JP6745869B2 - Composition, method for producing composition, cured film, color filter, light-shielding film, solid-state imaging device, and image display device - Google Patents

Description

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

Conventionally, a composition containing titanium nitride is known. The composition containing titanium nitride is used for various purposes, for example, for producing a light-shielding film provided in a liquid crystal display device, a solid-state imaging device, or the like.
Specifically, a color filter used in a liquid crystal display device is provided with a light-shielding film called a black matrix for the purpose of blocking light between colored pixels and improving contrast.
In addition, a black matrix is also provided in the solid-state image sensor for the purpose of preventing noise generation and improving image quality. 2. Description of the Related Art Currently, small and thin imaging units are mounted on mobile terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants). Such an image pickup unit generally includes a solid-state image sensor such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and a lens for forming a subject image on the solid-state image sensor. Equipped with.

As a composition for forming a black matrix for a liquid crystal display device and a solid-state imaging device, for example, Japanese Patent Application Laid-Open No. 2004-242242 discloses that "at least a light shielding material, a resin and a solvent are contained, and at least titanium nitride particles are contained as a light shielding material. A black resin composition for a resin black matrix, wherein a diffraction angle 2θ of a peak derived from the (200) plane of the titanium nitride particles when CuKα rays are used as an X-ray source is 42.5° or more and 42.8°. The following black resin composition for resin black matrix is disclosed (Claim 1).

Patent No. 5136139

A composition containing titanium nitride particles (titanium nitride-containing particles) as described above may be used to form a patterned cured film on a substrate on which an electrode pattern is formed. is there.
Therefore, when the present inventors applied a composition containing titanium nitride-containing particles on a substrate on which an electrode pattern was formed to produce a patterned cured film, titanium nitride-containing particles were obtained. It was revealed that, depending on the type, the electrode pattern deteriorates (corrosion) or a desired pattern cannot be obtained (decrease in patterning property).

Therefore, an object of the present invention is to provide a composition capable of producing a cured film having excellent patterning properties and electrode anticorrosion properties. Another object of the present invention is to provide a method for producing a composition, a cured film, a color filter, a light shielding film, a solid-state image sensor and an image display device.

As a result of diligent studies on the above problems, the present inventor has found that the content of Fe atoms in the titanium nitride-containing particles within a predetermined range makes it possible to produce a cured film having excellent patterning properties and electrode anticorrosion properties. Heading out, the present invention was reached.
That is, the present inventor has found that the above problems can be solved by the following configurations.

[1]
Containing titanium nitride-containing particles containing Fe atoms,
The composition, wherein the content of Fe atoms in the titanium nitride-containing particles is more than 0.001 mass% and less than 0.4 mass%.
[2]
In the above [1], the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is more than 42.6° and 43.5° or less when CuKα ray is used as the X-ray source. The composition as described.
[3]
The titanium nitride-containing particles further contain Si atoms,
The composition according to the above [1] or [2], wherein the content of the Si atoms in the titanium nitride-containing particles is more than 0.002 mass% and less than 0.3 mass %.
[4]
The composition according to any one of the above [1] to [3], wherein the number of the titanium nitride-containing particles having a size of 10 μm or more determined by the following particle number measuring method is 100 or less.
Particle number measurement method: A sample solution prepared by diluting the above composition 500 times with propylene glycol monomethyl ether acetate was prepared, and the number of particles containing titanium nitride having a size of 10 μm or more contained in 10 ml of the sample solution was calculated by a flow method. It is measured by a particle image analyzer.
[5]
Furthermore, the composition according to any one of the above [1] to [4], which contains two or more kinds of organic solvents.
[6]
Further, the composition according to any one of the above [1] to [5], which further contains a binder resin.
[7]
Furthermore, the composition according to any one of the above [1] to [6], which contains a polymerizable compound.
[8]
Furthermore, the composition according to any one of the above [1] to [7], which further comprises a polymerization initiator.
[9]
The composition according to any one of the above [1] to [8], wherein the solid content in the composition is 10 to 40 mass %.
[10]
The composition according to any one of the above [1] to [9], wherein the content of the titanium nitride-containing particles is 20 to 70 mass% with respect to the total solid content of the composition.
[11]
In addition, containing water,
The composition according to any one of the above [1] to [10], wherein the content of the water is 0.1 to 1 mass% with respect to the total mass of the composition.
[12]
Furthermore, containing a dispersant,
Any one of the above [1] to [11], wherein the dispersant has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and cyclic or chain polyester The composition as described.
[13]
The composition according to [12] above, wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.05 to 0.30 in mass ratio.
[14]
A method for producing the composition according to any one of the above [1] to [13], comprising:
A method for producing a composition, comprising the step of obtaining the titanium nitride-containing particles by a thermal plasma method.
[15]
A cured film obtained using the composition according to any one of [1] to [13].
[16]
A color filter having the cured film according to the above [15].
[17]
A light-shielding film having the cured film according to the above [15].
[18]
A solid-state image sensor having the cured film according to the above [15].
[19]
An image display device having the cured film according to the above [15].

As shown below, according to the present invention, it is possible to provide a composition capable of producing a cured film having excellent patterning properties and electrode anticorrosion properties. Further, according to the present invention, it is possible to provide a method for producing a composition, a cured film, a color filter, a light-shielding film, a solid-state image sensor, and an image display device.

The present invention will be described below.
In the present specification, the numerical range represented by "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.
In the description of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not included includes not only those having no substituent but also 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).
The term “actinic ray” or “radiation” as used herein means, for example, a bright line spectrum of a mercury lamp, deep ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. .. In the present invention, light means actinic rays or radiation. Unless otherwise specified, the term "exposure" in the present specification means not only exposure with a bright line spectrum of a mercury lamp, deep ultraviolet rays typified by excimer laser, X-rays, and EUV light, but also electron beam, ion beam, etc. Drawing with particle beam is also included in exposure.
In the present specification, “(meth)acrylate” means acrylate and methacrylate, “(meth)acrylic” means acrylic and methacrylic, “(meth)acryloyl” means acryloyl and methacryloyl, and “(meth ) "Acrylamide" refers to acrylamide and methacrylamide. In addition, in the present specification, “monomer” and “monomer” have the same meaning. The monomer in the present invention is a compound having a weight average molecular weight of 2,000 or less, which is distinguished from oligomers and polymers. 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 means a group involved in the polymerization reaction.

[Composition]
The composition of the present invention contains titanium nitride-containing particles containing Fe atoms, and the content of Fe atoms in the titanium nitride-containing particles is more than 0.001% by mass and less than 0.4% by mass. ..
According to the composition of the present invention, a cured film having excellent patterning properties and electrode anticorrosion properties can be produced.
As a result of intensive studies, the present inventors have found that the content of Fe atoms in the titanium nitride-containing particles is related to the patterning property and the anticorrosion property of the electrode.
The Fe atoms contained in the titanium nitride-containing particles have excellent adhesion to the electrode and the substrate, and the titanium nitride contained in the titanium nitride-containing particles was attached to the electrodes and the substrate via the Fe atoms. Conceivable. Therefore, it is considered that Fe atoms remained on the electrodes and the substrate after the patterning of the cured film such as the development process, and the titanium nitride was easily removed. Therefore, it is presumed that the patternability of the cured film was improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more.
On the other hand, when the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrode and the substrate is considered to increase, which causes corrosion of the electrode. Therefore, it is presumed that the corrosion resistance of the electrode was improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less.

The components contained in the composition and the components that can be contained therein will be described below.

<Titanium nitride-containing particles>
The composition of the present invention contains titanium nitride-containing particles containing Fe atoms. The titanium nitride-containing particles are preferably used as a black pigment.
A gas phase reaction method is usually used for producing titanium nitride-containing particles, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because it is less contaminated with impurities, has a uniform particle size, and has high productivity.
Examples of the method of generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, and hybrid plasma, and high frequency plasma in which impurities from the electrodes are less mixed is preferable. As a specific method for producing titanium nitride-containing fine particles by the thermal plasma method, for example, titanium powder is vaporized by high frequency thermal plasma, nitrogen is introduced into the device as a carrier gas, and the titanium powder is nitrided in the cooling process. , A method of synthesizing particles containing titanium nitride. The thermal plasma method is not limited to the above.

The method for producing the titanium nitride-containing particles contained in the composition of the present invention is not particularly limited, but refer to the production methods described in paragraphs <0037> to <0089> of WO 2010/147098. it can. For example, in place of the Ag powder of WO 2010/147098, a component containing Fe and/or a component containing Si described below is used, and a mixture thereof with a titanium powder material (titanium particles) is used as a raw material. The titanium nitride-containing particles included in the composition of the present invention can be manufactured.

The titanium powder material (titanium particles) used for producing the titanium nitride-containing particles is preferably highly pure. The titanium powder material is not particularly limited, but one having a titanium element purity of 99.99% or more is preferable, and one having a purity of 99.999% or more is more preferably used.

The titanium powder material (titanium particles) used for producing the titanium nitride-containing particles may contain atoms other than titanium atoms. Other atoms that can be contained in the titanium powder material include, for example, Fe atoms and Si atoms.
When the titanium powder material contains Fe atoms, the content of Fe atoms is preferably more than 0.001 mass% with respect to the total mass of the titanium powder material. Thereby, the patterning property of the cured film is more excellent. Further, when the titanium powder material contains Fe atoms, the content of Fe atoms is preferably less than 0.4 mass% with respect to the total amount of titanium powder material. Thereby, the corrosion resistance of the electrode by the cured film is more excellent (corrosion of the electrode by the cured film can be further suppressed). That is, the Fe atom contained in the titanium powder material used for the production of the titanium nitride-containing particles is within the above range (more than 0.001 mass and less than 0.4 mass%), so that the effect of the present invention is more remarkable. Can be obtained.
When the titanium powder material contains Si atoms, the content of Si atoms is preferably more than 0.002 mass% and less than 0.3 mass% with respect to the total mass of the titanium powder material, and 0.01 ˜0.15% by mass, more preferably 0.02 to 0.1% by mass. When the content of Si atoms is more than 0.002 mass %, the patterning property of the cured film is further improved. In addition, when the content of Si atoms is less than 0.3% by mass, the polarity of the outermost surface layer of the obtained titanium nitride-containing particles is stable, and the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed. It is considered that the adsorptivity of the dispersant to the titanium oxide is improved and the undispersed particles of the titanium nitride-containing particles are reduced, so that the generation of particles is suppressed. That is, the effect of the present invention can be more remarkably obtained when the Si atom contained in the titanium powder material used for producing the titanium nitride-containing particles is within the above range.
Further, the water content in the titanium powder material (titanium particles) used for producing the titanium nitride-containing particles is preferably less than 1% by mass, and less than 0.1% by mass with respect to the total mass of the titanium powder material. Is more preferable, and it is even more preferable that it is not substantially contained. When the water content in the titanium powder material used for producing the titanium nitride-containing particles is within the above range, the effect of the present invention can be more remarkably obtained.

Further, the titanium nitride-containing particles have a diffraction angle 2θ (details will be described later) of a peak derived from the (200) plane when CuKα rays are used as the X-ray source, because the titanium nitride-containing particles are obtained by using a thermal plasma method. It becomes easy to adjust in the range of more than 42.6° and 43.5° or less.

Here, the method of containing Fe atoms in the titanium nitride-containing particles is not particularly limited, and, for example, in the step of obtaining titanium particles (titanium powder) used as a raw material of the titanium nitride-containing particles described above, Fe atoms And the like. More specifically, when titanium is produced by the Kroll method or the like, a reaction vessel made of a material containing Fe atoms such as stainless steel (SUS) is used, or a press for crushing titanium is used. The Fe atom can be attached to the surface of the titanium particle by using a material containing Fe atom as the material of the crusher.
Further, when the thermal plasma method is used in the production of titanium nitride-containing particles, components such as Fe particles and Fe oxide are added in addition to titanium particles as a raw material, and these are nitrided by the thermal plasma method. As a result, the titanium nitride-containing particles can contain Fe atoms.
The Fe atoms contained in the titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides. It may be contained in any form such as and oxysulfide. Further, the Fe atom contained in the titanium nitride-containing particles may exist as an impurity at a crystal interstitial position, or may exist as an impurity in a crystal grain boundary in an amorphous state.

The content of Fe atoms in the titanium nitride-containing particles is more than 0.001 mass% and less than 0.4 mass% with respect to the total mass of the titanium nitride-containing particles. Among them, 0.01 to 0.2 mass% is preferable, and 0.02 to 0.1 mass% is more preferable. When the content of Fe atoms is more than 0.001% by mass, the patternability of the cured film is excellent. When the content of Fe atoms is less than 0.4% by mass, the corrosion resistance of the electrode by the cured film is excellent (corrosion of the electrode by the cured film can be suppressed).
That is, when the content of Fe atoms in the titanium nitride-containing particles is within the above range, the effects of the present invention (patterning property of the cured film and anticorrosion property of the electrode) are remarkably exhibited.
Here, the content of Fe atoms in the titanium nitride-containing particles is measured by ICP (high frequency inductively coupled plasma) emission spectroscopy.

The titanium nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of the cured film is further improved. It is considered that the reason why the patterning property is improved by containing the Si atom is the same as the Fe atom described above.
The content of Si atoms in the titanium nitride-containing particles is preferably more than 0.002 mass% and less than 0.3 mass% with respect to the total mass of the titanium nitride-containing particles, and 0.01 to 0.15. The content is more preferably the mass%, further preferably 0.02 to 0.1 mass%. When the content of Si atoms is more than 0.002 mass %, the patterning property of the cured film is further improved. Further, when the content is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles becomes stable, and the adsorptivity of the dispersant to the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed. It is considered that the improvement of the titanium nitride-containing particles and the reduction of the undispersed particles of the titanium nitride-containing particles have the effect of suppressing the generation of particles.
The content of Si atoms in the titanium nitride-containing particles is measured by the same method as that for the Fe atoms described above.

