TWI726075B - Composition, method for manufacturing composition, cured film, color filter, light-shielding film, solid-state imaging element, and image display device - Google Patents

Abstract

The present invention provides a composition capable of producing a cured film with excellent light-shielding, excellent resolution, and excellent electrode corrosion resistance, and a method for manufacturing the composition, a cured film, a color filter, a light-shielding film, Solid-state imaging device and image display device. The composition contains metal-containing nitride particles containing predetermined atoms, and the metal-nitride-containing particles contain transition metals that remove titanium among transition metals of groups 3 to 11 and have electronegativity of 1.22 to 2.36.化物。

Description

Composition, method for manufacturing composition, cured film, color filter, light-shielding film, solid-state imaging element, and image display device

The present invention is a composition, a method for manufacturing the composition, a cured film, a color filter, a light shielding film, a solid-state imaging element, and an image display device.

Conventionally, as a black powder, a composition containing titanium nitride has been known. The composition containing titanium nitride is used for various purposes, for example, for the production of light-shielding films installed in liquid crystal display devices and solid-state imaging devices. Specifically, a color filter used in a liquid crystal display device is provided with a light-shielding film called a black matrix in order to shield light between colored pixels and improve contrast. In addition, the solid-state imaging element is also provided with a light-shielding film in order to prevent the generation of noise, improve image quality, and the like. Currently, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin camera modules. This type of camera module usually has a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor (Complementary Metal-Oxide Semiconductor)) image sensor and other solid-state image sensors. A lens used to form a subject image on a solid-state imaging device.

Moreover, in recent years, focusing on the transmittance of light of a specific wavelength, research has been conducted to replace titanium nitride with black powders of metal oxynitride with lower transmittance (higher light-shielding properties) of light of a specific wavelength. For example, Patent Document 1 discloses "a blue shielding black powder, which is a black powder containing one or two nitrogen oxides of vanadium or niobium, and is characterized by an oxygen content of 16wt% or less and a nitrogen content of 10wt% Above, in the transmission spectrum of the dispersion liquid with a powder concentration of 50 ppm, the transmittance X at 450 nm is 10.0% or less.". [Prior Technical Document] [Patent Document]

[Patent Document 1]: JP 2012-96945 A

The blue-shielding black powder described in Patent Document 1 has excellent properties as a black pigment with high light-shielding properties. However, according to research conducted by the inventors, it has been found that when a composition containing the black pigment as described above is used to form a cured film processed into a pattern on a substrate on which an electrode pattern is formed, the resolution is improved and the electrode pattern is improved. There is room for further improvement in terms of degradation (corrosion) suppression. In addition, the resolution means that the obtained pattern shape is closer to the desired shape than the desired fine pattern. Specifically, the obtained pattern shape is not thicker or thinner than the desired shape.

The subject of the present invention is to provide a composition capable of producing a cured film having excellent light-shielding properties, excellent resolution, and excellent electrode corrosion resistance. In addition, the subject of the present invention is to provide a method of manufacturing a composition, a cured film, a color filter, a light-shielding film, a solid-state imaging element, and an image display device.

The inventors of the present invention conducted intensive studies in order to solve the above-mentioned problems. As a result, they found a composition containing metal nitride-containing particles containing predetermined atoms. The metal-nitride-containing particles contain transition metals in groups 3-11. The composition of the nitride of a transition metal other than titanium and a transition metal with an electronegativity of 1.22 to 2.36 can solve the above-mentioned problems, and the present invention has been completed. That is, it was found that the above-mentioned problem can be solved by the following structure.

[1] A composition containing metal nitride particles containing atom A, wherein the metal nitride particles contain transition metals other than titanium among transition metals of groups 3 to 11 and have an electronegativity of 1.22 ~2.36 transition metal nitride, atom A is an element different from the transition metal constituting the transition metal nitride, at least selected from the group consisting of boron, aluminum, silicon, manganese, iron, nickel and silver In one type, the content of atom A in the metal nitride-containing particles is 0.00005 to 10% by mass. [2] The composition according to [1], wherein the electrical conductivity of the metal nitride-containing particles is 100×10 ⁴ to 600×10 ⁴ S/m. [3] The composition according to [1] or [2], wherein the metal nitride-containing particles have an average primary particle size of 10 to 50 nm. [4] The composition according to any one of [1] to [3], which further contains a binding resin. [5] The composition according to [4], wherein the mass ratio of the binder resin to the metal nitride-containing particles is 0.3 or less. [6] The composition according to any one of [1] to [5], the transition metal is selected from the group consisting of V, Cr, Y, Zr, Nb, Hf, Ta, W and Re At least one. [7] The composition according to any one of [1] to [6], wherein the transition metal is at least one selected from the group consisting of V and Nb. [8] The composition according to any one of [1] to [7], which further contains a polymerizable compound. [9] The composition according to any one of [1] to [8], which further contains a polymerization initiator. [10] The composition according to any one of [1] to [9], which further contains a solvent and has a solid content of 10 to 40% by mass. [11] The composition according to [10], wherein the solvent contains water, and the water content is 0.1 to 1% by mass relative to the total mass of the composition. [12] The composition according to any one of [1] to [11], wherein the content of the metal nitride-containing particles is 20 to 70% by mass relative to the total solid content of the composition. [13] The composition according to any one of [1] to [12], which further contains a dispersant, and the dispersant contains polymethyl acrylate, polymethyl methacrylate, and cyclic or chain At least one structure in the group consisting of polyester. [14] The composition according to [13], wherein the mass ratio of the dispersant to the metal nitride-containing particles is 0.05 to 0.30. [15] The composition according to any one of [1] to [14], wherein the metal nitride-containing particles are metal nitride-containing particles coated with an inorganic compound containing aluminum hydroxide. [16] A method for producing a composition, which is a method for producing the composition described in any one of [1] to [15], which includes a process for obtaining metal nitride-containing particles by a thermoplasma method. [17] A cured film obtained using the composition described in any one of [1] to [15]. [18] A color filter containing the cured film described in [17]. [19] A light-shielding film containing the cured film described in [17]. [20] A solid-state imaging element containing the cured film described in [17]. [21] An image display device containing the cured film described in [17]. [Effects of the invention]

According to the present invention, it is possible to provide a composition capable of producing a cured film having excellent light-shielding properties, excellent resolution, and excellent electrode corrosion resistance (hereinafter, also referred to as "the effect of the present invention") composition. Furthermore, according to the present invention, it is possible to provide a method for manufacturing a composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, and an image display device.

