -S-, -NR ^1- , -CO-, vinylene group, ethynylene group, alkylene group (cyclic, branched or linear) And an arylene group, a heteroarylene group, or a divalent group formed by combining these.
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, an I atom And aryl groups (preferably aryl groups 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 any one hydrogen atom from the black dye.
Although it does not specifically limit as a black dye, The black dye mentioned above is mentioned. Among them, xanthene dyes or azo dyes are preferable from the viewpoint of being able to form a light shielding film excellent in light shielding performance.
When the dye polymer having the structural unit represented by the above general formula (1) has a polymerizable group, the position of the polymerizable group in the dye polymer is not particularly limited. As the position of the polymerizable group in the dye polymer, for example, Dye may have a polymerizable group or may have a structural unit having a polymerizable group. In addition, that Dye has a polymeric group means that the dye residue represented by Dye which one arbitrary hydrogen atom was remove | eliminated from black dye has a polymeric 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 based on all structural units, 85 % 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 which has a structural unit represented by the said General formula (1) can be manufactured by a well-known method.

When the black dye is a dye multimer, its molecular weight is not particularly limited, but preferably it has a weight average molecular weight (Mw) of 1,000 or more and 20,000 or less as a polystyrene conversion value by GPC (gel permeation chromatography) method And 2000 or more and 15000 or less are more preferable, and 2000 or more and 10000 or less are more preferable.
GPC method uses HLC-8020GPC (made by Tosoh Corp.), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ 2000 (made by Tosoh Corp., 4.6 mm ID × 15 cm) as columns, THF (tetrahydrofuran as the eluent) Based on the method using

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

  The content of the black dye is preferably 0.3 or less in mass ratio (black dye / inorganic pigment) to the content of the inorganic pigment, from the viewpoint of further improving the reworkability, and is 0.25 or less Is more preferably 0.2 or less. The lower limit of the content of the black dye is not particularly limited, but is preferably 0.01 or more by mass ratio 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, with respect to the total solid content of the composition, and 1 to 8 More preferably, it is mass%.
In the composition of the present invention, the black dye may be used alone or in combination of two or more.

<Dispersing agent>
The composition of the present invention preferably contains a dispersant. The dispersant contributes to the improvement of the dispersibility of pigment components such as the above-mentioned inorganic pigments. 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. Among these, high molecular compounds are preferable.
As the dispersant, polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymers, naphthalenesulfonic acid formalin condensates and the like], polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.

The polymer compound is adsorbed to the surface of the inorganic pigment and, if desired, the pigment to be used in combination, and acts to prevent reaggregation of the material to be dispersed. Therefore, terminal modified polymers, graft polymers, and block polymers having anchor sites on the pigment surface are preferred.
On the other hand, by modifying the surface of the inorganic pigment, the adsorptivity of the polymer compound to this can also be promoted.

The polymer compound preferably has a structural unit having a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
Since the polymer compound having a structural unit having such a graft chain has an affinity to a solvent by the graft chain, the dispersibility of the coloring pigment such as the above-mentioned inorganic pigment and the dispersion stability after aging are obtained. It is excellent. Further, due to the presence of the graft chain, the polymer compound having a structural unit having a graft chain has an affinity to a polymerizable compound or other usable resin and the like. As a result, alkaline development is less likely to produce a residue.
The longer the graft chain, the higher the steric repulsion effect and the better the dispersibility of the pigment etc. On the other hand, when the graft chain is too long, the adsorptivity to color pigments such as the above-mentioned inorganic pigments is reduced, and the dispersibility of the pigment or the like tends to be reduced. For this reason, the graft chain preferably has 40 to 10000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms is More preferably, it is 60-500.
Here, the graft chain means 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 as such a polymer structure, for example, poly (meth) acrylate structure (eg, poly (meth) acrylic structure), polyester structure, polyurethane structure, polyurea structure, polyamide structure And polyether structures and the like.
In order to improve the interaction between the graft chain and the solvent and thereby enhance the dispersibility, the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure. It is preferable that it is a graft chain which it has, and it is more preferable that it is a graft chain which has at least any one of polyester structure and polyether structure.

  The macromonomer having such a graft chain is not particularly limited, but a macromonomer having a reactive double bondable group can be suitably used.

  As a commercially available macromonomer which corresponds to a structural unit having a graft chain possessed by a polymer compound and which is suitably used for the synthesis of the polymer compound, AA-6 (trade name, Toagosei Co., Ltd.), AA-10 (a trade name) Trade name, Toa Gosei Co., Ltd. product, AB-6 (trade name, Toa Sogo Co., Ltd. product), AS-6 (trade name, Toa Sogo Co., Ltd.), AN-6 AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Sogo Co., Ltd.), AY-707 (trade name, manufactured by Toa Sogo Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Sogo Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (product Name, Toa Gosei Co., Ltd. product, Brenmer PP-100 (trade name, NOF Corporation), Brenmer PP-500 (trade name) Name, NOF Corporation (trade name), Blenmer PP-800 (trade name, NOF Corporation), Blenmer PP-1000 (trade name, NOF Corporation), Blenmer 55-PET-800 (Products) Name, NOF Corporation (trade name), Blenmar PME-4000 (trade name, NOF Corporation), Blenmar PSE-400 (trade name, NOF (trade)), Blenmer PSE-1300 (trade name, NOF Corporation (Brandomer 43PAPE-600B (trade name, NOF Corporation)) and the like are used. Among these, preferably, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.) , AS-6 (trade name, Toa Gosei Co., Ltd.), AN-6 (trade name, Toa Sogo Synthesis Co., Ltd.), and Blenmer PME-4000 (trade name, NOF Corporation). Be

The dispersant preferably has at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and cyclic or linear polyesters. Among them, it is preferable to have at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and linear polyester, and polycaprolactone, polyvalerolactone, polymethyl methacrylate and polymethacrylic acid. It is further preferred to have at least one structure selected from the group consisting of methyl. The dispersant may have the above structure alone in one dispersant, or may have a plurality of these structures in one dispersant.
Here, a polycaprolactone structure means what has a structure which ring-opened (epsilon) -caprolactone as a repeating unit. The polyvalerolactone structure refers to one having a structure in which δ-valerolactone is ring-opened as a repeating unit.
Specific examples of the dispersant having a polycaprolactone structure include those in which j and k in the following formulas (1) and (2) are 5. Moreover, as a specific example of the dispersing agent which has a poly valero lactone structure, what j and k in following formula (1) and following formula (2) are 4 is mentioned.
Specific examples of the dispersant having a methyl polyacrylate structure include those in which X ⁵ in the following 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 one 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 (4).

In formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ and W ⁴ are preferably oxygen atoms.
In formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. Each of X ¹ , X ² , X ³ , X ⁴ and X ⁵ is preferably independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, from the viewpoint of the restriction on synthesis, Is more preferably a hydrogen atom or a methyl group, and still 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 restricted in terms of structure. 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), and the like. . In the structures shown below, A and B respectively indicate bonding sites with the left end group and the right end group in the formulas (1) to (4). Among the structures shown below, (Y-2) or (Y-13) is more preferable from the easiness 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, alkyl group, hydroxyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, amino group and the like Can be mentioned. Among them, organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ are preferably those having a steric repulsion effect, particularly from the viewpoint of improvement of dispersibility, and each of them independently has 5 carbon atoms Among them, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. Is preferred. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

In formulas (1) to (4), n, m, p and q are each independently an integer of 1 to 500.
Moreover, in Formula (1) and Formula (2), j and k respectively independently represent the integer of 2-8. 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 Formula (3), R ³ represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, plural R ^{3 s} may be the same as or different from each other.
In Formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. Preferred examples of R ⁴ include a hydrogen atom, an alkyl group, an aryl group and a heteroaryl group, and more preferred is 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 alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. The linear alkyl group having 1 to 20 carbon atoms is more preferable, and the 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 in} the graft copolymer may be the same or different.

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

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability of the composition.
Moreover, as a structural unit represented by Formula (2), it is more preferable that it is a structural unit represented by following formula (2A) from a viewpoint of the dispersion stability of a composition, and developability.

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.

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

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 Formula (1A) as a structural unit having a graft chain.

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

  In addition, the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, does not correspond to a 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, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

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

ClogP values are from Daylight Chemical Information System, Inc. Is a value calculated by the program "CLOGP" available from This program provides the value of "computed logP" calculated by the fragment approach of Hansch, Leo (see the following document). The fragment approach is based on the chemical structure of the compound, dividing the chemical structure into substructures (fragments) and estimating the logP value of the compound by summing the logP contributions assigned to the fragment. 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 .; G. Sammnens, J.J. B. Taylor and C. 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.

log P means the common logarithm of partition coefficient P (Partition Coefficient), and it quantitatively determines how an organic compound is distributed in the equilibrium of oil (generally 1-octanol) and water. Is a physical property value represented as a numerical value, and is represented by the following equation.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value becomes larger than 0, the oil solubility increases, and when it is negative and the absolute value increases, the water solubility increases, which has a negative correlation with the water solubility of the organic compound, and the affinity of the organic compound is negative. It is widely used as a parameter to estimate water quality.

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

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

L is a single bond or a divalent linking group. As the divalent linking group, 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), 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} Are aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (-CO-), and combinations thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.

  6-20 are preferable, as for carbon number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. Also, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group and a heterocyclic group.