The method for incorporating Si atoms into the titanium nitride-containing particles is not particularly limited, and for example, introducing Si atoms in the stage of obtaining the titanium particles (titanium powder) used as the raw material of the titanium nitride-containing particles described above. Method etc. are mentioned. More specifically, when producing titanium by the Kroll method or the like, a reaction vessel made of a material containing Si atoms is used, or a Si atom is used as a material for a press or a crusher when crushing titanium. Si atoms can be attached to the surface of the titanium particles by using a material containing.
When the thermal plasma method is used in the production of titanium nitride-containing particles, components such as Si particles and Si oxide are added in addition to titanium particles as a raw material, and these are nitrided by the thermal plasma method. As a result, the titanium nitride-containing particles can contain Si atoms.
The Si atoms contained in the titanium nitride-containing particles include ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides and acids. It may be contained in any form such as sulfide. Further, the Si atom contained in the titanium nitride-containing particles may exist as an impurity at the crystal interstitial position, or may exist as an impurity in the crystal grain boundary in an amorphous state.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass, and more preferably 15 to 75% by mass, based on the total mass of the titanium nitride-containing particles. More preferably, it is more preferably 20 to 70 mass %. The content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP emission spectroscopy.
The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 3 to 60% by mass, and preferably 5 to 50% by mass, based on the total mass of the titanium nitride-containing particles. More preferably, it is more preferably 10 to 40% by mass. The content of nitrogen atoms can be analyzed by an inert gas melting-thermal conductivity method.
Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become prominent when oxygen is mixed in during its synthesis or when the particle size is small, but due to oxidation of the particle surface, etc. You may contain a part oxygen atom.
The content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass, based on the total mass of the titanium nitride-containing particles. It is more preferable that the content is ˜30% by mass. The content of oxygen atoms can be analyzed by an inert gas melting-infrared absorption method.

From the viewpoint of dispersion stability and light shielding properties, the specific surface area of the titanium nitride-containing particles is preferably 5 m ² /g or more and 100 m ² /g or less, and more preferably 10 m ² /g or more and 60 m ² /g or less. The specific surface area can be determined by the BET method.

The titanium nitride-containing particles may be composite particles composed of titanium nitride particles and metal particles.
The composite fine particles are particles in which titanium nitride particles and metal fine particles are combined or are highly dispersed. Here, "composite" means that the particles are composed of both components of titanium nitride and metal, and "highly dispersed" means that titanium nitride particles and metal particles are It means that each of them exists individually, and particles of minor components are not aggregated and are uniformly and uniformly dispersed.
The metal fine particles are not particularly limited and include, for example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium, bismuth. , Antimony and lead, and alloys thereof. Among them, at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, and copper, silver, gold, platinum and tin, and these More preferably, it is at least one selected from the above alloys. From the viewpoint of being more excellent in moisture resistance, silver is preferable.
The content of the metal fine particles in the titanium nitride-containing particles is preferably 5% by mass or more and 50% by mass or less, and 10% by mass or more and 30% by mass or less, based on the total mass of the titanium nitride-containing particles. Is more preferable.

The titanium nitride-containing particles preferably have a diffraction angle 2θ of a peak derived from the (200) plane of more than 42.6° and 43.5° or less when CuKα ray is used as the X-ray source. A cured film (for example, a black matrix) obtained by using a composition containing titanium nitride-containing particles having such characteristics has a high concentration while keeping the concentration of titanium nitride-containing particles in the composition low. It becomes possible to achieve the OD value. As a result, the cured film can secure high adhesion.

When an X-ray diffraction spectrum of a titanium compound was measured using CuKα ray as an X-ray source, TiN had a peak having a strongest intensity derived from the (200) plane near 2θ=42.5°, and TiO had a peak of (200 ) A peak derived from the plane is seen near 2θ=43.4°. On the other hand, most peaks not strength strong peak is anatase TiO ₂ is derived from the (200) plane in the vicinity 2 [Theta] = 48.1 °, rutile TiO ₂ and a peak derived from (200) plane is 2 [Theta] = 39 Observed near 2°. Therefore, the peak position shifts to a higher angle side with respect to 42.5° as the crystalline state contains more oxygen atoms.

The diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.6° and less than 43.5° from the viewpoint of the temporal stability of the particles, and further, at the time of production. It is more preferably 42.7° or more and less than 43.5° from the viewpoint of excellent process margin, and further preferably 42.7° or more and less than 43.4° from the viewpoint of excellent reproducibility of particle performance. When titanium oxide TiO ₂ is contained as an accessory component, a peak derived from anatase-type TiO ₂ (101) is the strongest peak near 2θ=25.3°, and a peak derived from rutile-type TiO ₂ (110). Is seen near 2θ=27.4°. However, since TiO ₂ is white and becomes a factor that deteriorates the light-shielding property of the black matrix, it is preferable that TiO ₂ is reduced to the 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 Scherrer's formula.

The crystallite size is preferably 20 nm or more, more preferably 20 to 50 nm. By forming a black matrix using titanium nitride-containing particles having a crystallite size of 20 nm or more, the light transmitted through the cured film exhibits a blue to violet color with a peak wavelength of 475 nm or less, and high light-shielding properties. It is possible to obtain a black matrix that also has ultraviolet sensitivity. When the crystallite size is 20 nm or more, the ratio of the active particle surface to the particle volume is small and the balance is good, and the titanium nitride-containing particles are more excellent in heat resistance and/or durability. Becomes

The content of the titanium nitride-containing particles is preferably 20 to 70% by mass, more preferably 30 to 70% by mass, and 40 to 70% by mass based on the total solid content of the composition. It is more preferable that the content is 45 to 70% by mass. When the content of the titanium nitride-containing particles is 20% by mass or more, the light shielding property is improved. When the content of the titanium nitride-containing particles is 70% by mass or less, the temporal stability of the composition is improved.
In addition, in this specification, a solid content intends the component which comprises the cured film formed of a composition, and does not contain a solvent. For example, since the polymerizable compound described below is a component that constitutes the cured film, even a liquid (liquid state) is included in the solid content.

The particle diameter D90 of the titanium nitride-containing particles in the composition is preferably 5 to 100 nm, more preferably 10 to 75 nm, and further preferably 10 to 60 nm. The particle size of the titanium nitride-containing particles in the composition is measured using a device according to a particle size distribution measuring device Nanotrack UPA-150EX manufactured by Microtrac.

In the composition of the present invention, the number of titanium nitride-containing particles having a size of 10 μm or more determined by the following particle number measuring method is preferably 100 or less, more preferably 0 to 100, More preferably, it is 0 to 20. This improves the filterability of the composition.
Particle number measurement method: A sample solution prepared by diluting the composition of the present invention 500 times with propylene glycol monomethyl ether acetate was prepared, and the number of particles containing titanium nitride having a size of 10 μm or more contained in 10 ml of the sample solution was calculated by a flow method. It is measured by a particle image analyzer.

The size of the titanium nitride-containing particles can be measured by using a flow particle image analyzer (Flow Particle Image Analyzer). A specific example of the flow type particle image analyzer is a flow type particle image analyzer FPIA?3000 manufactured by Sysmex Corporation. The FPIA-3000 is a device that measures a particle image using the imaging flow cytometry method and performs particle analysis.
The size of the titanium nitride-containing particles is determined by using a solvent such as an organic solvent or water in the flow path (flow path extending along the flow direction) of the flat and flat transparent flow cell (thickness of about 200 μm) of the flow type particle image analyzer. Is measured by passing a sample solution in which the composition is diluted.
In the flow-type particle image analyzer, a strobe and a CCD camera are mounted so as to be located on opposite sides of the flow cell in order to form an optical path that passes in a direction intersecting the thickness direction of the flow cell. .. The stroboscope irradiates stroboscopic light at 1/60 second intervals while the sample solution is flowing through the channel. As a result, each particle flowing through the flow cell is captured as a two-dimensional image having a certain range parallel to the flow cell. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the “size” of the present invention.
The sample used for measurement is preferably prepared by diluting the composition with a solvent such as an organic solvent or water. More preferably, the sample is a dispersion liquid containing titanium nitride-containing particles in a dispersed state. As for the method for preparing the sample, it is preferable to dilute the composition containing the titanium nitride-containing particles with a solvent such as an organic solvent or water so that the solid content becomes 10 to 40% by mass. It is more preferable to dissolve the components in a solvent and then redisperse the titanium nitride-containing particles.
For the sample, it is more preferable to further dilute the dispersion liquid in which the particles containing titanium nitride are redispersed by 10 to 2000 times. The state of the dispersion liquid in which the titanium nitride-containing particles are dispersed is preferably a state in which the average particle diameter (D90) of the titanium nitride-containing particles measured by the dynamic light scattering method is 1 μm or less.
The measuring device by the dynamic light scattering method is not particularly limited, and examples include Microtrac's product name “Nanotrack UPA-150EX” and the like.

<Dispersant>
The composition of the present invention preferably contains a dispersant. The dispersant contributes to improving the dispersibility of the pigment such as the titanium nitride-containing particles described above. In the present invention, the dispersant and the binder resin described below are different components.
As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
As the dispersant, a polymer dispersant (for example, polyamidoamine 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) Copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivative.
The polymer compound can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer based on its structure.

The polymer compound is adsorbed on the surface of the object to be dispersed, such as a black pigment, which is a preferred embodiment of the titanium nitride-containing particles, and a pigment, which is optionally used in combination, and acts to prevent reaggregation of the object to be dispersed. Therefore, a terminal modified polymer, a graft polymer, and a block polymer having an anchor site on the pigment surface are preferable.
On the other hand, by modifying the surface of the titanium nitride-containing particles, it is possible to promote the adsorptivity of the polymer compound to the particles.

The polymer compound preferably has a structural unit having a graft chain. In the present specification, “structural unit” has the same meaning as “repeating unit”.
Since the polymer compound having a structural unit having such a graft chain has affinity with a solvent due to the graft chain, it is excellent in dispersibility of a coloring pigment such as a black pigment and dispersion stability after aging. Is. Further, due to the presence of the graft chain, the polymer compound having the structural unit having the graft chain has affinity with the polymerizable compound or other resins that can be used in combination. As a result, residues are less likely to be generated in the alkali development.
When the graft chain is long, the steric repulsion effect is high and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptivity to a color pigment such as a black pigment decreases, and the dispersibility of the pigment tends to decrease. Therefore, the graft chain preferably has 40 to 10000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and has an atom number excluding hydrogen atoms. It is more preferably 60 to 500.
Here, the graft chain refers to the root of the main chain of the copolymer (atoms bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably has a polymer structure, and examples of such a polymer structure include a poly(meth)acrylate structure (for example, a poly(meth)acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. , And a polyether structure.
In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility, the graft chain should be at least one selected from the group consisting of a polyester structure, a polyether structure and a poly(meth)acrylate structure. A graft chain having a polyester structure or a polyether structure is more preferable.

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

Commercially available macromonomers corresponding to the structural unit having a graft chain of the polymer compound and suitably used for the synthesis of the polymer compound include AA-6 (trade name, Toagosei Co., Ltd.), AA-10 ( Trade name, manufactured by Toagosei Co., Ltd., AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS-6 (trade name, manufactured by Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei). Co., Ltd.), AW-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-714 (trade name, manufactured by Toagosei Co., Ltd.), AY-707 (trade name, manufactured by Toagosei Co., Ltd.), AY-714 (trade name, manufactured by Toagosei Co., Ltd.), AK-5 (trade name, manufactured by Toagosei Co., Ltd.), AK-30 (trade name, manufactured by Toagosei Co., Ltd.), AK-32 (product) Name, manufactured by Toagosei Co., Ltd., Bremmer PP-100 (trade name, manufactured by NOF Corporation), BREMMER PP-500 (trade name, manufactured by NOF Corporation), BREMMER PP-800 (trade name, manufactured by NOF CORPORATION). NOF CORPORATION, BREMMER PP-1000 (trade name, NOF Corporation), BREMMER 55-PET-800 (trade name, NOF Corporation), BREMMER PME-4000 (trade name, NOF CORPORATION, BREMMER PSE-400 (trade name, manufactured by NOF CORPORATION), BREMMER PSE-1300 (trade name, manufactured by NOF Corporation), BREMMER 43PAPE-600B (trade name, NOF Corporation) (Manufactured by Co., Ltd.), etc. Among them, AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.) are preferable. , AS-6 (trade name, Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), and Bremmer PME-4000 (trade name, manufactured by NOF CORPORATION), etc. To be

The dispersant of the present invention preferably has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and cyclic or chain polyester. More preferably, the dispersant of the present invention is at least one selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and chain polyester. More preferably, the dispersant of the present invention is at least one selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, polycaprolactone and polyvalerolactone. The dispersant may have the above structure alone in one dispersant, or may have a plurality of these structures in one dispersant.
Here, the polycaprolactone structure means a structure having a ring-opening structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure having a ring-opening structure of δ-valerolactone as a repeating unit.
Specific examples of the dispersant having a polycaprolactone structure include those having j and k of 5 in the following formulas (1) and (2). Further, specific examples of the dispersant having a polyvalerolactone structure include those having j and k of 4 in the following formulas (1) and (2).
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. Further, specific examples of the dispersant having a polymethylmethacrylate structure include those in which X ⁵ in the following formula (4) is a methyl group and R ⁴ is a methyl group.

The polymer compound preferably contains, as a structural unit having a graft chain, a structural unit represented by any of the following formulas (1) to (4), the following formula (1A), the following formula (2A), It is more preferable to include a structural unit represented by any one 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. From the viewpoint of synthetic constraints, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms). Is more preferable, each independently a hydrogen atom or a methyl group is more preferable, and a methyl group is further preferable.

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

In Formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, but specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group and the like. Is mentioned. Among these, as the organic groups represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Is preferred, and 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. 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 represent the integer of 2-8 each independently. From the viewpoint of dispersion stability and developability of the composition, j and k in the formulas (1) and (2) are preferably integers of 4 to 6, and most preferably 5.

In formula (3), R ³ represents a branched or straight-chain 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, a plurality of R ^3's may be the same or different.
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. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is further preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same as or different from each other.

Further, the polymer compound may have two or more kinds of structural units having different structures and having a graft chain. That is, in the molecule of the polymer compound, structural units represented by the formulas (1) to (4) having different structures may be contained, and n and m in the formulas (1) to (4) may be included. , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may have different structures in their side chains, and formula (3) and In the formula (4), a plurality of R ³ , R ⁴ and X ⁵ present in the molecule may be the same 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.
Further, the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability of the composition.