Hereinafter, the composition will be described in detail for each component constituting the composition. In this specification, the numerical range indicated by "～" means the range containing the numerical value described before and after "～" as the lower limit and the upper limit. In addition, in the expression of a group (atomic group) in this specification, expressions that do not describe substitution and unsubstituted include those that do not contain substituents, and include those that contain substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups). In addition, in this specification, "active light" or "radiation" means extreme ultraviolet, extreme ultraviolet (EUV: Extreme ultraviolet lithography), X-rays, electron beams, etc. represented by the bright-ray spectrum of mercury lamps and excimer lasers, for example. In addition, in this specification, "light" means active light or radiation. Regarding the "exposure" in this manual, unless otherwise specified, it is not limited to exposure based on the bright line spectrum of mercury lamps, extreme ultraviolet light represented by excimer lasers, X-rays and EUV light, and based on electron beams and ion beams, etc. The description of the particle beam is also included in the exposure. In addition, in this specification, "(meth)acrylate" means acrylate and methacrylate. In addition, in this specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. In addition, in this specification, "(meth)acryloyl group" means an acryloyl group and a methacryloyl group. In addition, in this specification, "(meth)acrylamide" means acrylamide and methacrylamide. In addition, in this specification, "monomer" and "monomer" have the same meaning. Monomers are distinguished from oligomers and polymers and refer to compounds with a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound refers to a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction. [Composition] The above-mentioned composition is a composition containing particles of metal nitride containing atom A, wherein the particles containing metal nitride contain transition metals other than titanium among the transition metals of groups 3 to 11 and are electronegative. Nitrides of transition metals with properties ranging from 1.22 to 2.36, atom A is an element different from the above transition metals, at least one selected from the group consisting of boron, aluminum, silicon, manganese, iron, nickel and silver, The content of atom A in the metal nitride-containing particles is 0.00005 to 10% by mass. Although the reason why the above-mentioned composition has the effect of the present invention is not clear, the present inventors inferred as follows. In addition, the mechanism by which the above-mentioned composition exerts the effect of the present invention is not limited based on the following estimation.

The above composition contains nitrides of transition metals other than titanium among transition metals of groups 3 to 11 and whose electronegativity is 1.22 to 2.36. The valence band of the above-mentioned nitrides is composed of nitrogen 2p orbitals, so the valence band is closer to the negative side than oxides. In addition, as described above, the nitride contains a transition metal having a predetermined electronegativity, so the band gap between the valence band and the conduction band becomes smaller. As a result, it is inferred that the nitride system of the transition metal absorbs light in a wider wavelength region (the light-shielding property becomes higher). In addition, the electronegativity in this specification means the electronegativity based on Pauling's definition. In addition, the aforementioned composition contains atom A. Not only the light shielding property is high, but also the transmittance of light in the wavelength used for pattern formation (for example, i-ray: 365nm) can be controlled. Specifically, it is possible to transmit light necessary for pattern formation. That is, the above composition has excellent resolution. In addition, the above composition has the content of atom A in a predetermined range, and therefore has excellent corrosion resistance of the electrode.

[Metal Nitride-Containing Particles] The above-mentioned metal nitride-containing particles are metal nitride-containing particles containing atom A. The aspect in which the metal nitride-containing particles contain atom A is not particularly limited, and may be ions, metal compounds (including complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, Any form such as nitrogen oxide, sulfide, and sulfur oxide is included. In addition, the atom A contained in the metal nitride-containing particle may exist as an impurity in the inter-lattice position, or may exist as an impurity in an amorphous state at the grain boundary.

<Atom A> The atom A is contained in the metal nitride-containing particles. The atom A is an element different from the following transition metals, and is at least one selected from the group consisting of boron, aluminum, silicon, manganese, iron, nickel, and silver. Among them, from the viewpoint that the composition has more excellent effects of the present invention, at least one selected from the group consisting of aluminum, silicon, iron, nickel and silver is preferably selected from the group consisting of iron, silicon and nickel. It is more preferable that at least one of the groups is formed. Atom A may be used singly, or two or more of them may be used.

The content of atom A in the metal nitride-containing particles is 0.00005 to 10% by mass. If the content of atom A is less than the lower limit, the resolution of the cured film that can be obtained from the above composition is poor. If the content of atom A exceeds the upper limit, the light-shielding property of the cured film obtainable from the above composition and the corrosion resistance of the electrode are inferior. Among them, from the viewpoint that the cured film obtained from the above composition has more excellent corrosion resistance of the electrode, the content of atom A is preferably 0.00005 mass% or more and less than 1%, and 0.00005 mass% or more and less than 0.1% For better. In addition, if it is 0.00005% by mass or more and less than 10% by mass, the cured film obtained from the above composition has more excellent light-shielding properties. Among them, the content of atom A in the metal nitride-containing particles is measured by ICP (Inductively Coupled Plasma) emission spectrometry.

<Nitrides of transition metals> The above-mentioned metal-containing nitride particles contain transition metals other than titanium among the transition metals of groups 3 to 11 and have an electronegativity of transition metal nitrides of 1.22 to 2.36. Examples of the transition metals (electronegativity in parentheses) include Sc (1.36), Dy (1.22), Ho (1.23), Er (1.24), Tm (1.25), Lu (1.27) of transition elements of group 3 ), Th(1.3), Pa(1.5), U(1.38), Np(1.36), Pu(1.28), Am(1.3), Cm(1.3), Bk(1.3), Cf(1.3), Es(1.3 ), Fm(1.3), Md(1.3), No(1.3), Lr(1.3); Zr(1.33), Hf(1.3) of group 4; V(1.63), Nb(1.6), Ta( 1.5); Group 6 Cr (1.66), Mo (2.16), W (2.36); Group 7 Mn (1.55), Tc (1.9), Re (1.9); Group 8 Fe (1.83), Ru (2.2 ), Os (2.2); Group 9 Co (1.88), Rh (2.28), Ir (2.2); Group 10 Ni (1.91), Pd (2.2), Pt (2.28); Group 11 Cu (1.9) , Ag (1.93). Among them, from the viewpoint of the composition having more excellent effects of the present invention, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag , Hf, Ta, W, Re, Os, Ir or Pt are preferred, Sc, V, Cr, Co, Cu, Y, Zr, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re, Os, Ir or Pt is more preferred, V, Cr, Y, Zr, Nb, Hf, Ta, W or Re is further preferred, V, Cr, Y, Nb, Ta, W or Re is particularly preferred, V or Nb Particularly better, Nb is the best.