The divalent heterocyclic group preferably has a 5- or 6-membered ring as a heterocyclic ring. The heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (= O), a thioxo group (= S), an imino group (= NH), and a substituted imino group (= N-R ³² , wherein R ³² is a fat) Group, aromatic group or heterocyclic group), aliphatic group, aromatic group or heterocyclic group.

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may contain a polyoxyalkylene structure containing an oxyalkylene structure repeated twice or more. As a 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) And heterocyclic groups or combinations 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 a heterocyclic group) or a carbonyl group (-CO-) may be included.

The aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group further includes a ring-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the ring-aggregated hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and -A cyclohexylphenyl group etc. are included. As a bridged cyclic hydrocarbon ring, for example, pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) 2 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 ring, and , Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecane, and, perhydro-1,4-methano-5,8 methanolate 4 cyclic hydrocarbon ring such as naphthalene ring and the like. In addition, as the crosslinked cyclic hydrocarbon ring, a fused cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and Also included are fused rings in which a plurality of 5- to 8-membered cycloalkane rings such as perhydrophenalene rings are fused.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. 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.

  6-20 are preferable, as for carbon number of an aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. Also, 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- or 6-membered ring as a heterocyclic ring. The heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (= O), a thioxo group (= S), an imino group (= NH), and a substituted imino group (= N-R ³² , wherein R ³² is a fat) Group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (For example, a methyl group, an ethyl group, a propyl group etc.), Z or L-Z. Here, L and Z are as defined 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 a hydrogen atom or a methyl group, and L is a single bond or an alkylene group or an oxyalkylene structure Compounds in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group are preferable.
Further, as the monomer represented by the general formula (ii), an R ¹ is hydrogen atom or a methyl group, L is an alkylene group, Z is an aliphatic group, a heterocyclic group or an aromatic group Compounds which are are preferred. Further, as the monomer represented by the general formula ^{(iii), R 4, R} 5, and R ⁶ is a hydrogen atom or a methyl group, Z is an aliphatic group, a heterocyclic group or an aromatic group Certain compounds are preferred.

Examples of representative compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes and the like.
In addition, as an example of a typical compound represented by Formula (i)-(iii), the compound as described in stage 0089-0093 of Unexamined-Japanese-Patent No. 2013-249417 can be referred, and these contents are this specification. Incorporated into

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

The polymer compound can introduce a functional group capable of forming an interaction with the color pigment such as the above-mentioned inorganic pigment. Here, the polymer compound preferably further includes a structural unit having a functional group capable of forming an interaction with a color pigment such as the above-mentioned inorganic pigment.
Examples of the functional group capable of forming an interaction with a color pigment such as the above-mentioned inorganic pigment include an acid group, a basic group, a coordinating group, and a functional group having reactivity.
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, a coordinating group, respectively It is preferable to have a structural unit having the structure or a structural unit having the 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 provided 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 dispersing agent contributing to the dispersion of the coloring pigment such as the above-mentioned inorganic pigment has alkali solubility. . The composition containing such a polymer compound is excellent in the light shielding property of the exposed area, and the alkali developability of the unexposed area is improved.
In addition, when the polymer compound has a structural unit having an acid group, the polymer compound tends to be compatible with the solvent, and the coating property also tends to be improved.
This is because the acid group in the structural unit having an acid group easily interacts with the color pigment such as the above-mentioned inorganic pigment, and the polymer compound stably disperses the color pigment such as the above-mentioned inorganic pigment, and It is presumed that the viscosity of the polymer compound in which the coloring pigment such as the pigment is dispersed is low, and the polymer compound itself is also easily dispersed stably.

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

  Examples of the acid group that is a functional group capable of forming an interaction with a color pigment such as the above-mentioned inorganic pigment include, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. At least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and more preferable ones have good adsorptivity to color pigments such as the above-mentioned inorganic pigments and the like, and the dispersibility of the color pigments is 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 relative to the total mass of the polymer compound in mass conversion. Preferably it is 5 to 80%, More preferably, it is 10 to 60% from the viewpoint of the damage suppression of the image intensity by alkali development.

Examples of the basic group which is a functional group capable of forming an interaction with a color pigment such as the above-mentioned inorganic pigment include, for example, a primary amino group, a secondary amino group, a tertiary amino group, a hetero atom containing an N atom. There are a ring, an amido group and the like, and preferred is a tertiary amino group in that the adsorptivity to color pigments such as the above-mentioned inorganic pigments is good and the dispersibility of the color pigment is high. 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. In contrast, 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 inhibition of developability inhibition.

As a coordinating group which is a functional group capable of forming an interaction with a color pigment such as the above-mentioned inorganic pigment, and a functional group having reactivity, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride And acid chloride and the like. Preferred is an acetylacetoxy group in that it has a good adsorptivity to color pigments such as the above-mentioned inorganic pigments and the like and a high dispersibility of the color 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 functional group having reactivity, but when it is contained, the content of these structural units is The ratio is preferably 10% to 80%, and more preferably 20% to 60%, from the viewpoint of inhibition of developability inhibition, in terms of mass, based on 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 color pigment such as the above-mentioned inorganic pigment in addition to the graft chain, the above-mentioned color pigments such as the above-mentioned various inorganic pigments There is no particular limitation as to how these functional groups are introduced as long as they contain functional groups capable of forming an interaction, 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 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, a methyl group, an ethyl group, a propyl group, etc.).
In the general formula (iv) to the general formula (vi), R ¹¹ , R ¹² and R ¹³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each of them is independently a hydrogen atom or a methyl group. In general formula (iv), it is particularly preferable that R ¹² and R ¹³ each be a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.
Moreover, Y in 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 the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , 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} '- Here, R ³¹ ′ 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 structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups and heterocyclic groups.

  6-20 are preferable, as for carbon number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are the most preferable. Also, 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- or 6-membered ring as a heterocyclic ring. One or more of other heterocycles, aliphatic rings or aromatic rings may be fused to the heterocycle. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (= O), a thioxo group (= S), an imino group (= NH), and a substituted imino group (= N-R ³² , wherein R ³² is a fat) Group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L ₁ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L ₁ may contain a polyoxyalkylene structure containing an oxyalkylene structure repeated twice or more. As a 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 color pigment such as the above-mentioned inorganic pigment other than the graft chain, a carboxylic acid group, and a tertiary group It is preferably an amino group, more preferably a carboxylic acid group.

In the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine or the like), or an alkyl group having 1 to 6 carbon atoms (eg, 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 >, a hydrogen atom or a C1-C3 alkyl group is preferable each independently, 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 each independently represent a hydrogen atom or a methyl group, and L ₁ is an alkylene group or an oxyalkylene structure The compound is preferable which is a bivalent coupling group containing, X ₁ is an oxygen atom or an imino group, and Z ₁ is a carboxylic acid group.
Further, as a 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 Compounds which are groups are preferred.
Furthermore, as the monomer represented by the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, and L ₁ represents a single bond or an alkylene group, Compounds in which Z ₁ is a carboxylic acid group are preferred.

Hereinafter, representative examples of the monomers (compounds) represented by General Formula (iv) to General Formula (vi) will be shown.
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, and a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) with succinic anhydride A reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, and a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule with a tetrahydroxyphthalic anhydride A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxy Phenyl methacrylamide, and the like.

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

Furthermore, for the purpose of improving various performances such as image strength and the like, the polymer compound is colored such as a structural unit having a graft chain, a hydrophobic structural unit, the above-mentioned inorganic pigment and the like as long as the effects of the present invention A structural unit having another structural unit having various functions (eg, a functional group having an affinity to a dispersion medium used for dispersion, etc.) different from a structural unit having a functional group capable of forming an interaction with a pigment ) May be further included.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles and the like.
The polymer compound can use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less based on the total mass of the polymer compound in terms of mass. Particularly preferably, it is 10% or more and 60% or less. Sufficient pattern formability is maintained in the above range of content.

The acid value of the polymer compound is preferably in the range of 0 mg KOH / g to 160 mg KOH / g. From the viewpoint of making the alkali developability better, the lower limit is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, and particularly preferably 50 mg KOH / g or more. If the acid value of the polymer compound is 50 mg KOH / g or more, the sedimentation of the color pigment such as the above-mentioned inorganic pigment can be further suppressed, and the number of coarse particles can be further reduced (in other words, the amount of particles in the liquid can be reduced). And the stability over time of the composition can be further improved.
In addition, from the viewpoint of more effectively suppressing pattern peeling during development when forming the light shielding film, the upper limit thereof is preferably 140 mg KOH / g or less, and more preferably 120 mg KOH / 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. Moreover, resin which has a desired acid value can be obtained by changing content of the structural unit containing the acidic radical which is a structural component of a high molecular compound.