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

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

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

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

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

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

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

The ClogP value is obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program "CLOGP" available from This program provides the value of "calculated logP" calculated by the Hansch, Leo fragment approach (see below). The fragment approach is based on the chemical structure of a compound and estimates the compound's logP value by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to that 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. Sammmens, J.M. B. Taylor and C.I. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoint from structure. Chem. Rev. , 93, 1281-1306, 1993.

logP means a common logarithm of a partition coefficient P (Partition Coefficient), and quantitatively shows how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. Is a physical property value expressed as a numerical value, and is represented by the following formula.
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.
It means that the oil solubility increases when the value of logP increases to a positive value across 0, and the water solubility increases when the absolute value increases to a negative value, and there is a negative correlation with the water solubility of organic compounds. It is widely used as a parameter for estimating the water content.

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

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

L is a single bond or 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, a substituted alkynylene group) and a divalent aromatic group (for example, an arylene group. , A substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ —, where R ^31. Is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.

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

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocycle. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. Moreover, 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), a substituted imino group (=NR ³² , where 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. Further, L may include a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. Polyoxyethylene structure, - _(OCH 2 _CH 2) represented by n-, n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

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

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 more preferable. The aliphatic group further includes a ring-assembled hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include bicyclohexyl group, perhydronaphthalenyl group, biphenyl group, 4-cyclohexyl group. A phenyl group and the like are included. As the crosslinked cyclic hydrocarbon ring, for example, a bicyclic type such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.) Hydrocarbon ring, tricyclic hydrocarbon ring such as homobredan, adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[4.3.1.1 ^2,5 ]undecane ring, tetracyclo[4 4.0.1 ^2,5 . 1 ^7,10 ]dodecane, perhydro-1,4-methano-5,8-methanonaphthalene ring, and other tetracyclic hydrocarbon rings. Further, the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydro. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Moreover, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. 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 more preferable. Moreover, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocycle. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. Moreover, 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), a substituted imino group (═N—R ³² , where R ³² is a fat. Group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (eg, A methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Here, L and Z have the same meanings as described 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 general formula (i), R ¹ , R ² , and R ³ are hydrogen atoms or methyl groups, and L is a single bond or an alkylene group or an oxyalkylene structure. A compound having a divalent linking group including, wherein X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
In addition, as the monomer represented by the general formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Are preferred. In addition, as the monomer represented by the general formula (iii), R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms or methyl groups, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.

Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, and styrenes.
As examples of typical compounds represented by formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.

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

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

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

Examples of the acid group that is a functional group capable of forming an interaction with a coloring pigment such as a black pigment include, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably a carboxylic acid. Group, a sulfonic acid group, and at least one kind of a phosphoric acid group, particularly preferable one is that the adsorption power to a color pigment such as a black pigment is good, and the dispersibility of the color pigment is high. It is a carboxylic acid group.
That is, the polymer compound 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 type or two or more types of structural units having an acid group.
The polymer compound may or may not contain a structural unit having an acid group, but in the case of containing, the content of the structural unit having an acid group is, in terms of mass, based on the total mass of the polymer compound. %, preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing image strength damage due to alkali development.

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

A coordinating group that is a functional group capable of forming an interaction with a coloring pigment such as a black pigment, and a reactive functional group, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chlorides. Preferred is an acetylacetoxy group because of its good adsorption to a color pigment such as a black pigment and high dispersibility of the color pigment. The polymer compound may have one type or two or more types of these groups.
The polymer compound may or may not contain a structural unit having a coordinating group, or a structural unit having a reactive functional group, but in the case of containing, the content of these structural units is In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less, from the viewpoint of suppressing development inhibition, with respect to the total mass of the polymer compound.

When the polymer compound in the present invention has a functional group capable of forming an interaction with a color pigment such as a black pigment in addition to the graft chain, it forms an interaction with a color pigment such as various black pigments as described above. It suffices that it contains a functional group capable of controlling, and the introduction of these functional groups is not particularly limited, but the polymer compound is represented by the following general formulas (iv) to (vi). It is preferable to have at least one structural unit selected from structural units derived from a monomer.

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number. Represents an alkyl group of 1 to 6 (eg, methyl group, ethyl group, propyl group, etc.).
In formulas (iv) to (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, and more preferably Each is independently a hydrogen atom or a methyl group. In general formula (iv), it is particularly preferable that R ¹² and R ¹³ are each a hydrogen atom.

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

In addition, L ₁ in the general formulas (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), divalent aromatic group (eg, , An arylene group, and a substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino bond (—NR ³¹ ′— Here, R ³¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—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 more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Moreover, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group and a heterocyclic group.

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. Moreover, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocycle. The heterocycle may be condensed with one or more other heterocycles, aliphatic rings or aromatic rings. Moreover, 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), a substituted imino group (═N—R ³² , where R ³² is a fat. Group, aromatic group or heterocyclic group), aliphatic group, aromatic group and 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 include a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. Polyoxyethylene structure, - _(OCH 2 _CH 2) represented by n-, n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In the general formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with a coloring pigment such as a black pigment other than the graft chain, a carboxylic acid group and a tertiary amino group. Is preferred, and a carboxylic acid group is more preferred.

In formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), - represents a _{Z 1} or _L 1 -Z _1,. Here, L ₁ and Z ₁ have the same meanings as L ₁ and Z ₁ described above, and preferred examples are also the same. R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as the monomer represented by the general formula (iv), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is an alkylene group or an oxyalkylene structure. And a divalent linking group containing X, wherein X ₁ is an oxygen atom or an imino group, and Z ₁ is a carboxylic acid group.
As the monomer represented by the general formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Further, 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 is a carboxylic acid group are preferred.

Below, the typical example of the monomer (compound) represented by General formula (iv)-General formula (vi) is shown.
Examples of the monomer include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) 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 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 with pyromellitic anhydride, Examples thereof include acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenylmethacrylamide.

The content of the structural unit having a functional group capable of forming an interaction with a color pigment such as a black pigment, the interaction with the color pigment such as a black pigment, dispersion stability, and from the viewpoint of penetrability to a developer, 0.05 mass%-90 mass% are preferable with respect to the total mass of a high molecular compound, 1.0 mass%-80 mass% are more preferable, 10 mass%-70 mass% are still more preferable.

Further, the polymer compound is a structural unit having a graft chain, a hydrophobic structural unit, and a coloring pigment such as a black pigment, for the purpose of improving various properties such as image strength, as long as the effects of the present invention are not impaired. Other structural units having various functions different from the structural unit having a functional group capable of forming an interaction (for example, a structural unit having a functional group having an affinity for the dispersion medium used for the dispersion) You may have further.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound may use one kind or two or more kinds 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. And particularly preferably 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.

The acid value of the polymer compound is preferably 0 mgKOH/g or more and 160 mgKOH/g or less, more preferably 10 mgKOH/g or more and 140 mgKOH/g or less, and further preferably 20 mgKOH/g or more and 120 mgKOH/g. The range is as follows.
When the acid value of the polymer compound is 160 mgKOH/g or less, pattern peeling during development during formation of a cured film can be more effectively suppressed. Further, when the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability becomes better. When the acid value of the polymer compound is 20 mgKOH/g or more, sedimentation of a coloring pigment such as a black pigment can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability of the composition can be further improved. it can.

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

The weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by GPC (gel permeation chromatography) method from the viewpoint of suppressing pattern peeling during development and developing property when forming a cured film. Or more and 300,000 or less, preferably 5,000 or more and 200,000 or less, more preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferable that
The GPC method uses HLC-8020GPC (manufactured by Tosoh Corp.), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corp., 4.6 mm ID×15 cm) as a column, and THF (tetrahydrofuran as an eluent). ) Is used.

The polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, Examples thereof include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound that can be used in the present invention include "DA-7301" manufactured by Kusunoki Kasei Co., Ltd., "Disperbyk-101 (polyamidoamine phosphate)" manufactured by BYK Chemie, 107 (carboxylic acid ester), 110 (acid group). Containing copolymer), 111 (phosphoric acid-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer), “BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", EFKA "EFKA4047, 4050-4010-4165 (polyurethane type), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester). Amide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", Ajinomoto Fine-Techno Co., Ltd. "Azisper PB821, PB822, PB880, PB881", Kyoeisha "Floren TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300 (acrylic copolymer)" manufactured by Kagaku Co., Ltd., "Disparlon KS-860, 873SN, 874, #2150 (fat) manufactured by Kusumoto Kasei Co., Ltd. Group polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725", "Demol RN, N (naphthalenesulfonic acid formalin polycondensate)" manufactured by Kao Corporation, MS, C, SN-B (formaldehyde polycondensate of aromatic sulfonic acid)", "homogenol L-18 (polymer polycarboxylic acid)", "emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", manufactured by Nippon Lubrizol Co., Ltd. "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine) 3000, 12000, 17000, 20000, 27000 (terminal part). Having a functional part in 2), 24000, 28000, 32000, 38500 (graft copolymer), Nikko Chemicals' Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate). )”, manufactured by Kawaken Fine Chemicals Co., Ltd., Hinoact T-8000E, manufactured by Shin-Etsu Chemical Co., Ltd., Organo Roxane polymer KP341, "W001: cationic surfactant" manufactured by Yusho Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonyl Nonionic surfactants such as phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", Morishita Sangyo Co., Ltd.'s "EFKA-46," EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", San Nopco Ltd. "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100". And the like, a polymer dispersant such as "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, manufactured by ADEKA CORPORATION. P-123", "Ionet (trade name) S-20" manufactured by Sanyo Kasei Co., Ltd., and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Moreover, as a commercial item of an amphoteric resin, for example, DISCERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBY manufactured by Big Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajinomoto Fine-Techno Azisper PB821, Azisper PB822, Azisper PB881 etc. are mentioned.
These polymer compounds may be used alone or in combination of two or more.

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

Further, as the dispersant, in addition to the above-described polymer compounds, the graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (corresponding paragraphs 0075 to 0133 of US2011/0124824) can be used. The contents of which are incorporated herein by reference.
In addition to the above, it has a side chain structure in which the acidic groups of paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding paragraphs 0075 to 0133 of US2011/0279759) are bonded via a linking group. Polymeric compounds containing components can be used, the contents of which are incorporated herein by reference.

When the composition contains a dispersant, the content of the dispersant is preferably 0.1 to 50 mass% and more preferably 0.5 to 30 mass% with respect to the total solid content of the composition.
The dispersants may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.

In the composition of the present invention, the content ratio of the dispersant to the titanium nitride-containing particles ((content of the dispersant in the composition (mass %))/(content of titanium nitride-containing particles in the composition (Mass %)), hereinafter also referred to as "D/P") is preferably 0.05 to 0.30, more preferably 0.10 to 0.30, and 0.12. More preferably, it is 0.30. When the content ratio (D/P) is within the above range, the stability of the composition over time becomes good.

In the composition of the present invention, the content ratio of the dispersant to the content of the Fe atom [(content of the dispersant in the composition (mass %))/(content of Fe atom in the composition (mass %) The lower limit value of ))] is preferably 0.8 or more, more preferably 1.0 or more, and further preferably 1.5 or more. The upper limit value is preferably 270 or less, more preferably 150 or less, and further preferably 50 or less.
The content (% by mass) of Fe atoms in the composition is the same as the content (% by mass) of Fe atoms in the titanium nitride-containing particles obtained as described above. It can be calculated by multiplying the content (% by mass) of the nitride-containing particles.
When the content ratio of the dispersant with respect to the content of Fe atoms is within the above range, the desired effect can be remarkably obtained. In particular, when the content ratio is within the range of 1.5 to 50, the desired effect can be obtained more remarkably. The reason for this is considered to be that the Fe atoms in the composition interact with the dispersant, which affects the patternability (curability and developability).

In the composition of the present invention, the content ratio of the polymerizable compound to the content of the Fe atom [(content of the polymerizable compound in the composition (% by mass))/(content of Fe atom in the composition ( The lower limit of (mass %))] is preferably 0.7 or more, more preferably 0.85 or more, still more preferably 1.0 or more. The upper limit value is preferably 50 or less, more preferably 11 or less, and further preferably 7.0 or less.
The Fe atom content (mass %) in the composition can be calculated as described above.
When the content ratio of the polymerizable compound to the Fe atom content is within the above range, the desired effect can be remarkably obtained. In particular, when the content ratio is within the range of 1.0 to 7.0, the desired effect can be obtained more remarkably. The reason for this is considered to be that the Fe atom in the composition and the polymerizable compound interact with each other to influence the patternability (curability and developability).

<Binder resin>
The composition of the present invention preferably contains a binder resin.
A linear organic polymer is preferably used as the binder resin. As such a linear organic polymer, any known one can be used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to allow water development or weak 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 styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, (meth)acrylic resin, (meth)acrylamide resin, (meth)acrylic/(meth)acrylamide copolymer resin, epoxy resin and A polyimide resin is preferable, and a (meth)acrylic resin, a (meth)acrylamide resin, a (meth)acrylic/(meth)acrylamide copolymer resin, and a polyimide resin are preferable from the viewpoint of developing property control.
Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Of these, those soluble in an organic solvent and developable with a weak alkaline aqueous solution are preferable, and an alkali-soluble resin having a structural unit derived from (meth)acrylic acid is more preferable. These acid groups may be only one kind or two or more kinds.

Examples of the binder resin include radical polymers having a carboxylic acid group in a side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, and JP-B-54-25957. Those described in JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048, that is, resins and acid anhydrides obtained by homopolymerizing or copolymerizing monomers having a carboxyl group. A resin in which an acid anhydride unit is hydrolyzed or half-esterified or half-amidated by homopolymerizing or copolymerizing a monomer having, and an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride, Can be mentioned. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene, and examples of the monomer having an acid anhydride include: Maleic anhydride etc. are mentioned. Similarly, an acidic cellulose derivative having a carboxylic acid group in its side chain is also given as an example. In addition, a polymer having a hydroxyl group and a cyclic acid anhydride added thereto is useful.
In addition, the acetal-modified polyvinyl alcohol-based binder resin having an acid group described in each of European Patent No. 993966, European Patent No. 1204000, and JP 2001-318463 A has film strength and developability. It is excellent in balance and suitable.
In addition to these, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. Further, 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 also useful.
In addition, the polyimide resin described in WO 2008/123097 is also useful.

In particular, among these, [benzyl (meth)acrylate/(meth)acrylic acid/optionally other addition-polymerizable vinyl monomer] copolymer, and [allyl(meth)acrylate/(meth)acrylic acid/required] Other addition-polymerizable vinyl monomers] copolymers are suitable because they have an excellent balance of film strength, sensitivity, and developability.
Examples of commercially available products include Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai Co., Ltd.), and Cyclomer P (ACA) manufactured by Daicel Ornex Co., Ltd. 230AA etc. are mentioned.