The content of the "transition metal constituting the nitride of the transition metal" in the metal nitride-containing particles is preferably 10 to 85% by mass, and more preferably 15 to 75% by mass relative to the total mass of the metal nitride-containing particles , 20 to 70% by mass is more preferable. The content of the "transition metal constituting the nitride of the transition metal" in the metal nitride-containing particles can be analyzed by ICP (Inductively Coupled Plasma) emission spectrometry. The content of nitrogen atoms (N atoms) in the metal nitride-containing particles relative to the total mass of the metal nitride-containing particles is preferably 3-60% by mass, more preferably 5-50% by mass, and 10-40% by mass % Is more preferable. The content of nitrogen atoms can be analyzed by the inert gas fusion thermal conductivity method. The metal nitride-containing particle contains a metal nitride as a main component, and may contain a part of oxygen atoms due to oxidation of the particle surface or the like. The oxidation of the particle surface becomes more pronounced when, for example, oxygen is mixed in during the synthesis of metal nitride or when the particle size is small. The content of oxygen atoms in the metal nitride-containing particles relative to the total mass of the metal nitride-containing particles is preferably 1-40% by mass, more preferably 1-35% by mass, and more preferably 5-30% by mass. good. The content of oxygen atoms can be analyzed by inert gas fusion infrared absorption method.

From the viewpoint of stability over time and light-shielding properties, the specific surface area of the metal 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 obtained by the BET (Brunauer, Emmett, Teller) method.

The metal nitride-containing particles may be composite particles including metal nitride-containing particles and metal fine particles. Composite particles refer to particles in which metal nitride-containing particles and metal particles are compounded or in a highly dispersed state. Among them, "combined" means that the particles are composed of two components of metal nitride and metal, and "highly dispersed state" means that the particles containing metal nitride and the metal particles exist separately, and the particles with a small amount of components are not Aggregate and disperse uniformly and uniformly. The metal particles are not particularly limited, and examples include those selected from copper, gold, platinum, palladium, tin, cobalt, rhodium, iridium, ruthenium, osmium, molybdenum, tungsten, niobium, tantalum, calcium, bismuth, antimony, and lead , And at least one of these alloys. Among them, at least one selected from copper, gold, platinum, palladium, tin, cobalt, rhodium and iridium, and these alloys is preferred, and at least one selected from copper, gold, platinum and tin, and these alloys One is better. The content of the metal fine particles in the metal nitride-containing particles is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass relative to the total mass of the metal nitride-containing particles.

<Method for producing metal nitride-containing particles> When producing metal nitride-containing particles, a gas phase reaction method is generally used. Specifically, an electric furnace method, a thermoplasma method, and the like are mentioned. Among these production methods, the thermoplasmic method is preferable from the viewpoint of less mixing of impurities, the viewpoint of easy uniformity of particle size, and the viewpoint of higher productivity. As a specific manufacturing method of metal nitride-containing particles by the thermoplasma method, for example, a manufacturing device using metal fine particles can be cited. The metal particle manufacturing device includes, for example, a plasma torch that generates thermoplasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber with a cooling function, a cyclone separator that classifies the generated metal particles, and recovery The structure of the recycling part of metal particles. In addition, in this specification, the metal fine particles refer to particles with a primary particle diameter of 20 nm to 40 μm containing a metal element.

The method for producing metal nitride-containing particles using the metal fine particle production device is not particularly limited, and a known method can be used. Among them, from the viewpoint of improving the yield of metal nitride-containing particles with the following prescribed average primary particle diameters, it is preferable that the method for producing metal nitride-containing particles using a metal fine particle manufacturing device includes the following process . Process A: A process in which inert gas without nitrogen is supplied as a plasma gas into the plasma torch to generate a thermal plasma flame. Process B: A process of supplying the metal raw material powder containing transition metal to the thermoplasma flame in the plasma torch, and evaporating the metal raw material powder to obtain the raw material metal in the gas phase. Process C: A process of cooling the raw material metal in the gas phase to obtain metal particles containing transition metals. Process D: A process in which inert gas containing nitrogen is supplied as a plasma gas into the plasma torch to generate a thermoplasma flame. Process E: A process in which metal particles containing transition metals are supplied to the thermoplasma flame in the plasma torch, and the metal particles are evaporated to obtain the raw material metal in the gas phase. Process F: A process of cooling the raw material metal in the gas phase to obtain metal nitride-containing particles. In addition, the method for manufacturing the metal nitride-containing particles may include the following process G after the aforementioned process C and/or process F as needed. Process G: The process of classifying the obtained particles. Moreover, the following process A2 may be included before process A, between process A and process B, between process C and process D, or between process D and E. Process A2: A process of mixing atoms A into metal raw material powders containing transition metals. Furthermore, the following processes A3-1 to A3-3 may be included before the above process A2. Process A3-1: The process of supplying inert gas without nitrogen as the plasma gas to generate the thermoplasma flame. Process A3-2: Supplying the raw material powder containing atom A to the thermoplasma flame in the plasma torch. The process of vaporizing the above-mentioned raw material powder to obtain atom A in the gas phase. Process A3-3: The process of cooling the atom A in the gas phase to obtain atom A that is atomized. In addition, process G can also be included after process A3-3 . In addition, in this specification, atom A to be atomized means a particle containing atom A with a primary particle diameter of 20 nm to 40 μm.

In addition, the method for manufacturing the metal nitride-containing particles described above preferably includes the following process H after the process F (when the process G is included, after the process G after the process F). Process H: A process in which the metal nitride-containing particles obtained in process F (or process G) are exposed to a mixed atmosphere of water vapor and nitrogen for nitriding treatment. In addition, the manufacturing method of the above-mentioned metal nitride-containing particles may also include a process G after the process H, if necessary. Hereinafter, the preferred state of each manufacturing process will be described in detail.