The weight average molecular weight of the polymer compound according to the present invention is 4,000 as a polystyrene conversion value by GPC (gel permeation chromatography) method from the viewpoint of suppression of pattern peeling during development and developability when forming a light shielding film. The number is preferably 300,000 or less, more preferably 5,000 or more and 200,000 or less, still more preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. Being particularly preferred.
GPC method uses HLC-8020GPC (made by Tosoh Corp.), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ 2000 (made by Tosoh Corp., 4.6 mm ID × 15 cm) as columns, THF (tetrahydrofuran as the eluent) Based on the method using

  The polymer compound can be synthesized based on a known method, and as a solvent used when synthesizing the polymer compound, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, 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, dimethyl sulfoxide, toluene, Ethyl acetate, methyl lactate, ethyl lactate and the like can be mentioned. 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 Tochigi Kasei Co., Ltd., “Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (acid group) manufactured by BYK Chemie Copolymers: 111) (phosphate dispersant) 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), "EFKA 4047, 4050 to 4010 to 4165 (polyurethane system), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester) manufactured by EFKA Amides), 5765 (high molecular weight polycarboxylates), 622 (Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Adispar PB 821, PB 822, PB 880, PB 881 "manufactured by Ajinomoto Fine Techno Co.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd. "Polyflow No. 50E, No. 300 (acrylic copolymer)", Kushimoto Chemical Co., Ltd. "Disparone KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester) , DA-703-50, DA-705, DA-725 ", Kao Corporation" Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate ""","Homogenol L-18 (polymeric polycarboxylic acid)", Emulgen 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether) "," Acetamine 86 (stearylamine acetate) ", manufactured by Nippon Lubrizol Co., Ltd." Sol Sparse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ", Nikko Chemical Co., Ltd." NIKKOL T106 ( Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), manufactured by Kawaken Fine Chemicals Co., Ltd. Hinoacto T-8000 E, etc., Shin-Etsu Chemical Co., Ltd. manufactured, Organo Silo Sunpolymer KP 341, Yusho Co., Ltd. "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl Nonionic surfactants such as ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", manufactured by Morishita Sangyo Co., Ltd. "EFKA-46, EFKA −47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 ”, Sannopco Co., Ltd.“ Dispers Aid 6, Disperse Polymer dispersants such as Perth Aid 8, Dispers Aid 15, Dispers Aid 9100, etc. "ADEKA PLURONIC L31, F38, L42, L44, L64, L64, F68, L72, P72, P77, P84" manufactured by ADEKA Co., Ltd. , F87, P94, L101, P103, F108, L121, P-123 "," Ionet (trade name) S-20 "manufactured by Sanyo Chemical Industries, Ltd., and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Further, as a commercial product of amphoteric resin, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2001, DISPERBYK-2001 manufactured by Bick Chemie, Inc. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajisper PB 821 manufactured by Ajinomoto Fine Techno Co., Ltd., an AZISPAR PB 822, an AGISPAR PB 881 and the like.
These high molecular compounds may be used alone or in combination of two or more.

  In addition, as an example of a specific example of the polymer compound, the polymer compounds described in paragraphs [0127] to [0129] of JP-A-2013-249417 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 compounds, graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (columns 0075 to 0133 of corresponding US 2011/0124824) can be used, The contents of are incorporated herein by reference.
Moreover, it has the side chain structure which the acidic group of Unexamined-Japanese-Patent No.2011-153283, Paragraph 0028-0084 (Correspondence US 2011/02729759 corresponding column 0075-0133 column) couple | bonds together via a coupling group. Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.

  When the composition contains a dispersant, the content of the dispersant is preferably in the range of 0.1 to 1 by mass ratio to the above-mentioned inorganic pigment, and is preferably 0.1 to 0.4. It is more preferable that it is a range. By setting the content of the dispersing agent in the range of 0.1 to 0.4 in mass ratio to the above-mentioned inorganic pigment, the amount of coarse particles in the composition can be further reduced, and the obtained light shielding film is obtained Excellent in 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, based on the total solid content of the composition. 0.5 to 10% by mass is more preferable.
The dispersant may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that a total amount becomes said range.

<Binder resin>
The composition of the present invention preferably contains a binder resin.
It is preferable to use a linear organic polymer as the binder resin. As such a linear organic polymer, known ones can be optionally used. Preferably, linear organic polymers that are soluble or swellable in water or weakly alkaline water are selected to enable water development 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, and promotes at least one alkali solubility in a molecule (preferably, a molecule having a (meth) acrylic copolymer or a styrenic copolymer as a main chain) It can select suitably from alkali-soluble resin which has the group to be. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins are preferable, and developability is preferable. From the viewpoint of control, (meth) acrylic resins, (meth) acrylamide resins, and (meth) acrylic / (meth) acrylamide copolymer resins are preferable.
Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include, for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Especially, what is soluble in an organic solvent and developable by weak alkali aqueous solution is preferable, and the alkali-soluble resin which has a structural unit derived from (meth) acrylic acid is mentioned as a more preferable thing. These acid groups may be of only one type, or of two or more types.

As the binder resin, for example, radical polymers having a carboxylic acid group in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, acid anhydride Resins obtained by hydrolyzing or half-esterifying or half-amidating acid anhydride units by homopolymerization or copolymerization of monomers having at least one monomer, and epoxy acrylates obtained by modifying an epoxy resin with unsaturated monocarboxylic acid and acid anhydride, etc. It can be mentioned. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, etc. Examples of monomers having an acid anhydride include Maleic anhydride etc. are mentioned. Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain can also be mentioned as an example. In addition to this, polymers obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
In addition, the acetal-modified polyvinyl alcohol-based binder resin having an acid group described in each publication of European Patent No. 993966, European Patent No. 1204000, and JP-A No. 2001-318463 has film strength and developability. Excellent balance and suitable.
Furthermore, polyvinyl pyrrolidone, polyethylene oxide and the like are useful as water-soluble linear organic polymers. Also, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition polymerizable vinyl monomers] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / needle Accordingly, other addition polymerizable vinyl monomers] copolymer is preferable because it is excellent in the balance of film strength, sensitivity and developability.
Commercially available products include, for example, Acrybase FF-187, FF-426 (Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokuhin Co., Ltd.), and Daicel Ornex Co., Ltd. Cyclomer P (ACA) 230 AA and the like.

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

Moreover, it is also preferable to use the polymer which has a structural unit which has a graft chain, and a structural unit which has an acidic radical (alkali soluble group) as binder resin.
The definition of the structural unit having a graft chain is the same as 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, and a phenolic hydroxyl group. Preferably, at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is used. And more preferred are carboxylic acid groups.

  As a structural unit which has an acidic radical, it is preferred to have one or more sorts of structural units chosen from a structural unit derived from a monomer denoted by the following general formula (vii)-general formula (ix).

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

X ₂ in the general formula (vii) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.
Moreover, Y in general formula (viii) represents a methine group or a nitrogen atom.

Further, L ₂ in the general formulas (vii) to (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group, and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino bond (-NR ⁴¹ '- Here, R ⁴¹ ′ represents 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 structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups and heterocyclic groups.

  6-20 are preferable, as for carbon number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. Also, 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- or 6-membered ring as a heterocyclic ring. One or more of other heterocycles, aliphatic rings or aromatic rings may be fused to the heterocycle. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (= O), a thioxo group (= S), an imino group (= NH), and a substituted imino group (= N-R ⁴² , wherein R ⁴² is a fat) Group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

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

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

In the general formula (ix), R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group 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 a C1-C3 alkyl group is preferable each independently, 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 each independently represent a hydrogen atom or a methyl group, and L ₂ is an alkylene group or an oxyalkylene structure And the like. A compound in which X ₂ is an oxygen atom or an imino group and Z ₂ is a carboxylic acid group is preferable.
Further, as a 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 Compounds which are groups are preferred.
Furthermore, as a monomer represented by general formula (ix), a compound in which R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom or a methyl group and Z ₂ is a carboxylic acid group is preferable.

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

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% in mass conversion, based on the total mass of the binder resin, and more preferably from the viewpoint of suppressing the image strength damage caused by the alkali development. 10 to 90%.

The content of the binder resin in the composition of the present invention is preferably 0.1 to 30% by mass, and more preferably 0.3 to 25% by mass, with respect to the total solid content of the composition.
The binder resin may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that a total amount becomes said 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 a compound having two or more groups, still more preferably three or more, and particularly preferably five or more. The upper limit is, for example, 15 or less. As a group which has an ethylenically unsaturated bond, a vinyl group, a (meth) allyl group, and a (meth) acryloyl group etc. are mentioned, for example.

The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof. Monomers are preferred.
100-3000 are preferable and, as for the molecular weight of a polymeric compound, 250-1500 are more preferable.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) and esters thereof, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. Also, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group etc. with monofunctional or polyfunctional isocyanates or epoxies, or the above unsaturated Dehydration condensation products of carboxylic acid esters or amides with monofunctional or polyfunctional carboxylic acids and the like are also suitably used. In addition, unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group and an epoxy group, and a reaction product of monofunctional or polyfunctional alcohols, amines, thiols, a halogen group or a tosyloxy group And the like. Reactants of unsaturated carboxylic acid esters or amides having a leaving substituent such as, for example, with monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, instead of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted by unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether and the like.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can be suitably 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 more under normal pressure is also preferable. As examples thereof, for example, the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and the contents thereof are incorporated in the present specification.

The polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; 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 an ethylene glycol residue or a propylene glycol residue (for example, commercially available from Sartomer, SR454, SR499 Is preferred. These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) can also be used.
The aspect of a preferable polymeric compound is 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 unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a nonaromatic carboxylic acid anhydride to produce an acid. The 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 ALONIX TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

  As a preferable acid value of the polymeric compound which has an acidic radical, it is 0.1-40 mgKOH / g, More preferably, it is 5-30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the developing dissolution property is good, and when it is 40 mg KOH / g or less, it is advantageous in terms of production or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

As a 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 examples thereof include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, and dipentaerythritol. Ε-caprolactone modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and (meth) acrylic acid and ε-caprolactone Be 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 of the six R's are groups represented by the following general formula (Z-2), or 1 to 5 of the six R's have the following general formula (Z And the remainder is a group represented by the following general formula (Z-3).