A known radical polymerization method, for example, 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, the type and amount of the radical initiator, and the type of solvent when the alkali-soluble resin is produced by the radical polymerization method.

It is also preferable to use a polymer having a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group) as the binder resin.
The definition of the structural unit having a graft chain is synonymous with the structural unit having a graft chain contained in the dispersant described above, and the preferred range is also the same.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Yes, and more preferred are carboxylic acid groups.

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

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

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

In addition, 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 (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), divalent aromatic group (eg, , An arylene group, and a substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino bond (—NR ⁴¹ ′— Here, R ⁴¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—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 more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Moreover, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group and a heterocyclic group.

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. Moreover, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocycle. The heterocycle may be condensed with one or more other heterocycles, aliphatic rings or aromatic rings. Moreover, 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), a substituted imino group (=N-R ⁴² , where R ⁴² is a fat). Group, aromatic group or heterocyclic group), aliphatic group, aromatic group and 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. In addition, L ₂ may include a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. Polyoxyethylene structure, - _(OCH 2 _CH 2) represented by n-, n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

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

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

In the present invention, as the monomer represented by the general formula (vii), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a methyl group, and L ₂ represents an alkylene group or an oxyalkylene structure. A compound having a divalent linking group including, wherein X ₂ is an oxygen atom or an imino group, and Z ₂ is a carboxylic acid group is preferable.
As the monomer represented by the general formula (vii), R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Further, as the monomer represented by the 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 dispersant having the 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 type or two or more types of structural units having an acid group.
The content of the structural unit having an acid group is, in terms of mass, based on the total mass of the binder resin, preferably 5 to 95%, and more preferably from the viewpoint of suppressing damage of image strength due to alkali development, It is 10 to 90%.

The content of the binder resin in the composition of the present invention is preferably 0.1 to 30 mass% and more preferably 0.3 to 25 mass% with respect to the total solid content of the composition.
The binder resins may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.

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

The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer 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 their esters, amides, and multimers thereof. However, preferred are esters of unsaturated carboxylic acids with aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids with aliphatic polyhydric amine compounds, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or the above unsaturated carboxylic acid A dehydration condensation reaction product of an acid ester or amide and a monofunctional or polyfunctional carboxylic acid is also preferably used. Also, a reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines, thiols, a halogen group or a tosyloxy group. Reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as, and 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 in which unsaturated phosphonic acid, vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is substituted.
As these specific compounds, the compounds described in JP-A 2009-288705, paragraphs [0095] to [0108] can be preferably used in the present invention.

In the present invention, the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100° C. or higher under normal pressure. For example, the compounds described in paragraph 0227 of JP2013-29760A and paragraphs 0254 to 0257 of JP2008-292970A can be referred to, and the contents thereof are incorporated in the present specification.

The polymerizable compound includes dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). , Dipentaerythritol penta(meth)acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd., and a structure in which these (meth)acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer Co., Ltd.). ) Is preferred. These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.
The preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid. A polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the developing dissolution property is good, and when it is 40 mgKOH/g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

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

In the general formula (Z-1), 6 Rs are all groups represented by the following general formula (Z-2), or 1 to 5 of 6 Rs are the following general formulas (Z -2), and the rest 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, m represents a number of 1 or 2, and “*” represents a bond.

In 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 commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m=1 in the above formulas (Z-1) to (Z-3), Number of groups represented by (Z-2)=2, compounds in which all R ¹ are hydrogen atoms, DPCA-30 (same formula, m=1, number of groups represented by formula (Z-2)) =3, a compound in which R ¹ is all hydrogen atoms), DPCA-60 (the same formula, m=1, the number of groups represented by formula (Z-2)=6, and a compound in which R ¹ is all hydrogen atoms ), DPCA-120 (m=2 in the formula, the number of groups represented by the formula (Z-2)=6, and compounds in which all R ^{1 s} 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) - represents, y represents each independently an integer of 0, X is each independently (meth) acryloyl group, a hydrogen atom Or represents a carboxyl group.
In the 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 5 or 6, n is each independently 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 sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and further preferably an integer of 6 to 12.
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) - , the oxygen A form in which the terminal on the atom side is bonded to X is preferable.

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 the general formula (Z-5), a form in which all six X are acryloyl groups, in the general formula (Z-5), a compound in which all six X are acryloyl groups and six X Among them, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a structure, the developability can be further improved.

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

The compound represented by the general formula (Z-4) or the general formula (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by a reaction and a step of reacting a terminal hydroxyl group of the ring-opening skeleton with, for example, (meth)acryloyl chloride to introduce a (meth)acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize the compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as “exemplary compounds (a) to (f)”), and among them, the exemplary compounds (a) and ( Preferred are b), (e) and (f).

As commercially available 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 Sartomer Co., Ltd., Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains, can be given.

Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, use of addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. This makes it possible to obtain a composition having an extremely high photosensitivity speed.
As commercially available products, urethane oligomer 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-. Examples include 306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha).

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

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

General formula (Q3)

In the general formula (Q3), Ar ^{11 to} Ar ¹⁴ each independently represent an aryl group containing a benzene ring surrounded by a broken line. X ^{1 to} X ⁴ each independently represent a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. a and b each independently represent an integer of 1 to 5, and c and d each independently represent an integer of 0 to 4. R ^{1 to} R ⁴ each independently represent a substituent, 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 Ar ^{11 to} Ar ¹⁴ respectively. It is a value obtained by subtracting a, b, c or d from the number of substituents that can be possessed. However, when Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each independently 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 are respectively The benzene ring surrounded by a broken line may be independently substituted, or the ring other than the benzene ring surrounded by a broken line may be substituted.

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

In the general formula (Q3), X ^{1 to} X ⁴ each independently represent a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. The substituent having a polymerizable group represented by X ^{1 to} X ⁴ is not particularly limited, but an aliphatic group having a polymerizable group is preferable.
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. An alkylene group is more preferable, and an alkylene group having 2 to 5 carbon atoms is further preferable.
Further, in the aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ , when the aliphatic group is substituted with a hetero atom, it is substituted with —NR— (R is a substituent), an oxygen atom or a sulfur atom. it is preferable that the, -CH 2 nonadjacent in the aliphatic group _- is more preferably is substituted with an oxygen atom or a sulfur atom, -CH 2 nonadjacent in the aliphatic group _- is More preferably, it is substituted with an oxygen atom. The aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is preferably substituted at 1 to 2 positions with a hetero atom, more preferably substituted at 1 position with a hetero atom, and Ar ^{11 to} Ar It is further preferable that one position adjacent to the aryl group containing a benzene ring surrounded by a broken line represented by ¹⁴ is substituted with a hetero atom.
The polymerizable group contained in the aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is a radically polymerizable or cationically polymerizable polymerizable group (hereinafter, also referred to as a radically polymerizable group and a cationically polymerizable group, respectively). Is preferred.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and a preferable example thereof is a polymerizable group having a radically polymerizable ethylenically unsaturated bond, and specifically, Examples thereof include a vinyl group and a (meth)acryloyloxy group. Among them, a (meth)acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, A vinyloxy group etc. can be mentioned. Of these, an alicyclic ether group and a vinyloxy group are preferable, and an epoxy group, an oxetanyl group, and a vinyloxy group are particularly preferable.
The polymerizable group contained in the substituent contained in Ar ^{1 to} Ar ⁴ is preferably a radical polymerizable group.
Two or more of Ar ¹ to Ar ⁴ include a substituent having a polymerizable ^group, preferably contains a substituent with 2-4 polymerizable group of Ar 1 ~Ar ^4, Ar 1 ~Ar It is more preferable that 2 or 3 of ⁴ contain a substituent having a polymerizable group, and it is further preferable that 2 of Ar ^{1 to} Ar ⁴ contain a substituent having a polymerizable group.
In the case where Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each independently containing a benzene ring surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ are each a benzene surrounded by a broken line. The ring may be substituted, or the ring other than the benzene ring surrounded by the broken line may be substituted.

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

In the general formula (Q3), R ^{1 to} R ⁴ each independently represent a substituent. The substituent represented by R ^{1 to} R ⁴ is not particularly limited, but 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 group. Examples thereof include an aryl group and an alicyclic group. The substituent represented by R ^{1 to} R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, 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 Ar ^{11 to} Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of condensed rings, R ^{1 to} R ⁴ are respectively The benzene ring surrounded by a broken line may be independently substituted, or the ring other than the benzene ring surrounded by a broken line may be substituted.

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

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

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

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

<Polymerization initiator>
The composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited and may be appropriately selected from known polymerization initiators. For example, those having photosensitivity (so-called photopolymerization initiators) are preferable.
When the composition of the present invention contains, in addition to titanium nitride-containing particles, a photopolymerization initiator and the above-mentioned polymerizable compound, it is cured by irradiation with actinic rays or radiation, so that the “photosensitive composition It is sometimes called.
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 visible light in the ultraviolet region are preferable. Further, it may be an activator which produces an active radical by causing some action with the photoexcited sensitizer, or an initiator which initiates cationic polymerization depending on the kind of the monomer.
Further, the photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. And other oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, compounds described in JP-A No. 53-133428, compounds described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), the compound described in JP-A-62-58241, the compound described in JP-A-5-281728, the compound described in JP-A-5-34920, and the specification of US Pat. No. 4,121,976. Compounds described in the book, and the like.

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

More preferably, trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, α-aminoketones. At least one compound selected from the group consisting of a compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is particularly preferable.

In particular, when the composition of the present invention is used for producing a light-shielding film for a solid-state imaging device, it is necessary to form a fine pattern in a sharp shape, and therefore, the curability is high and there is no residue in the unexposed area, and development is performed. It is important to be done. From such a viewpoint, it is particularly 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 photopolymerization initiator added must also be kept low. Therefore, taking these points into consideration, it is particularly preferable to use an oxime compound as the photopolymerization initiator for forming a fine pattern such as a solid-state image sensor. Further, by using an oxime compound, the color transfer property can be further improved.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

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

An oxime compound is more preferable as the photopolymerization initiator. In particular, an oxime-based initiator is preferable because it has high sensitivity, high polymerization efficiency, can be cured regardless of the concentration of the color material, and the concentration of the color material can be easily designed.
As specific examples of the oxime compound, the compounds described in JP 2001-233842 A, the compounds described in JP 2000-80068 A, and the compounds described in JP 2006-342166 A can be used.
In the present invention, examples of oxime compounds that can be preferably used include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane 2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
Also, J. C. S. Perkin II (1979) pp. 1653-1660), J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, the compounds described in JP-A-2000-66385, the compounds described in JP-A-2000-80068, JP-A-2004-534797, JP-A-2006-342166, and the like.
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), ADEKA ARKUL'S NCI-831 and ADEKA AARCULS NCI-930 (manufactured by ADEKA), N-1919 (carbazole/oxime ester skeleton-containing photo-start) Agents (made by ADEKA) can also be used.

In addition, as the oxime compound other than the above description, the compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole, the compound described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds described in JP 2010-15025 A and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye moiety, ketoxime compounds described in WO 2009-131189, triazine skeleton and oxime skeleton are the same molecule. The compounds described in U.S. Pat. No. 7,556,910, which are contained therein, and the compounds described in JP2009-221114A, which has a maximum absorption at 405 nm and has good sensitivity to a g-ray light source, may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime may be an (E)-form oxime compound, a (Z)-form oxime compound, or a mixture of the (E)-form and the (Z)-form. ..

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

In the present invention, an oxime compound having a fluorine atom may be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP2010-262028A, the compounds 24, 36 to 40 described in JP-A-2014-500852, and the compounds described in JP2013-164471A. C-3) etc. are mentioned. This content is incorporated herein.

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

In the formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or It represents an arylalkyl group having 7 to 30 carbon atoms, and when R ¹ and R ² are phenyl groups, phenyl groups may be bonded to each other 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 single 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 the 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 Represents an atom or a hydroxyl group, 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 0-4.

In the above formulas (1) and (2), R ¹ and R ² are each independently preferably 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.
Specific examples of the compounds represented by formula (1) and formula (2) include the compounds described in paragraph numbers 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein.

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

The oxime compound preferably has a maximum absorption wavelength in the wavelength range of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength range of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 405 nm.
The oxime compound has a molar absorption coefficient at 365 nm or 405 nm of preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and more preferably 5,000 to 200, from the viewpoint of sensitivity. It is particularly preferable that it is 1,000.
A known method can be used for the molar extinction coefficient of the compound. For example, an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian) is used with an ethyl acetate solvent 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, if necessary.

When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30% by mass, and 1 to 25% by mass based on the total solid content in the composition. %, and more preferably 1 to 10% by mass. The composition of the present invention may contain only one type or two or more types of polymerization initiators. When two or more kinds are contained, the total amount is preferably within the above 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, ethyl acetate, 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, Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate , Methyl lactate, ethyl lactate, and the like, but are not limited thereto.

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

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

<Water>
The composition of the present invention may contain water. Water may be added intentionally or may be unavoidably 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, and 0.1 to 0. It is more preferably 7% by mass. When the content of water is within the above range, generation of pinholes when a cured film is produced can be suppressed, or the moisture resistance of the cured film can be improved.

<Other ingredients>
The composition of the present invention may contain components other than the components described above.
Hereinafter, each component will be described in detail.

(Colorant)
The composition of the present invention can also use a colorant other than the above-mentioned titanium nitride-containing particles (hereinafter, also simply referred to as “colorant”). The colorant is used, for example, for adjusting the chromaticity of the composition, and it is possible to replace part of the titanium nitride with the colorant as long as the OD value does not decrease. Examples of such colorants include pigments (organic pigments such as black organic pigments and chromatic organic pigments, and inorganic pigments) and dyes.

A pigment is preferably used as the colorant. This makes it easy to manufacture a film having a small standard deviation of transmittance in the wavelength range of 400 to 700 nm. In particular, when a black pigment (a black organic pigment and a black inorganic pigment) is used as the pigment, it is easy to manufacture a film having a standard deviation of transmittance of 10% or less in the above range.

((Pigment))
Examples of the pigment include various conventionally known pigments.
The chromatic organic pigments include the following. However, the present invention is not limited to these.
Color Index (C.I.) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4 49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184. 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc.
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. C.I. I. Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80 etc.