・Process A Process A is a process in which an inert gas containing no nitrogen is supplied as a plasma gas into the plasma torch to generate a thermal plasma flame. The method of generating thermoplasma flame is not particularly limited. Examples include direct current arc discharge method, multiphase arc discharge method, high frequency plasma method, and hybrid plasma method. The plasma method is preferred. The method of generating a thermoplasma flame based on the high-frequency plasma method is not particularly limited. For example, a plasma torch containing a coil for high-frequency oscillation and a quartz tube can be supplied with plasma gas to react to the above-mentioned high-frequency oscillation. A method of using a coil to apply a high-frequency current to obtain a thermoplasma flame. As the above-mentioned plasma gas in process A, an inert gas that does not contain nitrogen can be used. Examples of the inert gas that does not contain nitrogen include argon, hydrogen, and the like. The inert gas that does not contain nitrogen can be used singly, or two or more of them can be used.

・Process A2 Process A2 is a process in which atom A is mixed with metal raw material powders containing transition metals. The mixing method of the raw metal powder and atom A is not particularly limited, and a known method can be used. For example, the aforementioned material supply device for supplying metal raw material powder into the plasma torch may include mixing and dispersing functions. Specifically, the material supply device described in paragraphs 0047 to 0058 of International Publication No. 2010/147098 can be used, and this content is incorporated into this specification. In addition, as a method of manufacturing metal nitride-containing particles, the following processes A3-1 to A3-3 may be included before process A2.

・Process B Process B is a process of supplying the metal raw material powder containing transition metal to the thermoplasma flame in the plasma torch, and evaporating the above metal raw material powder to obtain the raw material metal in the gas phase. The method of supplying the metal raw material powder to the thermoplasma flame in the plasma torch is not particularly limited. From the viewpoint that the obtained gas phase raw material metal becomes a more uniform state, it is preferable to spray with a carrier gas. In addition, as the carrier gas, an inert gas that does not contain nitrogen is preferably used. The state of the inert gas that does not contain nitrogen is as described above. In addition, when the method for producing metal nitride-containing particles includes the above-mentioned process A2, it is preferable that the metal raw material powder maintains a uniform dispersion state between the supply of the metal raw material powder into the plasma torch.

・Process C Process C is a process of cooling the raw metal in the gas phase to obtain metal particles containing transition metals. The cooling method is not particularly limited, and it is preferable to use a chamber containing a cooling function. The raw material metal in the gas phase obtained in the above process B is introduced into a chamber containing the above cooling function, and rapidly cooled in the chamber, whereby the following metal fine particles of the desired particle size can be produced. The produced metal particles are recovered by the above-mentioned recovery unit, for example. As the atmosphere in the chamber, an inert gas that does not contain nitrogen is preferable. The state of the inert gas that does not contain nitrogen is as described above. In addition, by going through the above-mentioned processes A to C, metal particles containing transition metals can be obtained. Metal particles containing transition metals are easy to evaporate in process E. In addition, when the metal raw material powder contains impurities, the impurities can also be removed by going through the above-mentioned processes A to C.

・Process D Process D is a process in which an inert gas containing nitrogen is supplied as a plasma gas into the plasma torch to generate a thermal plasma flame. Examples of the inert gas containing nitrogen include nitrogen and nitrogen containing inert gas. As the inert gas, argon gas, hydrogen gas, and the like can be cited. The nitrogen containing inert gas is not particularly limited, and the content of nitrogen is usually about 10 to 90 mol%, preferably about 30 to 60 mol%. Other aspects are the same as process A.

・Process E Process E is a process in which metal particles containing transition metals are supplied to the thermal plasma flame in the plasma torch, and the metal particles are evaporated to obtain the raw material metal in the gas phase. As a method of supplying metal particles to the thermoplasma flame in the plasma torch, as described above, as the carrier gas, an inert gas containing nitrogen is preferred. The state of the inert gas containing nitrogen is as described above. In the process E, the raw material metal that becomes the metal particles through the process A to the process C is supplied to the thermoplasma flame, so the gas phase raw material metal is easily obtained, and the state of the gas phase raw material metal becomes more uniform.

・Process F Process F is a process of cooling the raw material metal in the gas phase to obtain metal nitride-containing particles containing transition metal nitrides. The preferred aspect of the cooling method is as described above, but as the atmosphere in the chamber, an inert gas containing nitrogen is preferred. Preferred aspects of the inert gas containing nitrogen are as described above.

・Process G Process G is a process of classifying the obtained metal particles and/or metal nitride-containing particles. The classification method is not particularly limited. For example, a cyclone separator can be used. The cyclone separator has a container on a cone, which has the function of generating a swirling flow in the container and using centrifugal force to classify particles. In addition, classification is preferably performed in an atmosphere of inert gas. The state of the inert gas is as described above.

・Process H Process H is a process in which metal nitride-containing particles are exposed to a mixed atmosphere of water vapor and nitrogen for nitriding treatment. Through the process, the content of metal nitride in the metal nitride-containing particles can be increased. The method of exposing the metal nitride-containing particles to the mixed atmosphere of water vapor and nitrogen is not particularly limited. For example, it can be mentioned that the metal nitride-containing particles are introduced into a constant temperature filled with a gas mixed with water vapor and nitrogen. The method of standing or stirring for a predetermined time in the tank is more preferable from the viewpoint of stabilizing the surface and grain boundaries of the metal nitride-containing particles. In addition, as the mixing ratio of water vapor and nitrogen, if it is in the air, the relative humidity is preferably 25 to 95%. In addition, the time for standing or stirring is preferably 0.5 to 72 hours, and the temperature at this time is preferably 10 to 40°C.

・Processes A3-1～A3-3 Processes A3-1～A3-3 are the processes (A3-1) in which inert gas without nitrogen is supplied into the plasma torch as the plasma gas to generate the thermoplasma flame (A3-1). The thermoplasma flame in the torch supplies the raw material powder containing atom A and evaporates the raw material powder to obtain the atom A in the gas phase (A3-2), and cools the atom A in the gas phase to obtain the fine particles containing atom A Manufacturing process (A3-3). The state of each process is as in the above process A, process B (instead of the metal raw material powder containing transition metal, use the raw material powder containing atom A), and process C (instead of the metal particles containing transition metal to obtain atomized atoms A.) The content has been explained in. In addition, by going through the above process, the atom A is atomized, and the atom A becomes easy to evaporate in the process E. In addition, by going through the above process, impurities (metal components other than atom A, etc.) contained in the raw material powder containing atom A can be removed.