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

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

The polymerizable compound having a caprolactone structure is, for example, commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), the formula Number of groups represented by (Z-2) = 2, compounds wherein all R ¹ are hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (Z-2) = 3, compounds where R ¹ is all hydrogen atoms, DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, compounds where all R ¹ are hydrogen atoms And DPCA-120 (in the formula, m = 2, the number of groups represented by formula (Z-2) = 6, and compounds in which all R ¹ are hydrogen atoms), 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 formula (Z-4) and (Z-5), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{((CH 2) y CH (} CH 3) O) - And y each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 0 to 40 .
In general formula (Z-5), the total of (meth) acryloyl groups is five or six, n independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60 .

In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and, as for the sum of each m, the integer of 4-8 is still more preferable.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 3-60 is preferable, the integer of 3-24 is more preferable, and, as for the sum of each n, the integer of 6-12 is still more preferable.
In general formula (Z-4) or general formula (Z-5) in the _{- ((CH 2) y CH} 2 O) - , or _{((CH 2) y CH (} CH 3) O) - is an oxygen atom Preferred is a form in which the side end is bonded to X.

  The compounds represented by General Formula (Z-4) or General Formula (Z-5) may be used alone or in combination of two or more. In particular, in a form in which all six X's are an acryloyl group in the general formula (Z-5), a compound in which all six X's are an acryloyl group in the general formula (Z-5) Among them, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferred. With such a configuration, developability can be further improved.

  Moreover, as a total content in the polymeric compound of a compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compounds represented by the general formula (Z-4) or the general formula (Z-5) are obtained by ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol which is a conventionally known step. It can synthesize | combate from the process of couple | bonding the ring-opened frame by reaction, and the process of making (meth) acryloyl chloride react with the terminal hydroxyl group of ring-opened frame, and introduce | transducing a (meth) acryloyl group, for example. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by general formula (Z-4) or (Z-5).

Among the compounds represented by Formula (Z-4) or Formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplified compounds (a) to (f)”), and among them, exemplified compounds (a), (B), (e) and (f) are preferred.

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

As polymerizable compounds, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, or JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, or JP-B-62-39418 disclose urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860. . Also, use of addition polymerizable compounds having an amino structure or a sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Thus, it is possible to obtain a composition excellent in photospeed very much.
As commercially available products, urethane oligomers UAS-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- 306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha), etc. are mentioned.

Further, the polymerizable compound used in the present invention preferably has an SP (dissolution parameter) value of 9.50 or more, more preferably 10.40 or more, and preferably 10.60 or more. More preferable.
In the present specification, unless otherwise specified, the SP value is determined by the Hoy method (H. L. Hoy Journal of Painting, 1970, Vol. 42, 76-118). Moreover, although the unit is abbreviate ^| omitted and shown about SP value, the unit is cal1 ^{/ 2cm-3 /} 2.

Moreover, it is also preferable that a composition has a polymeric compound which has cardo frame | skeleton from a viewpoint of development residue improvement.
The polymerizable compound having a cardo skeleton is preferably a polymerizable compound having a 9,9-bisarylfluorene skeleton, and more preferably a compound represented by the following formula (Q3).

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. Each of X ^{1 to} X ⁴ independently represents a substituent having a polymerizable group, and a carbon atom in the substituent may be substituted by a hetero atom. a and b each independently represent an integer of 1 to 5; c and d each independently represent an integer of 0 to 4; R ^{1 to} R ⁴ each independently represent a substituent, e, f, g and h each independently represent an integer of 0 or more, and the upper limits of e, f, g and h are 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 each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ and R ^{1 to} R ⁴ each represent It may be substituted to the benzene ring enclosed with a dashed line independently, and you may substitute to rings other than the benzene ring enclosed with a dashed line.

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

In the general formula (Q3), X ^{1 to} X ⁴ each independently represent a substituent having a polymerizable group, and a carbon atom in the substituent may be substituted by 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 having 2 to 10 carbon atoms. It is more preferable that it is an alkylene group, and it is still more preferable that it is a C2-C5 alkylene group.
The substitution, the aliphatic group having a polymerizable group represented by X ¹ to X ^4, when the aliphatic group is substituted by a heteroatom, -NR- (R is a substituted group), an oxygen atom, by a sulfur atom It is preferable that the non-adjacent -CH _{2-in the} aliphatic group is more preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent -CH _2- in the aliphatic group is It is further preferred that the oxygen atom be substituted. The aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is preferably substituted at one or two places by a hetero atom, more preferably substituted at one place by a hetero atom, and Ar ^{11 to} Ar It is further preferable that one place adjacent to the aryl group containing a benzene ring surrounded by a dashed line represented by ¹⁴ be substituted by a hetero atom.
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 preferred.
As a radically polymerizable group, a generally known radically polymerizable group can be used, and as a preferable group, a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned, and specifically, A vinyl group, a (meth) acryloyloxy group, etc. are mentioned. Among them, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationically polymerizable group, generally known cationic polymerizability can be used, and specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiroorthoester group, vinyloxy And the like. Among them, alicyclic ether group and vinyloxy group are preferable, and epoxy group, oxetanyl group and vinyloxy group are particularly preferable.
It is preferable that the said polymeric group which the substituent which Ar < ¹ > -Ar < ⁴ > has has is a radically 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 out of ⁴ contain a substituent having a polymerizable group, and it is further preferable that 2 out of Ar ^{1 to} Ar ⁴ contain a substituent having a polymerizable group.
When Ar ^{11 to} Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ each independently represent benzene surrounded by a broken line The ring may be substituted, or may be substituted to a ring other than a 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 it is more preferable that both a and b be 1.
In the above general formula (Q3), c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and it is more preferable that both c and d be 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 examples thereof include a halogen atom, a halogenated alkyl 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 And aryl groups and alicyclic groups. 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, an alkoxy group having 1 to 5 carbon atoms or a phenyl group More preferably, it is a methyl group, a methoxy group or a phenyl group.
In the general formula (Q3), when each of Ar ^{11 to} Ar ¹⁴ is a polycyclic aromatic hydrocarbon group containing a benzene ring independently surrounded by a broken line as one of the condensed rings, R ^{1 to} R ⁴ It may be substituted to the benzene ring enclosed with a dashed line independently, and you may substitute to rings other than the benzene ring enclosed with a dashed 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 each a substituent which Ar ^{11 to} Ar ¹⁴ can have Is a value obtained by subtracting a, b, c or d from the number of.
Each of e, f, g and h is preferably independently 0 to 8, more preferably 0 to 2, and still more preferably 0.
When Ar ^{11 to} Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, it is preferable that e, f, g and h be 0 or 1 And 0 is more preferable.

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

  Examples of the polymerizable compound having a cardo skeleton include, but are not limited to, On Coat 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, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and still more preferably 20% by mass or less.
The polymerizable compounds may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that a total amount becomes said range.

<Polymerization initiator>
The composition of the present invention preferably contains a polymerization initiator.
There is no restriction | limiting in particular as a polymerization initiator, It can select suitably from well-known polymerization initiators, for example, what has photosensitivity (what is called, a photoinitiator) is preferable.
When the composition of the present invention contains a photopolymerization initiator and the above-described polymerizable compound in addition to the inorganic pigment and the black dye described above, the composition is cured by irradiation with an actinic ray or radiation. 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. In addition, it may be an activator that produces an action with a photoexcited sensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 in the range of about 300 nm to 800 nm (330 nm to 500 nm is more preferable).

  As the photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, one having a triazine skeleton, one having an oxadiazole skeleton, etc.), an acylphosphine compound such as an acylphosphine oxide, a hexaarylbiimidazole, an oxime derivative And oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, an F. compound. C. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Patent No. 4212976 Compounds described in the book, and the like.

  From the viewpoint of exposure sensitivity, trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, oniums A compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl substituted coumarin compound preferable.

  More preferably, a trihalomethyl triazine compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, an oxime compound, a triallyl imidazole dimer, an onium compound, a benzophenone compound, an acetophenone compound, a trihalomethyl triazine compound, an α-amino ketone Examples include at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds.

In particular, when the composition of the present invention is used for producing a light-shielding film of a solid-state imaging device, since it is necessary to form a fine pattern in a sharp shape, there is no residue in the unexposed area together with curability. It is important to From such a viewpoint, it is preferable to use an oxime compound as the photopolymerization initiator. In particular, when forming a fine pattern in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of addition of the photopolymerization initiator also needs to be suppressed low. Therefore, in consideration of these points, it is preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern as in a solid-state imaging device. In addition, color transfer can be further improved by using an oxime compound.
As a specific example of a photoinitiator, the paragraph 0265-0268 of Unexamined-Japanese-Patent No. 2013-29760 can be considered, for example, and this content is integrated in this-application specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As a hydroxyacetophenone type initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (brand name: all are BASF Corporation make) can be used.
As aminoacetophenone initiators, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF Corp.) can be used. As the aminoacetophenone initiator, compounds described in JP-A-2009-191179 in which the absorption wavelength is matched to a long wave light source such as 365 nm or 405 nm can also be used.
As an acyl phosphine type initiator, IRGACURE-819 or DAROCUR-TPO (brand name: all made by BASF Corporation) which are commercial items can be used.