Further, as the green pigment, use is made of a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, an average number of bromine atoms of 8 to 12 and an average number of chlorine atoms of 2 to 5. Is also possible. Specific examples thereof include the compounds described in WO 2015/118720.
These organic pigments can be used alone or in various combinations for increasing color purity.

As the black pigment, various known black pigments can be used. Examples thereof include carbon black and the black metal-containing inorganic pigments shown below. The black metal-containing inorganic pigments include metal oxides and metals containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti and Ag. Nitrogen substances are included. These may be used alone or as a mixture of two or more. In addition, the black pigment may be used in combination with an inorganic pigment having another hue to prepare a desired light-shielding property. Examples of specific inorganic pigments that can be used in combination include, for example, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, and yellow lead. , Zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), Ultramarine blue, Prussian blue (ferric cyanide iron) Zircon gray, Praseodymium yellow, Chrome titanium yellow, Chrome green, Peacock, Victoria green, Navy blue (Prussian blue) Irrelevant), vanadium zirconium blue, chrome tin pink, ceramic red, salmon pink and the like. In particular, for the purpose of developing a light-shielding property in a wide wavelength range from ultraviolet to infrared, these black pigments and inorganic pigments having other hues may be used not only alone but also as a mixture of plural kinds of pigments. Is possible.

The black pigment is preferably carbon black or chilan black, and titanium black is particularly preferable from the viewpoint of having a light-shielding property in a wide wavelength range from ultraviolet to infrared. Titanium black is black particles having titanium atoms. Preferred are low order titanium oxide and titanium oxynitride. Although not particularly limited, examples of titanium oxynitride include titanium oxynitrides such as those disclosed in WO 2008/123097, JP 2009-58946, JP 2010-14848, JP 2010-97210, and JP 2011-2274670. Further, a mixture of titanium oxynitride and titanium carbide as disclosed in JP-A-2010-95716 can be used. The surface of the titanium black particles can be modified, if necessary, for the purpose of improving dispersibility and suppressing cohesiveness. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can be treated with a water-repellent substance as disclosed in JP2007-302836A. .. Titanium black is a composite oxide of Cu, Fe, Mn, V, Ni or the like, and one or more black pigments such as cobalt oxide, iron oxide or carbon black is used for the purpose of adjusting dispersibility, colorability and the like. You may contain in combination.

As a method for producing titanium black, a mixture of titanium dioxide and metallic titanium is heated in a reducing atmosphere for reduction (JP-A-49-5432), and ultrafine carbon dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (JP-A-57-205322), and a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (JP-A-60-65069). 61-201610), a method of adhering a vanadium compound to titanium dioxide or titanium hydroxide, and reducing at high temperature in the presence of ammonia (JP-A 61-201610). However, the present invention is not limited to these.

The specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 5 m2/g or more and 150 m2/g or less, and 20 m2/g or more and 120 m2/g or less. Is more preferable.
Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corp.), Tilack. D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

The black pigment preferably has an average primary particle diameter of 5 nm or more, and more preferably 10 nm or more. From the same viewpoint, the upper limit is preferably 10 μm or less, more preferably 1 μm or less, and further preferably 100 nm or less. The average primary particle diameter of the black pigment is a value measured by the following method. A mixed solution containing a black pigment is diluted 80 times with propylene glycol monomethyl ether acetate, and the obtained diluted solution is used as a value measured by a dynamic light scattering method. This measurement is an average particle diameter obtained by using Microtrac (trade name) UPA-EX150 manufactured by Nikkiso Co., Ltd.

Further, it is also preferable to contain titanium black as a dispersed material containing titanium black and Si atoms.
In this form, titanium black is contained in the composition as a substance to be dispersed, and the content ratio (Si/Ti) of Si atoms and Ti atoms in the substance to be dispersed is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is further preferable.
Here, the dispersed material includes both titanium black in the state of primary particles and that in the state of agglomerates (secondary particles).
In order to change the Si/Ti of the substance to be dispersed (for example, to be 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 a reduction treatment at a high temperature (for example, 850 to 1000° C.) to mainly disperse the titanium black particles. A dispersed material containing Si and Ti as components can be obtained. The reduction treatment may be performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo).
Titanium oxide produced by the plasma method can be suitably used because its particle size is smaller than that of commercially available titanium oxide fine particles (see the Journal of the Japan Institute of Metals, Vol. 63, No. 1 (1999) 74-81). ..
Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name: manufactured by Evonik).
A dispersant may be used to disperse the titanium oxide and the silica particles. Examples of the dispersant include those described in the section of the dispersant described later.
The above dispersion may be carried out in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned.
The titanium black whose Si/Ti is adjusted to, for example, 0.05 or more can be prepared by the method described in paragraph No. [0005] and paragraphs [0016] to [0021] of JP 2008-266045 A, for example. It can be made.

By adjusting the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersed material containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), the composition containing the dispersed material. When the light-shielding film is formed using a substance, the residue derived from the composition outside the region where the light-shielding film is formed is reduced. The residue contains components derived from the composition, such as titanium black particles and a resin component.
Although the reason why the residue is reduced is not yet clear, the above-mentioned dispersed substance tends to have a small particle size (for example, the particle size is 30 nm or less), and further, the Si atom of this dispersed substance is It is speculated that the increased content of the components reduces the adsorptivity of the entire film to the underlying layer, which contributes to the improvement of the removability of the uncured composition (particularly titanium black) in the formation of the light-shielding film by development. There is.
Further, since titanium black is excellent in light-shielding property against light in a wavelength range covering a wide range from ultraviolet light to infrared light, the above-mentioned titanium black and a dispersion target containing Si atoms (preferably Si/Ti is converted into mass). The light-shielding film formed by using (1) is 0.05 or more) exhibits excellent light-shielding properties.
The content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersed material is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A. ) Can be used for measurement.
Whether the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersed material contained in the light-shielding film obtained by curing the composition is 0.05 or more. The method (2) described in paragraph 0035 of JP-A-2013-249417 is used to determine the above.

In the dispersion target containing titanium black and Si atoms, the above-mentioned titanium black can be used.
In addition, in this dispersed material, together with titanium black, for the purpose of adjusting dispersibility, colorability, etc., complex oxides of Cu, Fe, Mn, V, Ni, etc., cobalt oxide, iron oxide, carbon black, aniline. You may use together the black pigment which consists of black etc. as a to-be-dispersed body by combining 1 type(s) or 2 or more types.
In this case, it is preferable that titanium black occupies 50% by mass or more of the whole dispersed object.
Further, in this dispersion object, other colorants (organic pigments, dyes, etc.) may be optionally used together with titanium black for the purpose of adjusting the light-shielding property and the like, as long as the effects of the present invention are not impaired. Good.
Hereinafter, the materials used when introducing Si atoms into the substance to be dispersed will be described. When introducing Si atoms into the substance 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, and synthetic silica, 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. Therefore, it is preferable to use fine particle type silica as the silica particles. Note that examples of the fine particle type silica include, for example, silica described in paragraph 0039 of JP2013-249417A, the contents of which are incorporated in the present specification.

Further, as the pigment, a tungsten compound and a metal boride can also be used.
Tungsten compounds and metal borides have high absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light-shielding properties (shielding properties) with respect to infrared rays) and absorption with respect to visible light. It is a low infrared shielding material. Therefore, the photosensitive composition of the present invention can form a pattern having a high light-shielding property in the infrared region and a high light-transmitting property in the visible light region by containing the tungsten compound and/or the metal boride.
Further, the tungsten compound and the metal boride have small absorption for light having a shorter wavelength than the visible range used for exposure of a high pressure mercury lamp, KrF and ArF used for image formation.

Examples of the tungsten compound include a tungsten oxide-based compound, a tungsten boride-based compound, and a tungsten sulfide-based compound, and a tungsten oxide-based compound represented by the following general formula (compositional 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 metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Examples thereof include Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like, but an alkali metal is preferable. The metal of M may be one kind or two or more kinds.

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

When x/y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, it is possible to more surely avoid generation of an impurity phase in the tungsten compound. 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 compound represented by the above general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , 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 fine particles. The average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average particle diameter is in such a range, it becomes difficult for the tungsten fine particles to block visible light due to light scattering, so that it is possible to further ensure the translucency in the visible light region. From the viewpoint of avoiding light scattering, the smaller the average particle diameter is, the more preferable, but the average particle diameter of the tungsten fine particles is usually 1 nm or more for reasons such as ease of handling during production.

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

Although the tungsten compound is commercially available, 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 Japanese Patent No. 4096205).
Further, the tungsten oxide-based compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Examples of the metal boride include lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), and 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 ), boride One or more of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ) and the like can be mentioned, and lanthanum boride (LaB ₆ ) is preferable.

The metal boride is preferably fine particles. The average particle size of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. When the average particle diameter is in such a range, it becomes difficult for the metal boride fine particles to block visible light due to light scattering, so that the light transmittance in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the smaller the average particle size is, the more preferable. However, the average particle size of the metal boride fine particles is usually 1 nm or more for reasons such as ease of handling during production.

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

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

((dye))
As the dye, for example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, Tokubo 2592207, and US Pat. No. 4,808,501 are described. U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,050,950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-51. The dyes disclosed in Japanese Patent No. 194828 and the like can be used. When classified as chemical structures, pyrazole azo compounds, pyrromethene compounds, anilinoazo 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, a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

The composition of the present invention may contain an extender pigment, if necessary, in addition to the colorant. Examples of such extender pigment include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments may 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, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the colorant. In the present invention, the colorant and the extender pigment may be used by modifying their surface with a polymer as the case may be.

The colorants may be used alone or in combination of two or more. The colorant may contain color organic pigments such as red, blue, yellow, green, and purple. When the light-shielding pigment (specifically, titanium nitride-containing particles) and the coloring organic pigment are used in combination, it is preferable to use the coloring organic pigment in an amount of 1 to 40% by mass based on the light-shielding pigment. From the viewpoint of adjusting the tint, it is preferable to use a red pigment and a light-shielding pigment in combination, and the red pigment is preferably Pigment Red 254, although not particularly limited thereto. Further, it is preferable to use a yellow pigment and a light-shielding pigment in combination from the viewpoint of enhancing the light-shielding property, and although not particularly limited, Pigment Yellow 150 is preferable as the yellow pigment.

When the composition of the present invention contains a colorant, the content of the colorant is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and 35 based on the total solid content of the composition. -60 mass% is still more preferred.

(Pigment derivative)
The composition of the present invention may contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of an organic pigment is replaced with an acidic group, a basic group or a phthalimidomethyl group.
As the organic pigment for constituting the pigment derivative, diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, slene pigments, metal complex pigments and the like.
As the acidic group contained in the pigment derivative, a sulfonic acid group, a carboxylic acid group and its quaternary ammonium salt group are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is particularly preferable. As the basic group contained in the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.
Specific examples of the pigment derivative include the following compounds. Further, the description in paragraphs 0162 to 0183 of JP 2011-252065 A can be referred to, and the contents thereof are incorporated in the present specification.

When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the total mass of the colorant. The composition of the present invention may include only one type of pigment derivative, or may include two or more types. When two or more kinds are contained, the total amount is preferably within the above range.

(Silane coupling agent)
The silane coupling agent is a compound having a hydrolyzable group and a functional group other than that in the molecule. The hydrolyzable group such as an alkoxy group is bonded to the silicon atom.
The hydrolyzable group means a substituent directly bonded to a silicon atom and capable of forming a siloxane bond by a hydrolysis reaction and/or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the carbon number thereof is preferably 6 or less, more preferably 4 or less. Particularly, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
Further, the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded) in order to improve the adhesion between the substrate and the cured film. Includes silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), 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. Not desirable.

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

The silane coupling agent preferably has one or more curable functional groups selected from the group consisting of (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, a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.

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

As one of the preferred embodiments of the silane coupling agent, the silane coupling agent X represented by the formula (W) can be 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 preferable range is also as described above.
Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, the divalent linking group may be an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, —NR ¹² —, or —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 halogen atom having 2 to 10 carbon atoms and an arylene group which may be substituted by a halogen atom having 6 to 12 carbon atoms, or At least selected from the group consisting of these groups and —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, and SO ₂ —. A group consisting of a combination with one type of group is preferable, and an alkylene group having 2 to 10 carbon atoms, which may be substituted by a halogen atom, —CO ₂ —, —O—, —CO—, —CONR ¹² —, or A group consisting of a combination of these groups is more preferable. Here, R ¹² represents a hydrogen atom or a methyl group.

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 (Shin-Etsu Chemical Co., Ltd. trade name KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBE-602), γ-aminopropyl-trimethoxysilane. (Shin-Etsu Chemical Co., Ltd. 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), glycidoxyoctyltrimethoxysilane (trade name KBM-4803 manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

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

The silane coupling agent Y 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. The structure of the amino group may be present in the molecule in the form of a partial structure of the nitrogen-containing heterocycle, or may be present as a substituted amino group such as aniline.
Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a combination thereof. These may further have a substituent, and examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom and a sulfonamide. Examples thereof include a group, an alkoxycarbonyl group, a carbonyloxy group, an amide group, a urea group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, and a sulfo group.
Further, the nitrogen atom is preferably bonded to the curable functional group via any organic linking group. Examples of the preferable organic linking group include the above-mentioned nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferable range is also as described above.
The silane coupling agent Y may have at least one curable functional group in one molecule, but may have two or more curable functional groups in order to improve sensitivity and stability. From the viewpoint of, 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.

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

The content of the silane coupling agent in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content of the composition. 0 to 6 mass% is more preferable.

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

(UV absorber)
The composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of the pattern can be made more excellent (fine).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples thereof, the compounds of paragraphs 0137 to 0142 (corresponding paragraphs 0251 to 0254 of US2012/0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated into the present specification. ..
Besides, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Kagaku, trade name: UV-503) and the like are also suitably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The composition of the present invention may or may not contain an ultraviolet absorber, but in the case of containing it, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass based on the total solid content of the composition. , 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is further preferable.

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

By containing a fluorosurfactant in the composition of the present invention, the liquid properties (particularly the fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. be able to. That is, in the case of forming a film using a coating liquid to which a composition containing a fluorine-containing surfactant is applied, the interfacial tension between the coating surface and the coating liquid is lowered, and the wettability to the coating surface is reduced. It is improved and the coating property on the coated surface is improved. Therefore, it is possible to more favorably form a film having a uniform thickness with a small thickness unevenness.