(Preferred aspect of the method for producing metal nitride-containing particles containing atom A) As a preferable aspect of the method for producing metal nitride-containing particles containing atom A, there may be mentioned from top to bottom The following process is a method of manufacturing metal nitride-containing particles containing atom A.・Process A: A process in which inert gas without nitrogen is supplied as a plasma gas into the plasma torch to generate a thermal plasma flame.・Process B: The process of supplying the metal raw material powder containing transition metal to the thermoplasma flame in the plasma torch, and evaporating the above raw metal powder to obtain the raw material metal in the gas phase.・Process C: The process of cooling the above-mentioned raw material metal in the gas phase to obtain metal particles containing transition metals.・Process G: The process of classifying the obtained particles.・Process A3-1: Inert gas without nitrogen is supplied to the plasma torch as a plasma gas to generate a thermoplasma flame. ・Process A3-2: Supply raw material containing atom A to the thermoplasma flame in the plasma torch Powder, the process of evaporating the above-mentioned raw material powder to obtain atom A in the gas phase. Process A3-3: The process of cooling the atom A in the gas phase to obtain atom A that is atomized. Process G: The obtained particles are classified The manufacturing process.・Process A2: A process of mixing atom A (at this time, atom A to be atomized) into metal raw material powder containing transition metal (in this case, metal particles).・Process D: A process in which inert gas containing nitrogen is supplied as a plasma gas into the plasma torch to generate a thermoplasma flame.・Process E: A process in which metal particles containing transition metals are supplied to the thermoplasma flame in the plasma torch, and the metal particles are evaporated to obtain the raw material metal in the gas phase.・Process F: The process of cooling the above-mentioned raw material metal in the gas phase to obtain metal nitride-containing particles.・Process G: The process of classifying the obtained particles.・Process H: A process in which the metal nitride-containing particles obtained in Process G are exposed to a mixed atmosphere of water vapor and nitrogen for nitriding treatment. In addition, in the above series of processes, the order of process A to C and process A3-1 to A3-3 can be replaced. That is, the processes A to C may be implemented after the processes A3-1 to A3-3.

According to the preferred aspect of the method for producing metal-containing nitride particles containing atom A, the metal raw material powder and the impurities contained in the raw material particles can be removed, and the metal-containing nitride having the desired average primary particle size can be produced particle of. Although the mechanism by which impurities can be removed is not clear, the inventors of the present invention concluded as follows. That is, it is inferred that the transition metal and/or atom A are ionized by plasma treatment, and when the ions are cooled, the transition metal, atom A, and impurities are micronized by reflecting their respective melting points. At this time, the atomization of the atom with the lower melting point is faster, and the atomization of the atom with the higher melting point is slower. Therefore, as mentioned above, it is inferred that the particles (processes B and C, and processes A3-2 and A3-3) that have undergone a plasma treatment are likely to become a single component (single crystal). If the single-component particles obtained as described above are classified, the particles of the impurities can be removed by the difference in the density and/or particle size of the particles of the transition metal and/or the particles of the atom A and the particles of the impurities. In addition, the above-mentioned classification can be performed, for example, by using a cyclone or the like, and appropriately setting classification conditions.

(Purification of raw metal powder and raw material powder) As a transition metal-containing metal raw material powder (hereinafter, simply referred to as "metal raw material powder") that can be used in the above process B, and a raw material powder containing atom A (hereinafter, simply It is called "raw material powder".) There is no particular limitation, but high purity is preferred. The content of the transition metal in the metal raw material powder is not particularly limited, but 99.99% or more is preferable, and 99.999% or more is more preferable. In addition, the content of atom A in the raw material powder is also the same.

The metal raw material powder and/or raw material powder may contain the desired transition metal and/or atoms other than atom A as impurities. Examples of impurities contained in the metal raw material powder include boron, aluminum, silicon, manganese, iron, nickel, and silver. In addition, as the impurities contained in the raw material powder, metal elements and the like can be mentioned.

In the above composition, the effect of the present invention is exhibited by setting the content of atom A in the metal nitride-containing particles to 0.00005 to 10% by mass. Therefore, if the metal raw material powder and/or raw material powder contains the above-mentioned unexpected impurities, it is difficult to control the content of atom A within a predetermined range, and it becomes difficult to obtain the effects of the present invention. Therefore, the method for manufacturing the metal nitride-containing particles may include the following process A0 before the process B (when the process A2 is included, it is before the process A2). Process A0: A process for removing impurities from metal raw material powder and/or raw material powder.

・Process A0 In process A0, the method of removing impurities from raw metal powder and/or raw material powder (separation and purification method) is not particularly limited. For example, for niobium, paragraph 0013 of JP 2012-211048 A can be used The method described in ~0030 can also be used for other raw metal powders and/or raw material powders according to the method.

(Coating of metal nitride-containing particles) The above-mentioned metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, it may be a metal nitride-coated particle having a metal nitride-containing particle and a coating layer formed of an inorganic compound coating the metal-nitride-containing particle. The above composition containing metal nitride-containing particles coated with an inorganic compound has more excellent dispersion stability. The inorganic compound is not particularly limited, and includes oxides such as SiO ₂ , ZrO ₂ , TiO ₂ , GeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , and P ₂ O ₅ , aluminum hydroxide, and hydroxide Hydroxides such as zirconium. Among them, aluminum hydroxide is preferred from the viewpoint of easy formation of a thinner coating film and easy formation of a coating film with a higher coverage rate. In addition, when it is intended to control the refractive index of the metal nitride-containing particles, silicon oxide is preferred as the low refractive index coating, and zirconium hydroxide is preferred as the high refractive index coating. The method for coating metal nitride-containing particles with an inorganic compound is not particularly limited, and it is preferable that the method for producing metal nitride-containing particles includes the following inorganic compound coating process.

・Inorganic compound coating process The inorganic compound coating process is a process in which the above-mentioned metal nitride-containing particles are coated with oxides and/or hydroxides. The coating method is not particularly limited. For example, the following wet coating method and the like can be mentioned.