More preferably, an oxime compound (oxime type initiator) is mentioned as a photoinitiator. In particular, oxime compounds are preferable because they have high sensitivity and high polymerization efficiency, can be cured regardless of the colorant concentration, and can be easily designed to have a high colorant concentration.
As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.
In the present invention, as an oxime compound which can be suitably used, for example, 3-benzoyliminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-Acetoxyiminopentan-3-one, 2-Acetoxyimino-1-phenylpropan-1-one, 2-Benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
Also, J.J. C. S. Perkin II (1979) pp. 1653-1660), J.F. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. The compounds described in JP-A-2000-80068, JP-A-2000-80068, JP-A-2004-534797, JP-A-2006-342166, and the like can also be mentioned.
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also suitably used. In addition, TR-PBG-304 (made by Changzhou High Power Electronic New Material Co., Ltd.), Adeka Akurus NCI-831 and Adeka Akurus NCI-930 (made by ADEKA), N-1919 (carbazole oxime ester skeleton containing photoinitiator) (Made by ADEKA company) can also be used.

Further, as oxime compounds other than those described above, compounds described in JP-T-2009-519904, in which an oxime is linked to the carbazole N-position, and compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced in the benzophenone moiety, Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced to a dye site, ketooxime compounds described in WO2009-131189, triazine skeleton and oxime skeleton have the same molecule The compound described in U.S. Pat. No. 7,556,910, the compound described in JP-A 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. In addition, the N—O bond of the oxime may be an oxime compound of (E) form, an oxime compound of (Z) form, or a mixture of (E) form and (Z) form. .

In 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 nonmetal atomic group.
Examples of the monovalent nonmetal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Also, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by the other 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. As the substituent, the above-mentioned substituents can be exemplified.
As a bivalent organic group represented by A in general formula (OX-1), a C1-C12 alkylene group, a cycloalkylene group, or an alkynylene group is preferable. These groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.

  In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. As specific examples of the oxime compound having a fluorine atom, a compound described in JP-A-2010-262028, a compound 24 described in JP-A-2014-500852, a compound described in JP-A-2013-164471 ( C-3) and the like. 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 a photopolymerization initiator.

In Formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or R ⁷ 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 form a fluorene group, and R ³ and R ⁴ are each independently 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 represents 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, -CSOR 6, -CN, halogen R ⁶ represents an atom or a 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 of 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
As a specific example of a compound represented by Formula (1) and Formula (2), the compound described in stage number 0076-0079 of Unexamined-Japanese-Patent No. 2014-137466 is mentioned, for example. This content is incorporated herein by reference.

  Specific examples of oxime compounds 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 a wavelength range of 350 nm to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 nm to 480 nm, and still more preferably a high absorbance at 365 nm and 405 nm.
The oxime compound preferably has a molar absorption coefficient at 365 nm or 405 nm of 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, from the viewpoint of sensitivity. Is more preferably 1,000.
The molar absorption coefficient of the compound can be determined according to a known method, for example, using an ethyl acetate solvent in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), at a concentration of 0.01 g / L. It is preferable to measure.
The photopolymerization initiators used in the present invention may be used in combination of two or more as needed.

  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, based on the total solid content in the composition, and 1 to 25%. % Is more preferable, and 1 to 10% by mass is even more preferable. The composition of the present invention may contain only one type of polymerization initiator, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<Organic solvent>
The composition of the present invention preferably contains an organic solvent.
Examples of the organic solvent include, for example, 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, 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 Ter, 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, Examples include, but are not limited to, butyl acetate, methyl lactate, and ethyl lactate.

The composition of the present invention may contain one type of organic solvent, or may contain two or more types of organic solvents, but when adjusting the composition of the present invention, the particles of the above-mentioned inorganic pigment are mixed It is preferable to contain 2 or more types of organic solvents from the point that diameter fluctuation can be suppressed.
When containing two or more organic solvents, the above methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -It is preferable to be 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, and more preferably 60 to 90% by mass, based on the total mass of the composition. preferable. When two or more organic solvents are contained, the total amount thereof is preferably in the above range.

<Water>
The composition of the present invention may contain water. Water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention.
The content of water is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.8% by mass, relative to 100% by mass of the composition, and 0.1 to 0. More preferably, it is 7% by mass. When the water content is in the above range, the generation of pinholes when the light shielding film is produced can be suppressed, or the moisture resistance of the light shielding film can be improved.

<Other ingredients>
The composition of the present invention may contain other components in addition to the components described above.
Each component will be described in detail below.

(Silane coupling agent)
The silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. In addition, hydrolysable groups, such as an alkoxy group, are couple | bonded with the silicon atom.
The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group has a carbon atom, the carbon number 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 a fluorine atom and a silicon atom (but excluding the silicon atom to which the hydrolyzable group is bonded). Silicon atoms (but excluding silicon atoms to which hydrolyzable groups are attached), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched chain alkyl groups having 3 or more carbon atoms It is desirable not to include.

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

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

  The molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1000 in terms of handleability, and is preferably 270 or more, more preferably 270 to 1000 in that the effect of the present invention is more excellent.

As one of the suitable aspects of a silane coupling agent, the silane coupling agent X represented by Formula (W) is mentioned.
Formula (W) R _Z2- Lz-Si- (R _Z1 ) ₃
R _z1 represents a hydrolyzable group, and the definition 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 which may be substituted by a C 2-10 halogen atom and an arylene group which may be substituted by a C 6-12 halogen atom, or 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 And the group consisting of the combination of these groups is more preferable. Here, the above R ¹² represents a hydrogen atom or a methyl group.

  As the silane coupling agent X, N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trimethoxy Silane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name: KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBM-903), γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBE-903), 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name) KBM-503), and glycidoxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBM) 4803), and the like.

In another preferred embodiment of the silane coupling agent, 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 It 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 atoms, substituents or different. The bondable atom, substituent, hydrogen atom, halogen atom, hydroxyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group, alkynyl group, aryl group, amino group which can be substituted by alkyl group and / or aryl group, silyl Groups, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups and the like. These substituents may further be substituted with silyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, alkyl and / or aryl, amino, halogen, sulfonamide, and the like. It may be substituted with an alkoxycarbonyl group, an amido group, a urea group, an ammonium group, an alkyl ammonium group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof or the like.
In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by Formula (Z).

The silane coupling agent Y preferably has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is a substituent It is preferred to have at least one organic group. In addition, as a structure of an amino group, you may exist in a molecule | numerator in the form of the partial structure of a nitrogen-containing heterocyclic ring, and you may exist as substituted amino groups, such as aniline.
Here, as the organic group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a combination thereof, and the like can be mentioned. These may further have a substituent and examples of the substituent that can be introduced include silyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, thioalkoxy group, amino group, halogen atom, sulfonamide Groups, alkoxycarbonyl groups, carbonyloxy groups, amido groups, urea groups, alkyleneoxy groups ammonium groups, alkyl ammonium groups, carboxyl groups or salts thereof, sulfo groups and the like.
Further, the nitrogen atom is preferably bonded to the curable functional group through any organic linking group. Preferred organic linking groups include the aforementioned nitrogen atom and substituents which 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 is also possible to take an embodiment having two or more curable functional groups, and sensitivity and stability From the viewpoint of the above, it is preferable to have 2 to 20 curable functional groups, more preferably 4 to 15 and most preferably 6 to 10 curable functional groups in the molecule.

  Although the molecular weight in particular of the silane coupling agent X and the silane coupling agent Y is not restrict | limited, The range mentioned above (270 or more is preferable) is mentioned.

  0.1-10 mass% is preferable with respect to the total solid in a composition, as for content of the silane coupling agent in the composition of this invention, 0.5-8 mass% is more preferable, and 1. 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 a composition contains 2 or more types of silane coupling agents, the sum total should just be in the said 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 surfactant can be used.

  By containing a fluorine-based surfactant in the composition of the present invention, the liquid properties (in particular, the 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, in the case of film formation 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. This improves the coating property on the surface to be coated. For this reason, film formation with small uniform thickness can be more suitably performed.

  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. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film or the liquid saving property, and the solubility in the composition is also good.

Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. Same F482, same F554, same F780, RS-72-K (above, made by DIC Corporation), Florard FC430, same FC431, same FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, the same SC -101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like can be mentioned. As the fluorine-based surfactant, the compounds described in paragraphs [0015] to [0158] of JP-A-2015-117327 can also be used. A block polymer can also be used as a fluorine-type surfactant, and the compound described, for example in Unexamined-Japanese-Patent No. 2011-89090 is mentioned as a specific example.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy) (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.
Moreover, the fluorine-containing polymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. Specific examples thereof include compounds described in JP-A-2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, for example, Megaface RS-101, RS-102, RS-718K, or RS- manufactured by DIC. 72-K etc. are mentioned.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerine ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Lubrizol Japan Ltd.) and the like. Further, the product of Wako Pure Chemical Industries, Ltd., may be used NCW-101, NCW-1001, NCW-1002.

  Specific examples of cationic surfactants include 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 Co) polymer poly flow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

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

  As silicone type surfactant, for example, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (more than Toray Dow Corning ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, made by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) , BYK 307, BYK 323, BYK 330 (above, manufactured by Big Chemie Co., Ltd.), and the like.

  Only one surfactant may be used, or two or more surfactants may be combined. 0.001-2.0 mass% is preferable with respect to the total solid of the composition of this invention, and, as for content of surfactant, 0.005-1.0 mass% is more preferable.

<Polymerization inhibitor>
It is preferable that the said composition contains a polymerization inhibitor. When the polymerization inhibitor is contained, the above composition has more excellent stability over time.
The content of the polymerization inhibitor is preferably 0.00055 to 0.055% by mass, and more preferably 0.0015 to 0.01% by mass, with respect to 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. As a compound used as a polymerization inhibitor, a phenol type compound, a quinone type compound, a hindered amine type compound, a phenothiazine type compound, a nitrobenzene type compound etc. are mentioned, for example. The above compounds may be used alone or in combination of two or more.