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

Examples of the fluorinated surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, Same F482, Same F554, Same F780, RS-72-K (above, DIC Corporation), Florard FC430, Same FC431, Same FC171 (above, Sumitomo 3M Ltd.), Surflon S-382, Same SC. -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.). ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2005-117327 can also be used. A block polymer may be used as the fluorine-based surfactant, and specific examples thereof include the compounds described in JP 2011-89090 A.
The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
Further, a fluoropolymer having an ethylenically unsaturated group in its side chain can also be used as the fluorosurfactant. As specific examples, the compounds described in JP-A-2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, for example, Megafac RS-101, RS-102, RS-718K, RS-72- manufactured by DIC. K and the like.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (eg, glycerolpropoxylate, glycerinethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene. Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl 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, Solspers 20000 (manufactured by Nippon Lubrizol Co., Ltd.), etc. Also, NCW-101 manufactured by Wako Pure Chemical Industries, Ltd., NCW-1001 and NCW-1002 can also be used.

Specific examples of the cationic surfactant include phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based ( Co) Polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).

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

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

As the surfactant, only one kind may be used, or two or more kinds may be combined. The content of the surfactant is preferably 0.001 to 2.0 mass% and more preferably 0.005 to 1.0 mass% with respect to the total solid content of the composition of the present invention.

(Polymerization inhibitor)
The composition of the present invention may contain a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned.
When the composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass% with respect to the total solid content of the composition. The composition of the present invention may contain only one type or two or more types of polymerization inhibitors. When two or more kinds are contained, the total amount is preferably within the above range.
Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. .. When the added amount of the higher fatty acid derivative is included, the content of the higher fatty acid derivative is preferably 0.5 to 10 mass% with respect to the total solid content of the composition.

In addition to the above components, the following components may be added to the composition of the present invention. For example, a sensitizer, a co-sensitizer, a cross-linking agent, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, a diluent, an oil sensitizer, etc. may be mentioned, and further, an adhesion promoter to the substrate surface And other auxiliaries (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension adjusting agents, chain transfer agents, etc.) Known additives may be added as necessary.
These components are described, for example, in paragraph Nos. 0183 to 0228 of JP2012-003225A (<0237> to <0309> of corresponding US Patent Application Publication No. 2013/0034812) and JP2008-250074A. The description of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP2013-195480A 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, and more preferably 12 to 30% by mass. When the solid content of the composition is 10% by mass or more, the light-shielding property of the cured film is improved. In addition, when the solid content of the composition is 40% by mass or less, the stability of the composition over time becomes good.

<Method for 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 emulsifier, a wet pulverizer, a wet disperser).
At the time of producing the composition, the various components constituting the composition may be blended together, or the various components may be dissolved or dispersed in an organic solvent and then sequentially blended. In addition, there is no particular restriction on the order of introduction and the working conditions when compounding.
In the process of dispersing the pigment, the mechanical force used to disperse the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mill, sand mill, roll mill, high speed impeller, sand grinder, flow jet mixer, high pressure wet atomization and ultrasonic dispersion. In addition, "Dispersion Technology Taizen, published by Information Technology Co., Ltd., July 15, 2005" and "Dispersion technology centering on suspension (solid/liquid dispersion system) and practical application of comprehensive materials, published by the Management Development Center Issue, October 10, 1978” and the disperser can be preferably used.
Further, in the process of dispersing the pigment, the pigment may be refined by a salt milling process. The materials, equipment, processing conditions and the like used in the salt milling step can be those described in JP-A-2015-194521 and JP-A-2012-046629.
In addition, the method for producing the composition of the present invention preferably includes a step of obtaining the titanium nitride-containing particles by a thermal plasma method. The step of obtaining the titanium nitride-containing particles is performed before mixing the various components described above. The specific manufacturing process of the titanium nitride-containing fine particles by the thermal plasma method is as described in the section of the titanium nitride-containing particles above, and thus the description thereof is omitted.
Furthermore, the titanium nitride-containing particles obtained by the thermal plasma method were used in a closed container in which the oxygen concentration was controlled without immediately exposing the titanium nitride-containing particles to the atmosphere after producing the titanium nitride-containing particles (that is, after the thermal plasma treatment). It is preferably obtained by standing for a predetermined time (preferably 12 to 72 hours, more preferably 12 to 48 hours, further preferably 12 to 24 hours). Further, it is more preferable that the water content in the closed container is controlled, whereby the surface and the grain boundaries of the titanium nitride-containing particles that have been subjected to the thermal plasma are stabilized, and the performance of the composition is improved. Presumed to be. Specifically, the occurrence of pinholes in the cured film obtained using the composition of the present invention can be suppressed.
The oxygen (O ₂ ) concentration and the water content in the closed container are each preferably 100 ppm or less, more preferably 10 ppm or less, and further preferably 1 ppm or less.
The oxygen (O ₂ ) concentration and the water content in the closed container can be adjusted by adjusting the oxygen concentration and the water amount in the inert gas supplied into the closed container. Nitrogen gas and argon gas are preferably used as the inert gas, and among them, nitrogen gas is more preferably used. It is presumed that this stabilizes the surface and the grain boundaries of the titanium nitride-containing particles that have been subjected to the thermal plasma treatment and improves the performance of the composition. Specifically, the occurrence of pinholes in the cured film obtained using the composition of the present invention can be suppressed.
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign matters and reducing defects. The filter can be used without particular limitation as long as it has been conventionally used for filtration and the like. Examples thereof include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
A suitable pore size of the filter is about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, still more preferably 0.3 to 0.0 μm. It is 7 μm. Within this range, it is possible to reliably remove fine foreign matters such as impurities and agglomerates contained in the pigment while suppressing the filter clogging of the pigment.
When using the filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once, or may be performed twice or more. When different filters are combined to perform filtering two or more times, it is preferable that the pore diameter of the second and subsequent times is the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. For the pore size here, the nominal value of the filter manufacturer can be referred to. The commercially available filter can be selected from, for example, various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kits Micro Filter Co., Ltd., etc. ..
As the second filter, a filter made of the same material as the first filter described above can be used. A suitable pore size of the second filter is 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 contains the above-mentioned titanium nitride-containing particles. The cured film of the present invention is suitably used as a light-shielding film, specifically, it is suitably used for light-shielding the peripheral portion of the light receiving portion of the image sensor.
Hereinafter, a case where the cured film is used as a light shielding film around the light receiving portion of the image sensor will be described as an example.
The light-shielding film of the present invention is formed using the composition described above (particularly, the photosensitive composition described above). The light-shielding film obtained by using the composition of the present invention has excellent patterning properties and electrode anticorrosion properties.

The film thickness of the light shielding film is not particularly limited, but from the viewpoint of more effectively obtaining the effect of the present invention, the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and 0.3 μm or more and 10 μm or less. It is more preferably 0.3 μm or more and 5 μm or less. Since the composition of the present invention has a high optical density per unit volume, it is possible to reduce the film thickness as compared with a composition using a conventional black pigment.
The size of the light-shielding film (the length of one side of the light-shielding film provided around the light receiving portion of the sensor) is preferably 0.001 mm or more and 10 mm or less, and 0.05 mm or less, from the viewpoint of more effectively obtaining the effect of the present invention. 7 mm or less is more preferable, and 0.1 mm or more and 3.5 mm or less is more preferable. Since the composition of the present invention has a high optical density per unit volume, the coating amount can be reduced, which is advantageous for microfabrication, and has excellent patterning properties and electrode anticorrosion properties, and thus is particularly preferably used in the above range. be able to.

<Cured film manufacturing method>
Next, a color filter having a black matrix and a method of manufacturing the same will be described as an example of a method of manufacturing the cured film (light-shielding film) of the present invention.
A color filter having a black matrix of the present invention is characterized by having a cured film (black matrix) obtained by using the above-mentioned composition on a substrate.
Hereinafter, the color filter having the black matrix of the present invention will be described in detail through its manufacturing method.

The method for producing a color filter having a black matrix of the present invention comprises a step of applying a composition of the present invention on a substrate to form a composition layer (coating film) (hereinafter referred to as "composition layer forming step" as appropriate). Abbreviated) and a step of exposing the composition layer through a mask (hereinafter, appropriately abbreviated as “exposure step”), and developing the exposed composition layer to form a patterned cured film. And a step of forming (hereinafter, appropriately abbreviated as “developing step”).

Specifically, the composition of the present invention is applied to a substrate directly or through another layer to form a composition layer (composition layer forming step), and exposure is performed through a predetermined mask pattern. A method of manufacturing the color filter of the present invention by curing only the coating film portion irradiated with light (exposure step) and developing with a developer (developing step) to form a patterned cured film composed of pixels. You can
Hereinafter, each step in the method of manufacturing a color filter having a black matrix of the present invention will be described.

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

Examples of the substrate include non-alkali glass used in liquid crystal display devices, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by adhering a transparent conductive film to these, photoelectric sensors used in solid-state imaging devices, and the like. Examples thereof include a conversion element substrate (for example, a silicon substrate), a CCD (Charge Coupled Device) substrate, and a CMOS (Complementary Metal-Oxide Semiconductor) substrate.
If necessary, an undercoat layer may be provided on these substrates in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the substrate surface.

As a method for applying the composition of the present invention onto a substrate, various application methods such as slit application, ink jet method, rotary application, cast application, roll application, and screen printing method can be applied.

When producing a color filter having a black matrix for a solid-state imaging device, the coating thickness of the composition is preferably 0.35 μm or more and 1.5 μm or less, and 0.40 μm or more from the viewpoint of resolution and developability. It is more preferably 1.0 μm or less.

The composition applied onto the substrate is usually dried under the conditions of 70° C. or higher and 110° C. or lower for 2 minutes or longer and 4 minutes or shorter. Thereby, the composition layer can be formed.

(Exposure process)
In the exposure step, the composition layer (coating film) formed in the composition layer forming step is exposed through a mask to cure only the light-irradiated coating film portion.
The exposure is preferably performed by irradiation with actinic rays or radiation, and ultraviolet rays such as g rays, h rays, and i rays are particularly preferably used, and a high pressure mercury lamp is more preferable. Irradiation intensity 5~1500mJ / cm ² is more preferably preferably 10~1000mJ / cm ^2. Further, from the viewpoint of improving resolution, exposure by an i-line stepper is preferable in forming a light-shielding film for a solid-state image sensor.

(Development process)
After the exposure step, an alkali development treatment (development step) is performed to elute the unirradiated portion in the exposure step into the alkaline aqueous solution. As a result, only the photo-cured portion (light-irradiated coating film portion) remains.
As the developer, an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable when manufacturing a light-shielding color filter having a black matrix for a solid-state image sensor. The developing temperature is usually 20 to 30° C., and the developing time is 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developing solution and an organic developing solution. As the inorganic developing solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium metasilicate are used at a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution which is dissolved so as to be% is included. Examples of organic developers include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7. An alkaline aqueous solution in which an alkaline compound such as undecene is dissolved to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be added to the alkaline aqueous solution. When a developer made of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

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

In addition, in the method for producing a color filter having a cured film (black matrix) of the present invention, after the above-described composition layer forming step, exposure step, and developing step, the formed cured film is optionally formed. A curing step of curing by heating and/or exposure may be included.

Since the color filter having the cured film (black matrix) of the present invention uses the composition of the present invention, the formed cured film has excellent patterning properties and electrode anticorrosion properties.
Therefore, it can be suitably used for a solid-state image pickup device such as a liquid crystal display device and a CCD, and is particularly suitable for a high-resolution CCD device having more than 1 million pixels or a CMOS. That is, the color filter provided with the cured film of the present invention is preferably applied to a solid-state image sensor. Further, the color filter may have a structure in which a cured film for forming each color pixel is embedded in a space partitioned by a partition wall in a grid pattern, for example.
The cured film (black matrix) of the present invention is arranged, for example, between the light receiving portion of each pixel forming the CCD or CMOS and the microlens for condensing.

[Solid-state image sensor]
The solid-state image sensor of the present invention has the above-described cured film (black matrix) of the present invention. The solid-state imaging device of the present invention is preferably configured to include a color filter having a black matrix and, if necessary, a patterned film including pixels of other colors (three colors or four colors).
The structure of the solid-state imaging device of the present invention is not particularly limited as long as it is a structure provided with the black matrix of the present invention and functions as a solid-state imaging device. For example, on the substrate, the solid-state imaging device ( CCD image sensor, CMOS image sensor, etc.) having a plurality of photodiodes constituting a light receiving area and a light receiving element made of polysilicon or the like, and the black matrix of the present invention is provided on the surface of the substrate opposite to the light receiving element forming surface. And the like. Further, the color filter may have a structure in which a cured film for forming each color pixel is embedded in a space partitioned by a partition wall in a grid pattern, for example. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include the devices described in JP 2012-227478 A and JP 2014-179577 A.

[Infrared light cut filter with light-shielding film, solid-state imaging device]
The cured film described above can be suitably applied as a so-called light-shielding film. Further, such a light shielding film can be suitably applied to an infrared light cut filter with a light shielding film and a solid-state image pickup device. Examples of such solid-state imaging devices include solid-state imaging devices described in paragraphs 0011 to 0033 and paragraphs 0125 to 0127 of JP-A-2005-034983.

[Image display device, color filter]
The cured film described above can be used for image display devices such as liquid crystal display devices and organic electroluminescence display devices. Further, the cured film can be used for a color filter.

For the definition of the image display device and details of each image display device, see, for example, “Electronic display device (Akio Sasaki, published by Industrial Research Institute Co., Ltd., 1990)”, “Display device (Junsho Ibuki, Sangyo Tosho Co., Ltd.) ) Published in 1989)" etc. The liquid crystal display device is described, for example, in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industrial Research Institute Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned “next-generation liquid crystal display technology”.

Here, the liquid crystal display device of the present invention has the above-mentioned cured film.
One mode of the liquid crystal display device of the present invention includes, for example, a color filter, a liquid crystal layer, and a liquid crystal driving means (a simple matrix driving method and an active matrix driving method) between at least one pair of light transmissive substrates. ) Is provided, the color filter has a plurality of pixel groups, and each pixel forming the pixel group is separated from each other by the black matrix of the present invention. ..