As the first wet coating method, first, the above-mentioned metal nitride-containing particles and water are mixed to prepare a slurry. Next, the above slurry is reacted with a water-soluble compound (for example, sodium silicate) containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y, and P, by decantation After removing excess alkali ions by method and/or ion exchange resin, the slurry is dried to obtain oxide-coated metal nitride-containing particles.

As a second wet coating method, first, the above-mentioned metal nitride-containing particles and an organic solvent such as alcohol are mixed to prepare a slurry. Next, an organometallic compound such as alkoxide containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y, and P is generated in the slurry, and the slurry is fired at a high temperature. If the above-mentioned slurry is fired at a high temperature, a sol-gel reaction proceeds, and metal nitride-containing particles coated with an oxide can be obtained.

As a third wet coating method, in the presence of metal nitride-containing particles, urea and aluminum chloride are used to form a slurry containing an ionic liquid. The metal nitride-containing particles are taken out from the slurry and dried. After that, the above-mentioned metal-nitride-containing particles are fired to obtain metal-nitride-containing particles coated with a hydroxide containing aluminum hydroxide. .

<Physical properties of metal nitride-containing particles> (Conductivity) The electrical conductivity of the metal nitride-containing particles is not particularly limited. 100×10 ⁴ to 600×10 ⁴ S/m is preferable, and 165×10 ⁴ to 340×10 ⁴ S/m is more preferable, 165×10 ⁴ S/m to 220×10 ⁴ S/m is still more preferable, and 170 to 190×10 ⁴ S/m is particularly preferable. If the lower limit value of the conductivity of the metal nitride-containing particles is 165×10 ⁴ S/m or more, and the upper limit value is 340×10 ⁴ S/m or less, the composition will be obtained by containing the metal nitride-containing particles The obtained cured film has more excellent light-shielding properties, and has excellent electrode corrosion resistance. In addition, in this specification, the electrical conductivity means the electrical conductivity measured by the following method using the powder resistance measurement system MCP-PD51 manufactured by Mitsubishi Chemical Analytech CO., LTD. First, a predetermined amount of metal nitride-containing particles is put into the measurement container of the above-mentioned measuring device, and then pressurization is started, and the pressure is changed to 0 kN, 1 kN, 5 kN, 10 kN, and 20 kN to measure the volume resistivity (ρ) of the particles. From the measurement result, the saturated volume resistivity under the condition that the volume resistivity is not affected by pressure is obtained, and the conductivity (σ) is calculated according to the relationship of σ=1/ρ using the obtained saturated volume resistivity. In addition, the above-mentioned test was carried out at room temperature.

(Average Primary Particle Size) The average primary particle size of the metal nitride-containing particles is not particularly limited, and is preferably 10 to 50 nm, more preferably 10 to 30 nm, and even more preferably 10 to 27 nm. If the average primary particle size is 27 nm or less, in a composition containing metal nitride-containing particles, the metal nitride-containing particles become less likely to precipitate, and as a result, the composition has more excellent stability over time. In addition, in this specification, the average primary particle diameter means the average particle diameter of primary particles, and the average primary particle diameter means the average primary particle diameter measured by the following method. Sample: A dispersion liquid (25% by mass of metal nitride-containing particles, 7.5% by mass of dispersant, PGMEA; 67.5% by mass of propylene glycol monomethyl ether acetate solvent) was prepared by the method described in the following examples. After the obtained dispersion is diluted 100 times, it is dropped on the carbon foil and dried. In addition, as the dispersing agent, a dispersing agent that disperses the metal nitride containing example to the extent that the primary particles of the metal nitride-containing particles can be recognized in the image obtained by the following method is used. As a specific example of the above-mentioned dispersing agent, the dispersing agents described in the examples can be given. In addition, the primary particle refers to an independent particle without agglomeration. Using a transmission electron microscope (TEM: Transmission Electron Microscope), the sample was observed at a magnification of 20,000 times to obtain an image. Among the metal nitride-containing particles in the obtained image, a primary particle is selected, and the area of the above-mentioned primary particle is calculated by image processing. Next, calculate the diameter when the obtained area is converted into a circle. This operation was performed on the primary particles of a total of 400 metal nitride-containing particles with 4 fields of view, and the diameter converted into a circle to be evaluated was arithmetic averaged as the average primary particle size of the metal nitride-containing particles.

[Solvent] The above composition preferably contains a solvent. Examples of the solvent include water and organic solvents. Among them, it is preferable that the above-mentioned composition contains an organic solvent.

<Organic solvent> The organic solvent is not particularly limited. Examples include acetone, methyl ethyl ketone, cyclohexane, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene diethyl ketone. Alcohol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene two Alcohol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene two Alcohol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, two Methyl sulfenite, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate, etc.

The above composition may contain one organic solvent or two or more organic solvents. From the viewpoint of suppressing the variation in the particle size of the metal nitride-containing particles when the composition is adjusted, it contains two or more organic solvents. Solvents are preferred. When two or more organic solvents are contained, it is selected from the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol Two or more types in the group consisting of monomethyl ether and propylene glycol monomethyl ether acetate are preferable.

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

<Water> The above composition may contain water. Water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the above-mentioned composition. The content of water relative to the total mass of the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.1% by mass or more, more preferably 1% by mass or less, and more preferably 0.8% by mass or less , 0.7% by mass or less is more preferable. When the water content is within the above range, the occurrence of pinholes when the cured film is produced is suppressed, and the moisture resistance of the cured film is improved. In addition, if the water content is within the above range, the particles contained in the composition tend to become fewer.

When the composition further contains a solvent, the solid content of the composition is preferably 10 to 40% by mass. If the solid content of the composition is equal to or less than the upper limit, the number of particles contained in the composition tends to decrease. In addition, if the solid content of the composition is equal to or greater than the lower limit, the composition has more excellent coatability. In addition, the content of the metal nitride-containing particles is preferably 20 to 70% by mass relative to the total solid content of the composition. If the content of the metal nitride-containing particles is more than the lower limit, the composition has more excellent stability over time. In addition, if the content of the metal nitride-containing particles is less than the upper limit, the number of particles contained in the composition is likely to be reduced, and a composition capable of producing a cured film with more excellent resolution can be obtained.