  Examples of the above-mentioned phenolic compound include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-diphenol. -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-hydroxyhydrocinnamate), 4-methoxy-1-naphthol, 1,4-dihydroxynaphthalene and the like.

  As a phenol type compound, the phenol type compound shown by Formula (IH-1) is preferable.

In formula (IH-1), R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a hydroxy group, an amino group, an aryl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl Represents a group. R _{1 to} R ₅ may be linked each other to form a ring.

As R _{1 to} R ₅ in the formula (IH-1), a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group and an ethyl group), an alkoxy group having 1 to 5 carbon atoms (eg, methoxy) And ethoxy group, an alkenyl group having 2 to 4 carbon atoms (e.g., a vinyl group), or a phenyl group is preferable.
Among them, R ₁ and R ₅ are each independently more preferably a hydrogen atom or a tert-butyl group, R ₂ and R ₄ are more preferably a hydrogen atom, and R ₃ is a hydrogen atom, 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 compounds include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.

  As a hindered amine compound, the polymerization inhibitor represented by a following formula (IH-2) is mentioned, for example.

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.
Moreover, R < ₇ > -R < ₁₀ > in Formula (IH-2) respectively independently represents a hydrogen atom or an alkyl group. The alkyl group R ₇ to R ₁₀ represent preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.

As a polymerization inhibitor, each said compound may be used individually by 1 type, may use 2 types together, and may use 3 or more types together.
The polymerization inhibitor preferably contains a phenolic compound. Among them, from the viewpoint of temporal stability, the polymerization inhibitor preferably contains two or more kinds of phenolic compounds.
Moreover, it is preferable that the said polymerization inhibitor contains a phenol type compound and a hindered amine type compound from a viewpoint of a time-lapse stability.

<UV absorber>
The composition may contain a UV absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
As the UV absorber, UV absorbers of salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type and triazine type can be used. As specific examples of these, the compounds of paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding to paragraphs 0251 to 0254 of corresponding US 2012/0068292) can be used, and the contents of these can be incorporated and incorporated herein. .
In addition, diethylamino-phenylsulfonyl type ultraviolet absorber (made by Daito Kagaku Co., Ltd., trade name: UV-503) and the like are suitably used.
As an ultraviolet absorber, the compound illustrated by Unexamined-Japanese-Patent No.2012-32556, Paragraph 0134-0148 is mentioned.
0.001-15 mass% is preferable with respect to the total solid of a composition, as for content of a ultraviolet absorber, 0.01-10 mass% is more preferable, and 0.1-5 mass% is still more preferable. As an ultraviolet absorber, each above-mentioned compound may be used individually by 1 type, or 2 or more types may be used together.

(Organic pigment)
The composition may contain an organic pigment.
As an organic pigment, for example, 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, 108, 109, 110, 113, 114, 115, 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 Etc. 169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214;
C. I. Pigment orange 2, 5, 13, 16, 17: 1, 13, 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, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 25: 2, 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, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 226, 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 pigments may be used alone or in combination of two or more.

<Achromatic dye>
As the dye, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP-B-2592207 and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,505,950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-6. Dyes disclosed in JP-A-194828 can be used. When classified as chemical structures, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. Further, as the dye, a dye multimer may be used. As a pigment | dye multimer, the compound described in Unexamined-Japanese-Patent No. 2011-213925, Unexamined-Japanese-Patent No. 2013-041097 is mentioned. In addition, a chromatic dye-polymerizable dye having a polymerizability in the molecule may be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries, Ltd.

<Infrared absorber>
The colorant may further contain an infrared absorber.
An infrared absorber means the compound which has absorption in the wavelength range of infrared region (preferably wavelength of 650-1300 nm). Preferably, the infrared absorbing agent is preferably a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squalilium compounds, naphthalocyanine compounds, quaterrylene Examples thereof include compounds, dithiol metal complex compounds, and croconium compounds.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squalium compound, and croconium compound, the compounds disclosed in paragraphs [0010] to [0081] of JP-A-2010-117750 may be used, and the contents thereof are described in this specification. Incorporated into The cyanine compound can be referred to, for example, "Functional dye, Shin Ookawara / Ken Matsuoka / Keijiro Kitao / Tsunehiro Hiraiso, Kodansha Scientific", the contents of which are incorporated herein.

Compounds disclosed in paragraphs 0004 to 0016 of JP-A 07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A 2002-146254 as colorants having the above-mentioned spectral characteristics, JP-A 2011-164583 It is also possible to use near-infrared absorbing particles comprising crystallites of oxides containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the gazette and having a number average aggregate particle diameter of 5 to 200 nm.
In addition, an infrared absorber may be used individually by 1 type, or may use 2 or more types together.

  When the composition of the present invention contains another 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, and 2 -7 mass% is more preferable.

In addition to the above components, the following components may be further added to the composition of the present invention. For example, sensitizers, pigment dispersants other than those described above, co-sensitizers, cross-linking agents, curing accelerators, fillers, heat curing accelerators, plasticizers, diluents, and sensitizing agents, etc. may be mentioned. Adhesion promoters to substrate surfaces and other auxiliary agents (eg, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension regulators, and If necessary, known additives such as chain transfer agents may be added.
These components are described, for example, in JP-A-2012-003225, paragraph Nos. 0183 to 0228 (corresponding US patent application publication No. 2013/0034812, [0237] to [0309]), JP-A-2008-250074, and the like. The descriptions of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP 2013-195480 A can be referred to, and the contents thereof 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. Moreover, since the amount of particles of a composition can be reduced more because the solid content of a composition is 40 mass% or less, 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.

<Method of producing 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 emulsifying device, a wet crusher, a wet disperser).
In the production of the composition, various components constituting the composition may be blended at one time, or may be sequentially blended after dissolving or dispersing the various components in an organic solvent. In addition, the order of introduction and working conditions at the time of blending are not particularly limited.
In the process of dispersing the pigment, examples of mechanical force used to disperse 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, "Distribution Technology, issued by Information Technology Co., Ltd., July 15, 2005" and "Dispersion technology centering on suspension (solid / liquid dispersion system) and actual practical application materials of industrial application, Management Development Center publication" Partly, Oct. 10, 1978 "can be preferably used.
Further, in the process of dispersing the pigment, the pigment may be finely divided by a salt milling process. As materials, equipment, processing conditions, and the like used in the salt milling step, those described in, for example, JP-A-2015-194521 and JP-A-2012- 046629 can be used.
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter may be used without particular limitation as long as it is conventionally used for filtration applications and the like. For example, a filter made of a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, or a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP) may be mentioned. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably 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 still more preferably 0.3 to 0. It is 7 μm. Within this range, it is possible to reliably remove fine foreign matters such as impurities or aggregates contained in the pigment while suppressing filter filtration clogging.
When using filters, different filters may be combined. At this time, the filtering with the first filter may be performed only once or may be performed twice or more. When different filters are combined to perform filtering twice or more, it is preferable that the second and subsequent pore sizes be the same or larger than the pore size of the first filtering. Moreover, you may combine the 1st filter of the hole diameter which is different within the range mentioned above. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it is possible to select from various filters provided by Nippon Pall Ltd., Advantech Toyo Ltd., Nippon Entegris Ltd. (old Japan Microlith Ltd.) or Kitz Micro Filter Inc. .
The second filter can be formed of the same material as the first filter described above. The pore diameter of the second filter is suitably 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.

[Cured film (light shielding film)]
The cured film of the present invention is obtained using the composition described above. The cured film of the present invention mainly includes 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 suitably used as a light shielding film, and more specifically, suitably used as an image sensor peripheral light shielding film (frame light shielding film) such as a CCD image sensor or a CMOS image sensor.
The light shielding film around the image sensor obtained using the composition of the present invention is excellent in the light shielding performance. That is, there is no deterioration in the light shielding performance in a specific wavelength region, and the minimum optical density in a predetermined region (for example, visible light region to 1200 nm) is in a range that can provide sufficient light shielding performance.

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

<Method of manufacturing 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 representative example, a method for producing a patterned cured film will be described in detail.

  In the method for producing a patterned cured film of the present invention, a step of applying a composition of the present invention on a substrate to form a composition layer (coated film) (hereinafter referred to as “composition layer forming step” and abbreviation) And exposing the composition layer through a mask (hereinafter simply referred to as “exposure step” as appropriate) and developing the exposed composition layer to form a patterned cured film And (e.g., appropriately abbreviated as "developing step").

Specifically, the composition of the present invention is applied onto a substrate directly or through another layer to form a composition layer (composition layer forming step) and exposed through a predetermined mask pattern. By curing only the composition layer irradiated with light (exposure step) and developing with a developer (development step), it is possible to form a patterned cured film consisting of pixels.
Each step will be described below.

(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 (coated film).

As the substrate, for example, non-alkali glass used in liquid crystal display devices, soda glass, Pyrex (registered trademark) glass, quartz glass, those obtained by attaching a transparent conductive film thereto, photoelectrics used in solid-state imaging devices, etc. A conversion element substrate (for example, a silicon substrate etc.), a CCD substrate, a CMOS substrate etc. are mentioned.
In addition, on these substrates, if necessary, a subbing layer may be provided to improve adhesion with the upper layer, to prevent diffusion of substances, or to planarize the substrate surface.

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

  From the viewpoint of resolution and developability, the coating thickness of the composition is preferably 0.35 μm or more and 1.5 μm or less, and more preferably 0.40 μm or more and 1.0 μm or less when the light shielding film for the image sensor is manufactured. preferable.