In another aspect of the liquid crystal display device of the present invention, at least one of the pair of light-transmissive substrates is provided with at least a color filter, a liquid crystal layer, and a liquid crystal drive means, and the liquid crystal drive means is an active element ( For example, it has a TFT (Thin Film Transistor) and includes a color filter obtained by using the composition of the present invention between each active element.
The color filter using the composition of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (Kyoritsu Shuppan Co., Ltd., 1996)". Further, the present invention is a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and STN (Super-Twist Nematic). , TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optical Compensated).
Further, the color filter of the present invention can be applied to a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter may require the required characteristics for the interlayer insulating film, that is, low dielectric constant and stripping solution resistance, in addition to the ordinary required characteristics. The color filter of the present invention can provide a COA type liquid crystal display device having high resolution and excellent long-term durability. A resin coating may be provided on the color filter layer in order to satisfy the required characteristics of low dielectric constant.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest market trends-(published by Toray Research Center, Research Department 2001)". Further, the color filter may have a structure in which a cured film for forming each color pixel is embedded in a space partitioned by a partition wall in a grid pattern, for example.
In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include the devices described in JP2012-227478A and JP2014-179577A.

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 assurance 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 device composed of these known members. As for these materials, for example, “The market of peripheral materials and chemicals for liquid crystal displays in '94 (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current status and future outlook of 2003 liquid crystal related market (second volume)” Fuji Chimera Research Institute, Inc., 2003)."
Regarding backlights, see SID meeting Digest 1380 (2005) (A. Konno et. al), December 2005 page 18 to 24 (Yasuhiro Shima), and pages 25 to 30 (Takaaki Yagi), etc. Have been described.

Further, the cured film of the present invention can be applied to portable devices such as personal computers, tablets, mobile phones, smartphones and digital cameras; OA (Office Automation) devices such as printer multifunction peripherals and scanners; surveillance cameras, bar code readers, and cash automatic devices. Industrial equipment such as ATM (ATM), high-speed camera and personal identification using facial image authentication; vehicle-mounted camera equipment; medical camera equipment such as endoscopes, capsule endoscopes and catheters; biometric sensors, Optical filters used in biosensors, military reconnaissance cameras, 3D map cameras, weather and ocean observation cameras, land resource exploration cameras, and space equipment such as exploration cameras for space astronomical and deep space targets and It can be used as a light shielding member and a light shielding layer of a module, and also as an antireflection member and an antireflection layer.

The cured film of the present invention can also be used for applications such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode). Although not particularly limited, it is preferably used for optical filters and optical films used for micro LEDs and micro OLEDs, as well as members that impart a light shielding function or an antireflection function.
Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.

The cured film obtained by curing the composition of the present invention can also be used for applications such as quantum dot displays. Although not particularly limited, it is suitably used for a member that has a light-shielding function and an antireflection function, as well as an optical and an optical film used for a quantum dot display.
Examples of quantum dot displays are US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. The ones mentioned are mentioned.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this. In addition, "part" and "%" are based on mass unless otherwise specified.

[Composition]
In preparing the compositions of Examples and Comparative Examples, each component contained in the compositions will be described below.

<Titanium nitride-containing particles>
As the titanium nitride-containing particles, titanium nitride-containing particles TiN-1 to TiN-19 produced as described below were used.
Table 1 shows the components used in the production of the titanium nitride-containing particles and the amounts added. In Table 1, of the added amount of titanium particles (Ti particles), the "residual amount" means the amount excluding the content of the added particles. Moreover, "wt%" means the mass %.

(Titanium nitride-containing particles TiN-1)
Titanium nitride-containing particles TiN-1 were produced using the components shown in Table 1.
First, the Ti particles shown in Table 1 were plasma-treated in Ar gas to form Ti nanoparticles. The Ti nanoparticles after the plasma treatment were allowed to stand for 24 hours under an Ar gas atmosphere under an O ₂ concentration of 50 ppm or less and 30° C., and then O ₂ gas was introduced into the Ar atmosphere so that the O ₂ concentration became 100 ppm. In this state, it was left standing at 30° C. for 24 hours (pretreatment of Ti particles).
Thereafter, the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition that the yield was 10%, and powder of Ti nanoparticles was obtained. The primary particle diameter of the obtained powder was 120 nm when the average particle diameter of 100 particles was obtained by arithmetical averaging by TEM observation.
The titanium nitride-containing particles TiN-1 were produced using an apparatus similar to the apparatus for producing black composite fine particles shown in FIG. 1 of WO 2010/147098.
Specifically, in the black composite fine particle manufacturing apparatus, a high frequency voltage of about 4 MHz and about 80 kVA is applied to the high frequency oscillation coil of the plasma torch, and argon gas of 50 L/min and nitrogen is supplied as plasma gas from the plasma gas supply source. A mixed gas of 50 L/min was supplied and an argon-nitrogen thermal plasma flame was generated in the plasma torch. Further, a carrier gas of 10 L/min was supplied from the atomizing gas supply source of the material supply device.
Then, the titanium particles obtained as described above and the additive particles described in Table 1 were added as the additive amount described in Table 1, and together with the argon gas as the carrier gas, in the thermal plasma flame in the plasma torch. And was vaporized in a hot plasma flame and highly dispersed in the gas phase.
Further, nitrogen was used as the gas supplied into the chamber by the gas supply device. The flow rate in the chamber at this time was 5 m/sec, and the supply rate was 1000 L/min. The pressure inside the cyclone was 50 kPa, and the feed rate of each raw material from the chamber to the cyclone was 10 m/s (average value).
In this way, titanium nitride-containing particles TiN-1 were obtained.

Regarding the obtained titanium nitride-containing particles TiN-1, the content of titanium (Ti) atoms, Fe (iron) atoms and silicon (Si) atoms was measured by ICP emission spectroscopy. The results are shown in Table 1. For the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analysis device “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
Further, the content of nitrogen atoms was measured using an oxygen/nitrogen analyzer “EMGA-620W/C” (trade name) manufactured by Horiba Ltd., and calculated by an inert gas fusion-thermal conductivity method. The results are shown in Table 1.
In addition, regarding titanium nitride-containing particles TiN-2 to TiN-19 described later, the content of Ti atoms, Fe atoms, silicon atoms, and nitrogen atoms was measured by the same method as that for titanium nitride-containing particles TiN-1. .. The results are shown in Table 1.

The X-ray diffraction of the titanium nitride-containing particles TiN-1 was measured by packing a powder sample in an aluminum standard sample holder and using a wide-angle X-ray diffraction method (manufactured by Rigaku Denki Co., Ltd., trade name "RU-200R"). As the measurement conditions, the X-ray source was CuKα ray, the output was 50 kV/200 mA, the slit system was 1°-1°-0.15 mm-0.45 mm, the measurement step (2θ) was 0.02°, and the scan speed was 2°/min.
Then, the diffraction angle 2θ of the peak derived from the TiN(200) plane observed near the diffraction angle 2θ (42.6°) was measured. Further, the crystallite size constituting the particles was determined from the half-width of the peak derived from the (200) plane using Scherrer's formula. The results are shown in Table 1. No X-ray diffraction peak due to TiO ₂ was found.
The diffraction angle 2θ and crystallite size of the following titanium nitride-containing particles TiN-2 to TiN-19 were measured by the same method as that for the titanium nitride-containing particles TiN-1. The results are shown in Table 1. Note that no X-ray diffraction peak due to TiO ₂ was found for any of the titanium nitride-containing particles.

(Titanium nitride-containing particles TiN-2)
Titanium nitride-containing particles TiN-2 were produced in the same manner as the production of titanium nitride-containing particles TiN-1 except that the raw materials used in the production of TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-3)
Titanium nitride-containing particles TiN-3 were produced in the same manner as the production of titanium nitride-containing particles TiN-1 except that the raw materials used in the production of TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-4)
Titanium nitride-containing particles TiN-4 were produced in the same manner as the production of titanium nitride-containing particles TiN-1 except that the raw materials used in the production of TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-5)
Titanium nitride-containing particles TiN-5 were produced in the same manner as in the production of titanium nitride-containing particles TiN-1 except that the raw materials used in the production of TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-6)
Titanium nitride-containing particles TiN-6 were produced in the same manner as the production of titanium nitride-containing particles TiN-1 except that the raw materials used in the production of TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-7)
In the same manner as in the production of titanium nitride-containing particles TiN-6, except that the supply rate of each raw material from the chamber to the cyclone in the production of TiN-6 particles was changed to 8 m/s (average value), Particle TiN-7 was produced.

(Titanium nitride-containing particles TiN-8)
Titanium nitride-containing, except that the raw materials used for the production of TiN-1 particles and the addition amounts were as shown in Table 1, and the feed rate of each raw material from the chamber to the cyclone was changed to 15 m/s (average value). Titanium nitride-containing particles TiN-8 were produced in the same manner as the production of particles TiN-1.

(Titanium nitride-containing particles TiN-9)
Titanium nitride-containing material except that the raw material used for the production of TiN-1 particles and the addition amount were as shown in Table 1 and the feed rate of each raw material from the chamber to the cyclone was changed to 20 m/s (average value). Titanium nitride-containing particles TiN-9 were produced in the same manner as the production of particles TiN-1.

(Titanium nitride-containing particles TiN-10)
Titanium nitride-containing particles TiN-10 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials used for producing the TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-11)
The same as the production of the titanium nitride-containing particles TiN-1 except that the raw materials used for the production of the TiN-1 particles and the addition amount were set as shown in Table 1 and the pretreatment and the standing treatment of the Ti particles were not carried out. Then, titanium nitride-containing particles TiN-11 were manufactured.

(Titanium nitride-containing particles TiN-12)
Titanium nitride-containing particles TiN-12 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials used for producing the TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-13)
Titanium nitride-containing particles TiN-13 were produced in the same manner as the production of titanium nitride-containing particles TiN-1 except that the raw materials used in the production of TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-14)
Titanium nitride-containing particles TiN-14 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials used in the production of the TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-15)
Titanium nitride-containing particles TiN-15 were produced in the same manner as in the production of titanium nitride-containing particles TiN-1 except that the raw materials used in the production of TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-16)
Titanium nitride-containing particles TiN-16 were produced in the same manner as the production of titanium nitride-containing particles TiN-1 except that the raw materials used in the production of TiN-1 particles and the addition amounts were as shown in Table 1. ..

(Titanium nitride-containing particles TiN-17, TiN-18 and TiN-19)
In the production of TiN-4 particles, the same as titanium nitride-containing particles TiN-4, except that the standing time under the oxygen (O ₂ ) concentration control after the production of titanium nitride-containing particles described below is set as shown in Table 1. Then, titanium nitride-containing particles TiN-17, TiN-18 and TiN-19 were produced.

<Standing period under control of oxygen (O ₂ ) concentration after production of titanium nitride-containing particles (Standing under introduction of O ₂ after production of TiN particles)>
The titanium nitride-containing particles obtained as described above were subjected to nitrogen (N ₂ ) gas in which the oxygen (O ₂ ) concentration and the water content were controlled to 100 ppm or less for the periods described in Tables 1 to 5, respectively. After standing still in the introduced closed container, each composition was prepared.
In Tables 1 to 5, "None" means that the produced titanium nitride-containing particles were immediately opened to the atmosphere and used. Further, 12 hr, 24 hr, 48 hr, and 72 hr respectively indicate the time when the produced titanium nitride-containing particles were allowed to stand in a container having an oxygen (O ₂ ) concentration of 100 ppm or less.

<Dispersant>
As the dispersant, Dispersants A to G having the following structures were used. The numerical value described in each structural unit means the mass% of each structural unit based on all structural units.

<Binder resin>
Acrycure RD-F8 (trade name, manufactured by Nippon Shokubai Co., Ltd.) was used as the resin A which is a binder resin. The structure of Resin A is shown below.

<Polymerizable compound>
-Polymerizable compound M1 (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA", refer to the following formula)
Polymerizable compound M2 (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD RP-1040", see the following formula)

<Polymerization initiator>
OXE-01: Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd.)
OXE-02: Irgacure OXE02 (trade name, manufactured by BASF Japan Ltd.)
-I-1: Polymerization initiator of the following formula (I-1)-I-2: Polymerization initiator of the following formula (I-2) (Brand name "B-CIM", Hodogaya Chemical Co., Ltd.)
-I-3: Polymerization initiator of the following formula (I-3)-I-4: Polymerization initiator of the following formula (I-4)-I-5: Polymerization initiator of the following formula (I-5)-NCI -831: Adeka Archurus NCI-831 (trade name, manufactured by Adeka)
・N-1919: trade name, manufactured by ADEKA

<Organic solvent>
・PGMEA: Propylene glycol monomethyl ether acetate ・Cyclopentanone ・Butyl acetate

<Surfactant>
F-1: The following mixture (weight average molecular weight (Mw)=14000)

<Polymerization inhibitor>
p-methoxyphenol

<Preparation of pigment dispersion>
First, the titanium nitride-containing particles, the dispersant, and the organic solvent were mixed for 15 minutes by a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion. Next, the obtained dispersion was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. to obtain a pigment dispersion. The ratio (D/P) of the dispersant to the titanium nitride-containing particles was added so as to be the ratio shown in each of Examples and Comparative Examples in Tables 2 to 5.
(Dispersion condition)
・Bead diameter: φ0.05 mm, (Nikkato zirconia beads, YTZ)
・Bead filling rate: 65% by volume
・Mill peripheral speed: 10 m/sec
・Separator peripheral speed: 13m/s
・Amount of mixed liquid for dispersion treatment: 15kg
・Circulation flow rate (pump supply rate): 90 kg/hour
・Treatment temperature: 19~21℃
・Cooling water: Water・Treatment time: About 22 hours

<Preparation of composition>
Next, the pigment dispersion, the binder resin, the polymerizable compound, the surfactant, the polymerization inhibitor and the organic solvent are mixed and stirred, and each composition of Examples and Comparative Examples shown in Tables 2 to 5 below. I got a thing.
The content (% by mass) of each component contained in each composition of Examples and Comparative Examples is shown in Tables 2 to 5.

<Measurement of water content in composition>
The water content of each composition of Examples and Comparative Examples was measured by MKV-710 (trade name, manufactured by Kyoto Electronics Manufacturing Co., Ltd.) using the Karl Fischer method as a measurement principle. The results are shown in Tables 2-5.