[Dispersant] The above composition preferably contains a dispersant. The dispersant contributes to improving the dispersibility of black pigments such as the aforementioned metal nitride-containing particles. In this specification, the dispersant is a different component from the binder resin described later. As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Among them, polymer compounds are preferred. As the dispersant, a polymer dispersant [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, Modified poly(meth)acrylate, (meth)acrylic acid copolymer, formalin naphthalenesulfonate condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine and pigment derivatives, etc. Polymer compounds can be further classified into linear polymers, end-modified polymers, grafted polymers, and block polymers according to their structures.

<Polymer compound> The polymer compound is adsorbed on black pigments, which are a preferred form of metal nitride-containing particles, and pigments that are used as needed (hereinafter, also simply referred to as "black pigments, etc.") to be dispersed The surface of the dispersion prevents the re-agglomeration of the dispersed body. Therefore, terminal-modified polymers, graft-type polymers, and block-type polymers containing fixed sites on the surface of the pigment are preferred. On the other hand, by modifying the surface of the metal nitride-containing particles, it is also possible to promote the adsorbability of the polymer compound to the metal nitride-containing particles.

The polymer compound preferably contains a structural unit including a graft chain. In addition, in this specification, "structural unit" has the same meaning as "repeating unit". The polymer compound containing the structural unit containing the graft chain has affinity with the solvent through the graft chain, so it is the dispersibility of black pigments and other colored pigments and the dispersion stability after time (stability with time) Outstanding person. In addition, the presence of the graft chain allows the polymer compound containing the structural unit including the graft chain to have affinity with the polymerizable compound or other usable resins. As a result, residues are less likely to be generated during alkali development. If the graft chain becomes longer, the steric repulsion effect is improved and the dispersibility of black pigments and the like is improved. On the other hand, if the graft chain is too long, the adsorption power to color pigments such as black pigments will decrease, and the dispersibility of black pigments and the like will tend to decrease. Therefore, the graft chain is preferably 40 to 10,000 atoms other than hydrogen atoms, more preferably 50 to 2000 atoms other than hydrogen atoms, and more preferably 60 to 500 atoms other than hydrogen atoms. good. Wherein, the graft chain means the root of the main chain of the copolymer (atoms bonded to the main chain from the group branched from the main chain) to the end of the group branched from the main chain.

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

The macromonomer containing this kind of graft chain is not particularly limited, and a macromonomer containing a reactive double bond group can be suitably used.

Corresponding to the structural unit containing the graft chain contained in the polymer compound, as a commercially available macromonomer suitable for synthesizing polymer compounds, AA-6 (trade name, TOAGOSEI CO., LTD.), AA can be used -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 (product 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, TOAGOSEI CO., LTD.), AK-32 (trade name, TOAGOSEI CO., LTD.), Blemmer PP-100 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-500 (trade name, NOF CORPORATION. Manufacturing), Blemmer PP-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-1000 (trade name, manufactured by NOF CORPORATION.), Blemmer 55-PET-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PME- 4000 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-400 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-1300 (trade name, manufactured by NOF CORPORATION.), Blemmer 43PAPE-600B (trade name, NOF CORPORATION. Manufacturing) and so on. 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 used , AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.), etc. are preferred .

The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyesters. It is more preferable that the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. It is more preferable that the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, polycaprolactone, and polyvalerolactone. The dispersant may contain the above-mentioned structure in one dispersant alone, or may contain a plurality of these structures in one dispersant. Among them, the polycaprolactone structure refers to a structure containing a ring-opening structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opening structure for δ-valerolactone as a repeating unit. As a specific example of the dispersing agent containing a polycaprolactone structure, j and k in the following formula (1) and following formula (2) are mentioned. In addition, as a specific example of the dispersant containing a polyvalerolactone structure, those in which j and k are 4 in the following formula (1) and the following formula (2) can be given. As a specific example of the dispersant containing a polymethyl acrylate structure, in the following formula (4), X ⁵ is a hydrogen atom, and R ⁴ is a methyl group. In addition, as a specific example of the dispersant containing a polymethyl methacrylate structure, X ⁵ in the following formula (4) is a methyl group and R ⁴ is a methyl group.

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

[Chemical formula 1]

In formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. Preferably, W ¹ , W ² , W ³ and W ⁴ are oxygen atoms. In formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. As X ¹ , X ² , X ³ , X ⁴ and X ⁵ , from the viewpoint of restriction on synthesis, each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms) is preferred , Each independently being a hydrogen atom or a methyl group is more preferred, and a methyl group is even more preferred.

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

[Chemical formula 2]

In formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited. Specifically, it includes an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an arylene sulfide group, and a heteroarylene sulfide group. And amine groups and so on. Among these, as ^{the organic groups represented by Z 1} , Z ² , Z ³ and Z ⁴ , especially from the viewpoint of improving dispersibility, those having a steric repulsive effect are preferred, and each independently has a carbon number of 5 to The alkyl group or alkoxy group of 24 is preferred, wherein each independently is 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. Kie is better. In addition, the alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic.

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

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

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

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

[Chemical formula 3]

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

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

[Chemical formula 4]

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

As the structural unit containing the graft chain, the polymer compound preferably contains the structural unit represented by formula (1A).

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

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

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

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

logP represents the common logarithm of the partition coefficient P (Partition Coefficient), which is a quantitative value that represents the physical property value of how a certain organic compound is distributed in the two-phase equilibrium of oil (usually 1-octanol) and water, as follows式 expression. logP=log(Coil/Cwater) In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase. If the value of logP sandwiches 0 and increases in the positive direction (plus), it means that the oil solubility increases. If the absolute value (minus) increases in the negative direction, it means that the water solubility increases, which is negatively correlated with the water solubility of organic compounds. It is widely used to estimate the hydrophilic and hydrophobic parameters of organic compounds.

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

[Chemical formula 5]

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

L is a single bond or a divalent linking group. Examples of the divalent linking group include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), divalent Aromatic groups (for example, aryl group, substituted aryl group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted arylene group An amino group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl group (-CO-), a combination of these, and the like.