  The composition applied on the substrate is usually dried at 70 ° C. or more and 110 ° C. or less for 2 minutes or more and 4 minutes or less. Thereby, a 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 to cure only the coating film portion irradiated with light.
The exposure is preferably performed by irradiation with an actinic ray or radiation, and in particular, ultraviolet light such as g-ray, h-ray or i-ray is 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 alkali development process (development step) is performed to elute the non-light-irradiated portion in the exposure step into an aqueous alkaline solution. As a result, only the photocured portion (the coated film portion irradiated with light) remains.
As the developing solution, an organic alkaline developing solution which does not cause damage to the circuit of the base or the like is desirable. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.

  Examples of the alkaline aqueous solution include inorganic developers and organic developers. As the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium borate, or sodium metaborate, the concentration is 0.001 to 10% by mass, preferably 0.01 to The alkaline aqueous solution melt | dissolved so that it may be 1 mass% is mentioned. Examples of organic developers include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5.4. An alkaline aqueous solution in which an alkaline compound such as .0] -7-undecene is dissolved to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, may be mentioned. 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. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinses) with a pure water after image development.

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

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

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

(Color filter)
The color filter can be suitably used for a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for a high resolution CCD or CMOS having a size of more than one million pixels. The color filter can be disposed, for example, between the light receiving portion of each pixel constituting the CCD or CMOS and the microlens for collecting light. In addition, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned in a lattice shape, for example, by partition walls. The partition walls in this case preferably have a low refractive index for each color pixel. As an example of the imaging device which has such a structure, the apparatus of Unexamined-Japanese-Patent No. 2012-227478 and Unexamined-Japanese-Patent No. 2014-179577 is mentioned.
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, for example, as a pixel black matrix of a color filter.

(Light shielding film)
The light shielding film is formed on various members in the image display device or sensor module (for example, an infrared light cut filter, an outer peripheral portion of a solid imaging device, an outer peripheral portion of a wafer level lens, or a back surface of a solid imaging device) It can be used.
In addition, 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.
Although the thickness in particular of a light shielding film is not restrict | limited, 0.2-25 micrometers is preferable and 0.2-10 micrometers is more preferable. The thickness is an average thickness, and it 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, still more preferably 6% or less, and particularly preferably 4% or less. The reflectance of the light shielding film is a value obtained by entering light of 400 to 700 nm at an incident angle of 5 ° into the light shielding film and measuring the reflectance with a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. .

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

A plurality of photodiodes constituting a light receiving area of a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and transfer electrodes made of polysilicon and the like are provided on a substrate, and the photodiodes and the light reception of photodiodes are on transfer electrodes. The device has a light shielding film opened only at the portion, a device protection film made of silicon nitride or the like formed so as to cover the entire light shielding film and the photodiode light receiving portion on the light shielding film, and a color filter is formed on the device protection film. Configuration.
Furthermore, a configuration having a condensing means (for example, a micro lens etc. hereinafter the same) on the device protection layer and under the color filter (closer to the substrate), a configuration having a condensing means on the color filter, etc. May be

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

  For details of the definition of the display device or details of each display device, for example, “Electronic display device (authored by Akio Sasaki, published by Industry Research Association, 1990)”, “Display device (authored by Ibuki, authored by Sangyo Tosho Co., Ltd.) It is described in the original year issue). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industry Research Association, 1994)”. There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology."

When the color filter of the present invention is applied to a liquid crystal display device, the form is not particularly limited.
Below, the aspect in the case of applying the color filter of this invention to a liquid crystal display device is explained in full detail.
The color filter of the present invention may be used in a liquid crystal display device of a color TFT (Thin Film Transistor) system. The color TFT liquid crystal display device is described, for example, in “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., published in 1996)”. Furthermore, the color filter of the present invention may be a liquid crystal display device with an enlarged viewing angle such as a horizontal electric field drive system such as IPS (In Plane Switching) or a pixel division system such as MVA (Multi-domain Vertical Alignment), or STN ( The present invention is also applicable to Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), R-OCB (Reflective Optically Compensated Bend), and the like.
In addition, the color filter of the present invention can also be used for a bright and high-definition color-filter on array (COA) 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, the low dielectric constant and the stripping solution resistance, in addition to the above-mentioned normal requirements. Sometimes. The color filter of the present invention is excellent in light resistance and the like, so that it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability. 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)".

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 ensuring film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display composed of these known members. For these members, for example, “'94 Liquid crystal display peripheral materials and chemicals market (Kentaro Shima, Inc., CMSC Co., Ltd. 1994 issue),” “Present state and future prospects of liquid crystal related market in 2003 (second volume) Co., Ltd. Fuji Chimera Research Institute, published in 2003).
For backlights, see SID meeting Digest 1380 (2005) (A. Konno et. Al), or pages 18 to 24 of the monthly display December 2005 (Yasuhiro Shima), pages 25 to 30 (Takaaki Yagi), etc. It is described in.

  In addition, the cured film of the present invention may be 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 complex machine or a scanner; a surveillance camera, a barcode reader, cash deposit Dispensers (ATM) or industrial devices such as personal identification using high-speed cameras or face image authentication; automotive camera devices; medical camera devices such as endoscopes, capsule endoscopes or catheters; Optical filters used in space equipment, such as biosensors, cameras for military reconnaissance, cameras for three-dimensional maps, weather or ocean observation cameras, land resource exploration cameras, or exploration cameras for space astronomy or deep space targets Or a light shielding member or a light shielding layer of a module; It can be used for antireflection member or antireflective layer.

Moreover, the cured film of this invention can be used also for uses, such as micro LED (Light Emitting Diode) or micro OLED (Organic Light Emitting Diode). Although it does not specifically limit, In addition to the optical filter or optical film used for micro LED or micro OLED, it is suitably used with respect to the member which provides a light shielding function or an anti-reflective function.
Examples of micro LEDs or micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.

The cured film obtained by curing the composition of the present invention can also be used for applications such as quantum dot display. Although it does not specifically limit, In addition to the optical or optical film used for a quantum dot display, it is used suitably with respect to the member which provides a light shielding function or a reflection preventing function.
Examples of quantum dot displays are disclosed in U.S. Patent Application Publication No. 2013/0335657, 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 Those mentioned are mentioned.

Hereinafter, the present invention will be described in more detail based on examples. Materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.
In addition, unless there is particular notice, "part" and "%" are mass references.

〔Composition〕
Hereinafter, in preparation of the composition of an Example and a comparative example, first, each component contained in a composition is demonstrated.

<Inorganic pigment (pigment containing nitride or oxynitride)>
(TiN-1) Nisshin Engineering Co., Ltd. (Titanium nitride-containing particles, BET specific surface area 55 m ² / g, average primary particle diameter 24.2 nm)
(TiN-2) Hefei Corporation, trade name "TiN 20 nm" (particles containing titanium nitride, average primary particle diameter 41.7 nm)
(TiN-3) Mitsubishi Materials Co., Ltd., trade name “13M-T” (particles containing titanium oxynitride, average primary particle diameter 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. After dropwise adding 5.5 g of methacrylic acid chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) at an internal temperature of 5 ° C. or less, the mixture was allowed to react at room temperature for 90 minutes. The resulting 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 polymerizable group-containing compound was dissolved in 45 g of N, N-dimethylacetamide in a flask and heated to 70 ° C. In a nitrogen atmosphere, 0.5 g of thermal polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 45 g of N, N-dimethylacetamide was added dropwise over 30 minutes. After the dropwise addition, 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 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. After 5 g of methacrylic acid chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dropped thereto while keeping the internal temperature at 5 ° C. or less, the reaction was carried out at room temperature for 90 minutes. The resulting reaction solution was poured into a large excess of ethyl acetate, filtered, and the following polymerizable group-containing xanthene oligomers were removed (yield: 98%).

(Dye B)
According to JP 2013-253170 A, a xanthene skeleton compound having no polymerizable group represented by the following structure was obtained.

(Dye C)
An azo compound having no polymerizable group represented by the following structural formula was obtained according to JP-A-2004-534121. In the following structural formulae, M represents a hydrogen atom and / or a sodium atom depending on pH.

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

<Dispersing agent>
As a dispersant, dispersants A to E having the following structures were used. In the dispersants A, B and D, the numerical values described for each structural unit are intended to indicate the mass% of each structural unit with respect to the total structural unit. In addition, in the dispersant C, the numerical values (a to e) described in each structural unit mean the molar ratio of each structural unit to the total structural unit, and x and y mean the number of linkages. Moreover, in the dispersing agent E, the numerical value described in the linking group linked to Z intends the number of linking linked to Z.

<Polymerizable compound>
The following polymerizable compounds M1 were used as the polymerizable compounds.
・ Polymerizable compound M1
(Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA", see the following formula)

<Polymerization initiator>
The following oxime type initiator was used as a polymerization initiator.
-OXE-02: Irgacure OXE 02 (trade name, manufactured by BASF Japan Ltd.)