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

<Variation in particle size during preparation>
A test solution was prepared by diluting each composition of Examples and Comparative Examples 100-fold with PGMEA, and the obtained test solution was stored in an environment of 45°C for 3 days. Then, the average particle size (D90) of the titanium nitride-containing particles contained in the test solution before and after storage was measured by a particle size distribution measuring device (manufactured by Microtrac, product name "Nanotrack UPA-150EX"). Based on the value of the average particle diameter (D90) of the test solution before and after storage, the particle size fluctuation during preparation of the solution was evaluated according to the following criteria.
A: 0≦(D90 of titanium nitride-containing particles after storage)-(D90 of titanium nitride-containing particles before storage)<0.010 μm
B: 0.010 μm≦(D90 of titanium nitride-containing particles after storage)−(D90 of titanium nitride-containing particles before storage)<0.015 μm
C: 0.015 μm≦(D90 of titanium nitride-containing particles after storage)−(D90 of titanium nitride-containing particles before storage)<0.020 μm
D: 0.020 μm≦(D90 of titanium nitride-containing particles after storage)−(D90 of titanium nitride-containing particles before storage)

<Number of particles>
A sample solution prepared by diluting the above composition 500 times with PGMEA was prepared, and the number of particles containing titanium nitride having a size of 10 μm or more contained in 10 ml of this sample solution was measured by a flow-type particle image analyzer (trade name “FPIA”). Manufactured by Malvern Instruments Inc.).

<Filterability>
The filterability of each composition of Examples and Comparative Examples was evaluated by filtration using a capsule filter DFA (manufactured by Nippon Pall Ltd., nylon pore size 0.45 μm, 2 inches). The filtration was performed by sending 16 kg of the composition under a pressure condition of 0.05 MPa. The filterability was evaluated based on the following criteria.
A: All 16 kg could be filtered.
B: Filter clogging occurred at 10 kg or more and less than 16 kg.
C: Filter clogging occurred in the range of 5 kg or more and less than 10 kg.
D: Filter clogging occurred in less than 5 kg.

<Stability of viscosity over time>
Each composition of Examples and Comparative Examples was stored at 23° C. for 10 days and then at 7° C. for 90 days. Then, the viscosities of the respective compositions before and after storage were measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., trade name "R85 viscometer") under the conditions of a rotation speed of 10 rpm and 23°C. Then, the value (%) of [(viscosity of the composition after storage)-(viscosity of the composition before storage)/(viscosity of the composition before storage)] x 100 was calculated. The evaluation criteria are as follows.
A: Within ±3% B: Within ±3%, Within ±5% C: Within ±5%, Within ±10% D: Over ±10%

<Corrosion resistance of electrode>
By using each composition of Examples and Comparative Examples as a photosensitive resin composition, an electrode pattern (copper layer) formed on the surface of a silicon wafer so that the dry film thickness of the coating film of each composition was 0.7 μm. ) Was coated with a spin coater. The coating film was formed by leaving it in that state for 10 minutes after coating, and then using a hot plate at 100° C., heat-treating (pre-baking) the silicon wafer coated with each composition for 120 seconds. , I-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) was used to expose the coating film at a wavelength of 365 nm and an exposure dose of 500 mJ/cm ² through a pattern mask having an Island pattern of 20 μm square.
The compositions of Examples and Comparative Examples are negative photosensitive resin compositions in which the exposed areas are cured.
After that, the silicon wafer on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film Electronics Material). Paddle development was performed at 23° C. for 60 seconds using an organic alkaline liquid developer manufactured by SUZU CORPORATION.
Then, the silicon wafer after paddle development is fixed to the horizontal rotary table by a vacuum chuck method, and while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device, pure water is sprayed from above the center of rotation into a shower shape from a jet nozzle. It was supplied and rinsed. Then, the silicon wafer was spray-dried to produce a wafer having a frame-shaped black matrix.
A wafer having a frame-shaped black matrix was stored for 3 months in an environment of a temperature of 25° C. and a humidity of 65% RH, and then the number of rust occurrence points on the electrode pattern of the 300 electrode pads formed on the wafer was measured with an optical microscope ( It was observed under the trade name “LEXT OLS4500” manufactured by Olympus Corporation. The anticorrosion property of the electrode was evaluated according to the following criteria based on the number of rusting points.
A: 0 to 5 rust occurrence points B: 6 to 10 rust occurrence points C: 11 to 20 rust occurrence points D: 21 or more rust occurrence points

<Patterning property (development residue)>
For a wafer having a frame-shaped black matrix obtained in the same manner as the above "corrosion resistance of the electrode", the unexposed portion was used with a scanning electron microscope (Hitachi High-Technologies Corporation, trade name "SU8010"). The surface of the substrate was observed at a magnification of 20,000 times, the number of particulate residues confirmed in the obtained observed image was counted, and the patterning property (development residue) was evaluated according to the following criteria.
A: No development residue is observed in the unexposed area B: 1 to 49 particles of development residue in the unexposed area C: 50 to 100 particles of development residue in the unexposed area D: Particles in the unexposed area 101-like development residue

<Reworkability>
A wafer having a frame-like black matrix similar to the wafer used for evaluating the anticorrosion property of the electrode was immersed in a 25% aqueous solution of TMAH (tetramethylammonium hydroxide) at 85° C. for 5 hours, and then 2 L of DIW( A rinse treatment was carried out by immersing in a (pure water) bath at room temperature for 2 minutes. The removal state of the frame-shaped black matrix of the obtained rinsed wafer was observed with an optical microscope (Olympus, trade name "LEXT OLS4500"), and the reworkability was evaluated based on the following evaluation criteria.
A: No pattern is observed B: Particulate removal residue is observed in 5% or less of the pattern formation area C: Particulate removal residue is observed in more than 5% and 10% or less of the pattern formation area D: Pattern Particulate removal residue is observed in more than 10% of the formed area, or a pattern or part of the pattern is observed.

<Appearance during humidity resistance test>
A wafer having a frame-like black matrix similar to the wafer used for evaluating the anticorrosion property of the electrode was exposed to an environment of 90° C. and a humidity of 85% RH for 1000 hours. With respect to the exposed wafer, the appearance change of the black matrix was observed with an optical microscope (manufactured by Olympus, trade name “LEXT OLS4500”), and the appearance at the time of the moisture resistance test was evaluated based on the following evaluation criteria.
A: No difference is observed before and after the moisture resistance test, or surface roughness with unevenness difference of 10 nm or less is observed after the humidity resistance test.
B: Surface roughness with unevenness difference of more than 10 nm and 50 nm or less is observed after the humidity resistance test.
C: After the moisture resistance test, surface roughness with unevenness difference of more than 50 nm and 100 nm or less is observed.
D: Surface roughness with unevenness difference of more than 100 nm is observed after the humidity resistance test.

<Pinhole>
Except for forming a coating film on the entire surface of the glass substrate without using a pattern mask having an Island pattern in the production of the wafer used for evaluating the corrosion resistance of the electrodes, using a glass substrate of 10 cm square instead of the silicon wafer. In the same manner as in the production of the wafer used for the evaluation of the anticorrosion property of the above electrode, a cured film obtained by using each composition of Examples and Comparative Examples was formed on the entire surface of one surface of the glass substrate. ..
A light source is installed on the side of the glass substrate opposite to the side where the cured film is provided, and the appearance of the cured film is visually observed from the side where the light source is installed, and pinholes (diameter of 10 μm or more) existing on the glass substrate are observed. ) Was counted. The following criteria were evaluated.
A: 0 to 1 pinholes B: 2 to 10 pinholes C: 11 to 20 pinholes D: 21 or more pinholes

<Spectral (light blocking)>
Each composition of Examples and Comparative Examples was applied onto a glass plate (EagleXG, Corning) having a thickness of 0.7 mm and a 10 cm square by spin coating at a rotation speed of 1.0 μm to form a coating film. Formed. Then, using 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 obtained dried film was measured by a spectrophotometer U-4100 (manufactured by Hitachi High Technologies). Based on the lowest OD at wavelengths of 400 to 1200 nm, the spectrum (light-shielding property) was evaluated according to the following criteria.
AA: Minimum OD>4.2
A: 4.2≧minimum OD>4.0
B: 4.0≧minimum OD>3.7
C: 3.7≧minimum OD>3.5
D:3.5≧minimum OD

Tables 2 to 5 show the above evaluation results. In Tables 2 to 5, "dispersant/Fe (content ratio)" means the content ratio of the dispersant to the content of Fe atom [(content of the dispersant in the composition (mass %))/(composition Content of Fe atoms (mass %))]. In addition, the “polymerizable compound/Fe (content ratio)” means the content ratio of the polymerizable compound with respect to the content of the Fe atom [(content of the polymerizable compound in the composition (mass %))/(composition Content of Fe atoms (mass %))].

As shown in Tables 2 to 5, when the content of Fe atoms in the titanium nitride-containing particles is in the range of more than 0.001 mass% and less than 0.4 mass%, the patterning property and the corrosion resistance of the electrode It was shown that a cured film excellent in heat resistance can be produced (Example).
On the other hand, when the content of Fe atoms in the titanium nitride-containing particles was 0.001% by mass or less, it was shown that the patternability was poor (Comparative Example 1 and Comparative Example 3).
Further, it was shown that when the content of Fe atoms in the titanium nitride-containing particles was 0.4% by mass or more, the anticorrosion property of the electrode was inferior (Comparative Example 2).

A composition was prepared in the same manner as in Example 1 except that the polymerizable compound M1 used for preparing the composition was changed to the polymerizable compound U15HA (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "U15HA"), and each evaluation was performed. went. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

A composition was prepared in the same manner as in Example 1 except that the polymerizable compound M1 used for the preparation of the composition was changed to a cardo monomer (trade name “Ogsol” manufactured by Osaka Gas Chemicals Co., Ltd.), and each evaluation was performed. .. As a result of the evaluation, it was found that the same results as in Example 1 were obtained except that the evaluation result of the patterning property was "A".

A composition was prepared and evaluated in the same manner as in Example 1, except that the composition was prepared without using the polymerization inhibitor. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

A composition was prepared in the same manner as in Example 1 except that the surfactant F-1 was not used, and each evaluation was performed. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

<Preparation of carbon black dispersion (CB dispersion)>
In the preparation of the above pigment dispersion, instead of the titanium nitride-containing particles, carbon black (trade name “Color Black S170”, manufactured by Degussa Co., average primary particle diameter 17 nm, BET specific surface area 200 m ² /g, gas black method) A pigment dispersion was prepared in the same manner except that the carbon black manufactured by 1. was used to obtain a carbon black dispersion.

In the preparation of the composition of Example 1, titanium nitride-containing particles TiN-1 are contained instead of the pigment dispersion added so that the titanium nitride-containing particles TiN-1 are contained in the composition in an amount of 16% by mass. A mixture of the pigment dispersion and the above CB dispersion [titanium nitride-containing particles in the composition TiN-1: carbon black of the composition=4:1 (mass ratio) (containing titanium nitride in the composition The total content of the particles TiN-1 and carbon black is 16% by mass)], and a composition was prepared in the same manner as above, and each evaluation was performed. As a result of the evaluation, it was found that the same light-shielding property as in Example 1 was obtained.

<Preparation of chromatic pigment dispersion (PY dispersion)>
In the preparation of the above pigment dispersion, the same method was used except that Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN) was used instead of the titanium nitride-containing particles. A dispersion was prepared to obtain a chromatic color pigment dispersion (PY dispersion).

In the preparation of the composition of Example 1, titanium nitride-containing particles TiN-1 are contained instead of the pigment dispersion added so that the titanium nitride-containing particles TiN-1 are contained in the composition in an amount of 16% by mass. A mixture of the pigment dispersion and the above PY dispersion [titanium nitride-containing particles in the composition TiN-1: Pigment Yellow in the composition 150=5:1 (mass ratio) (titanium nitride in the composition The total content of the content particles TiN-1 and Pigment Yellow 150 is 16% by mass)], and a composition was prepared in the same manner, and each evaluation was performed. As a result of the evaluation, it was found that the same light-shielding property as that of Example 1 was obtained and a film having a deep black tint was obtained.

Claims (18)

Containing titanium nitride-containing particles containing Fe atoms and a polymerization initiator ,
The composition in which the content of the Fe atoms in the titanium nitride-containing particles is 0.0030 to 0.30 mass% . Containing titanium nitride-containing particles containing Fe atoms and Si atoms,
The content of the Fe atoms in the titanium nitride-containing particles is 0.0030 to 0.30 mass%,
The composition, wherein the content of the Si atoms in the titanium nitride-containing particles is more than 0.002 mass% and less than 0.3 mass%. Containing titanium nitride-containing particles containing Fe atoms and a dispersant,
The content of the Fe atoms in the titanium nitride-containing particles is 0.0030 to 0.30 mass%,
The composition wherein the dispersant has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and cyclic or chain polyester. Diffraction angle 2θ of peak derived from the (200) plane of the titanium nitride-containing particles, in a case of providing a CuKα ray as an X-ray source, is less than 42.6 ° Ultra 43.5 °, claim 1-3 The composition according to any one of 1 . The number of following the titanium nitride-containing particles of 10μm or more size obtained by the particle number measuring method, is 100 or less, the composition according to any one of claims 1-4.
Particle number measurement method: A sample solution prepared by diluting the composition 500 times with propylene glycol monomethyl ether acetate was prepared, and the number of particles containing titanium nitride having a size of 10 μm or more contained in 10 ml of the sample solution was calculated by a flow method. It is measured by a particle image analyzer. Further, containing two or more organic solvents, Composition according to any one of claims 1-5. Furthermore, a binder resin composition according to any one of claims 1-6. Further, a polymerizable compound, composition according to any one of claims 1-7. The composition according to claim 1, wherein the solid content in the composition is 10 to 40% by mass. The composition according to any one of claims 1 to 9, wherein the content of the titanium nitride-containing particles is 20 to 70 mass% with respect to the total solid content of the composition. In addition, containing water,
The composition according to any one of claims 1 to 10, wherein the content of water is 0.1 to 1% by mass based on the total mass of the composition. The composition according to claim 3 , wherein the content ratio of the dispersant with respect to the titanium nitride-containing particles is 0.05 to 0.30. A method for producing a composition , comprising titanium nitride-containing particles containing Fe atoms, wherein the content of Fe atoms in the titanium nitride-containing particles is 0.0030 to 0.30% by mass ,
A method for producing a composition, comprising the step of obtaining the titanium nitride-containing particles by a thermal plasma method. A cured film obtained using a composition containing titanium nitride-containing particles containing Fe atoms, wherein the content of the Fe atoms in the titanium nitride-containing particles is 0.0030 to 0.30% by mass . A color filter comprising the cured film according to claim 14 . A light-shielding film having the cured film according to claim 14 . A solid-state image sensor having the cured film according to claim 14 . An image display device comprising the cured film according to claim 14 .