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

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

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

<Preparation of pigment dispersion>
First, a pigment containing a nitride or an oxynitride, a dispersant and an organic solvent were mixed for 15 minutes with a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion. Next, the resulting dispersion was subjected to dispersion treatment using NPM-Pilot manufactured by Shinmaru Enterprises, Inc. under the following conditions to obtain a pigment dispersion. The ratio (mass ratio) (hereinafter also referred to as “D / P”) of the dispersant to the pigment containing the nitride or the oxynitride (hereinafter, also referred to as “D / P”) becomes the ratio shown in each example and comparative example of Table 1. Added to
(Distribution condition)
· Bead diameter: φ 0.05 mm, (Nikkato zirconia beads, YTZ)
・ Bead packing rate: 65% by volume
・ Mill circumferential speed: 10 m / sec
・ Separator circumferential speed: 13 m / s
・ The amount of mixed liquid to be dispersed: 15 kg
Circulating flow rate (pump supply rate): 90 kg / hour
Processing solution temperature: 19 to 21 ° C.
・ Cooling water: Water ・ Processing 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 each composition of the examples and comparative examples shown in Table 1 below. I got In addition, about black dye, the composition which mixed the "carry-on agent" described in the table | surface and black dye was prepared previously, and this was mixed with other components, such as a pigment dispersion liquid.
Table 1 shows the content (% by mass) of each component contained in each composition of Examples and Comparative Examples.

<Measurement of the amount of water in the composition>
About the moisture content of each composition of an Example and a comparative example, it measured by MKV-710 (a brand name, the Kyoto Electronic Industry Co., Ltd. make) which makes Karl Fischer method a measurement principle. The results are shown in Table 1.
The water in the composition is derived from various raw materials.

[Evaluation test]
Each evaluation test below was done about each composition of an example and a comparative example.

<Number of particles>
Each composition of an Example and a comparative example was put into 100 mL Bloom bottle, and was left to stand in a 45 degreeC environment for 7 days. Then, 90 mL of the supernatant was removed, and the remaining 10 mL of the composition was diluted 500 times 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 solution was counted with a flow type particle image analyzer (trade name “FPIA”, manufactured by Malvern Co., Ltd.).

<Spectrum (light blocking property)>
The composition is applied by spin coating on a glass plate (EagleXG, Corning) of 0.7 mm in thickness and 10 cm square at a film thickness of 1.0 μm to form a coated film, and on a hot plate, The coated film was heat-treated at 100 ° C. for 2 minutes to obtain a dried film. The OD (optical density) of the resulting dried film was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the lowest OD at a wavelength of 400 to 1200 nm, the evaluation of the spectrum (light shielding property) was performed according to the following criteria. At this time, by preparing the composition of the composition, 50% by mass of the solid content of the coating solution was used as a pigment.
"A": Minimum OD> 2.5
"B": 2.5 最低 minimum OD> 2.3
"C": 2.3 ≧ minimum OD> 2.1
"D": 2.1 最低 minimum OD

<Temporal viscosity stability>
The compositions of Examples and Comparative Examples were stored at 23 ° C. for 10 days, and then stored at 7 ° C. for 90 days. Further, the viscosity of each composition before and after storage was measured using an E-type viscometer (trade name "R85-type viscometer" manufactured by Toki Sangyo Co., Ltd.) under the conditions of 10 rpm and 23 ° C. Then, the value (%) of [{(viscosity after time-viscosity immediately after preparation) / viscosity immediately after preparation} × 100] was calculated. Evaluation criteria are as follows.
"A": ± 3% or less "B": ± 3% or more, ± 5% or less "C": ± 5 or more%, ± 10% or less "D": ± 10% or more

<Reworkability>
On each electrode pattern of a silicon wafer having an electrode pattern (copper) formed on the surface, such that the dry film thickness of the coating film of each composition is 0.7 μm, using each composition of Examples and Comparative Examples. And each composition was spin-coated. Thereafter, the wafer was kept waiting for 10 minutes, and heat treatment (pre-baking) was performed for 120 seconds on a silicon wafer coated with each composition using a hot plate at 100 ° C. to form a coated film.
Then, the coated film was exposed at an exposure dose of 500 mJ / cm ² through a 20 μm square Island pattern mask at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon).
In addition, each composition of an Example and a comparative example is a negative photosensitive resin composition which an exposure part hardens | cures.
After that, the silicon wafer substrate on which the exposed coating film is formed is placed on a horizontal rotation table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics Co., Ltd.) Paddle development was carried out at 23 ° C. for 60 seconds using an organic alkaline solution developer (manufactured by Materials Co., Ltd.).
Next, the silicon wafer after paddle development is fixed to the above-mentioned horizontal rotary table by a vacuum chuck system, and while rotating the silicon wafer substrate at a rotation speed of 50 rpm by a rotary device, pure water is showered from above the rotation center , And 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 (tetramethyl ammonium hydroxide) at 85 ° C. for 5 hours, and immersed in a 2 L DIW (pure water) bath at room temperature for 2 minutes The rinse process was performed by doing. The reworkability was evaluated by observing the removal state of the frame-like pattern from the wafer after cleaning with an optical microscope (trade name “LEXT OLS 4500” manufactured by Olympus Corporation). Evaluation criteria are as follows.
"A": No pattern is observed "B": Particulate removal residue is observed in 5% or less of the pattern formation area "C": Particulate removal residue in more than 5% and 10% or less of the pattern formation area Observed "D": Particulate removal residue is observed over 10% of the patterned area, or a pattern or part of a pattern is observed

<Heat resistance>
The composition is applied by spin coating on a glass plate (EagleXG, Corning) of 0.7 mm in thickness and 10 cm square at a film thickness of 1.0 μm to form a coated film, and on a hot plate, The coated film was heat-treated at 100 ° C. for 2 minutes to obtain a dried film. The OD (optical density) of the resulting 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, spectral (light shielding property) was evaluated to obtain the minimum OD before the heat resistance test. The dried film was heat-treated on a hot plate at 265 ° C. for 10 minutes, and spectral evaluation was performed in the same manner as described above to obtain a minimum OD after the heat resistance test. The spectral variation in the heat resistance test was calculated by the following equation and evaluated.
"Variation = {(minimum OD after heat test-minimum OD before heat test) / minimum OD before heat test} x 100"
"A": ± 3% or less "B": ± 3% or more, ± 5% or less "C": ± 5 or more%, ± 10% or less "D": ± 10% or more

<Patternability (resolution)>
A coating was formed on an image sensor device substrate by a spin coater using the compositions of Examples and Comparative Examples. Next, the obtained coating film was subjected to prebaking treatment at 100 ° C. for 2 minutes on a hot plate. Subsequently, the coating film which has undergone the above-mentioned pre-baking treatment is exposed using an i-line exposure apparatus (FPA, manufactured by Canon) and further developed to cover the outer periphery of the light receiving portion on the substrate except 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 were formed.

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

  From the results of Table 1, it was confirmed that the light shielding films formed from the compositions of Examples 1 to 21 exhibit 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.

  In comparison with Examples 1, 6, 7 and 8, the content of the black dye is 0.3 or less (preferably 0.25 or less, more preferably) in mass ratio to the nitride or oxynitride-containing pigment. Was less than 0.2), it was shown that reworkability is further improved.

  When Examples 1, 4 and 5 are compared, it was shown that rework property, heat resistance and patternability are further improved by the black dye having a polymerizable group. Moreover, in Example 5 using an azo dye, it was confirmed that heat resistance is excellent.

  When Examples 1 and 9 to 12 are compared, 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 mg KOH / g or more. In particular, in Example 1, it was shown that the amount of particles in the liquid is smaller and the patterning property is also excellent by using the dispersing agent A containing benzyl methacrylate which is a hydrophobic component.

  When Examples 1, 16 and 17 are compared, when the solid content amount with respect to the composition total mass is 10-40 mass%, it was shown that a particle amount reduces more and stability over time becomes better. The results of Examples 13, 14 and 15 show that the light shielding performance of the obtained light shielding film is further improved when the solid content relative to the total mass of the composition is 12% by mass or more.

  Comparison of Examples 1, 20 and 21 shows that when the content of the 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 further improved. It was done. On the other hand, when the content of the pigment is 70% by mass or less with respect to the solid content, it was shown that the reworkability and the patternability are further improved.

(Example 22)
A composition was prepared in the same manner as in Example 1 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 and evaluated. It turned out that it has performance equivalent to Example 1.

(Example 23)
A dye A and a polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) are used instead of the dye A in Example 1, and the same procedure is followed except that the weight ratio is 1: 1. The composition was prepared and evaluated. It was found that the composition had performance equivalent to that of Example 1.

(Example 24)
A dye B and a polymerizable black dye “RDW-K01” (manufactured by Wako Pure Chemical Industries, Ltd.) are used instead of the dye B in Example 4 in the same manner, except that the mass ratio is 1: 1. The composition was prepared and evaluated. As a result, a better evaluation than in Example 4 was obtained, and specifically, the evaluation of reworkability, heat resistance and patterning were all "B". I understand.

(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 similarly prepared except that it was used as a mass ratio of 7: 3 using the carbon black manufactured by the above, and was evaluated. It was found that the same performance as Example 1 was obtained.

(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 at a mass ratio of 9: 1. The composition was prepared and evaluated in the same manner as in Example 1 except that it was found to have the same performance as Example 1, and it was found that a darker light-shielding film was obtained. From this result, it is presumed that the desired effect of the present invention can be obtained even when used in combination with other organic pigments or chromatic dyes.

Claims (20)

  A composition comprising 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, 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 dispersant has an acid value of 50 mg KOH / g or more.   The composition according to claim 7 or 8, wherein the dispersing agent 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 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.   The cured film obtained using the composition of any one of Claims 1-15.   A color filter comprising the cured film according to claim 16.   The light shielding film which has a cured film of Claim 16.   The solid-state imaging device which has a cured film of Claim 16.   The image display apparatus which has a cured film of Claim 16.