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

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

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

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

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

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group also includes a ring assembly hydrocarbyl group and a cross-linked cyclic hydrocarbyl group, and examples of the ring assembly hydrocarbyl group include bicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. As the crosslinked cyclic hydrocarbon ring, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2 ]Octane ring, bicyclic [3.2.1] octane ring, etc.) and other 2-cyclic hydrocarbon rings; homobredane, adamantane, tricyclic [5.2.1.02,6] decane, tricyclic [4.3. 1.12,5] Undecane ring and other 3-cyclic hydrocarbon ring; tetracyclic [4.4.0.12,5.17,10] dodecane, perhydro-1,4-methylene-5,8-methylene naphthalene ring Etc. 4-cyclic hydrocarbon ring and so on. In addition, the cross-linked cyclic hydrocarbon ring also includes a fused-ring hydrocarbon ring, such as perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydronaphthalene The condensed ring is a condensed ring of 5-8 member cycloalkane rings. Compared with unsaturated aliphatic groups, aliphatic groups are preferably saturated aliphatic groups. In addition, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

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

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

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

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

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

In the polymer compound, the hydrophobic structural unit is calculated in terms of mass, and it is preferably contained in the range of 10 to 90%, and more preferably contained in the range of 20 to 80% relative to the total mass of the polymer compound. The content in the above range can achieve sufficient pattern formation.

(Functional groups that can interact with black pigments, etc.) The polymer compound can introduce functional groups that can interact with colored pigments such as black pigments. Among them, the polymer compound preferably further includes a structural unit containing a functional group that can interact with color pigments such as black pigments. Examples of functional groups that can interact with color pigments such as black pigments include acid groups, basic groups, coordinating groups, and reactive functional groups. When a polymer compound has an acid group, a basic group, a coordination group or a reactive functional group, it contains a structural unit with an acid group, a structural unit with a basic group, a structural unit with a coordination group, or It is preferable to include reactive structural units. In particular, the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, whereby the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound that serves as a dispersant that contributes to the dispersion of color pigments such as black pigments in the above-mentioned composition contains alkali-solubility. A composition containing this type of polymer compound has an excellent light-shielding property of the exposed portion, and the alkali developability of the unexposed portion is improved. In addition, since the polymer compound contains a structural unit containing an acid group, the polymer compound becomes easy to integrate with the solvent and the coating properties are also improved. It is presumed that this is because the acid group in the structural unit containing the acid group easily interacts with color pigments such as black pigments, and the polymer compound makes the color pigments such as black pigments stably disperse and disperses the color pigments such as black pigments. The viscosity becomes lower, and the polymer compound itself is easily dispersed stably.

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

As a functional group that can interact with color pigments such as black pigments, that is, acid groups, for example, there are carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, or phenolic hydroxyl groups. At least one of carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups One type is preferable, and the carboxylic acid group is more preferable from the viewpoint of good adsorption power of color pigments such as black pigments and higher dispersibility of the color pigments. That is, the polymer compound preferably further includes a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one type or two or more types of structural units containing acid groups. The polymer compound may or may not contain structural units containing acid groups, but when it contains, the content of structural units containing acid groups is calculated by mass. Relative to the total mass of the polymer compound, 5 to 80% is preferred. From the viewpoint of suppressing damage to the image strength based on alkali development, 10 to 60% is more preferable.

Functional groups that can interact with color pigments such as black pigments, that is, basic groups, include, for example, first-level amino groups, second-level amino groups, third-level amino groups, heterocycles containing N atoms, and amide groups. For example, from the viewpoint of good adsorption force for color pigments such as black pigments and high dispersibility of the color pigments, a tertiary amino group is preferred. The polymer compound can contain one kind or two or more kinds of these basic groups. The polymer compound may or may not contain a structural unit containing a basic group, but when it contains, the content of the structural unit containing a basic group is calculated by mass, relative to the total mass of the polymer compound, 0.01% or more and 50% or less Preferably, it is more preferably 0.01% or more and 30% or less from the viewpoint of suppressing the hindrance of developability.

As the functional group that can interact with color pigments such as black pigments, that is, coordination groups and reactive functional groups, for example, acetylacetoxy, trialkoxysilyl, isocyanate, Acid anhydride and chlorinated acid etc. From the viewpoints of good adsorption force for color pigments such as black pigments and high dispersibility of the color pigments, the acetylacetoxy group is preferred. The polymer compound may have one kind or two or more kinds of these groups. The polymer compound may contain a structural unit containing a coordination group or a structural unit containing a reactive functional group, or not, but when it contains, the content of these structural units is calculated by mass, relative to the total polymer compound The quality is preferably 10% or more and 80% or less, and from the viewpoint of inhibiting the developmental property from being inhibited, 20% or more and 60% or less is more preferable.

When the above-mentioned polymer compound contains a functional group capable of interacting with black pigments and other coloring pigments in addition to the graft chain, it is sufficient to contain the above-mentioned various functional groups capable of interacting with coloring pigments such as black pigments, and it is not particularly limited. How these functional groups are introduced, it is preferable that the polymer compound contains one or more structural units selected from structural units derived from monomers represented by the following general formulas (iv) to (vi).

[Chemical formula 6]

In general formula (iv) to general formula (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 the number of carbon atoms is 1 to 6 alkyl groups (for example, methyl, ethyl, propyl, etc.). In general formula (iv) to general formula (vi), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently is a hydrogen atom or methyl group. The base is better. In the 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 an oxygen atom is preferred. In addition, Y in the general formula (v) represents a methine group or a nitrogen atom.

_{In addition, L 1 in} general formula (iv) to general formula (v) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), 2 Valence aromatic groups (for example, aryl and substituted aryl groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imine bond (-NR ³¹ '-, wherein, R ^31' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and the like, and combinations of the these.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. Compared with an unsaturated aliphatic group, the aliphatic group is preferably a saturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

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

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

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

In general formula (iv) to general formula (vi), Z ₁ represents a functional group other than the graft chain that can interact with color pigments such as black pigments. Carboxylic acid groups and tertiary amino groups are preferred. Carboxylic acid groups For better.

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

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

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

From the viewpoints of interaction with black pigments and other colored pigments, stability over time, and permeability to developing solutions, the content of structural units containing functional groups that can interact with colored pigments such as black pigments is relative to that of macromolecules. The total mass of the compound is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and more preferably 10% by mass to 70% by mass.

(Other structural units) Moreover, in order to improve various properties such as image intensity, the polymer compound can further contain a structural unit containing a graft chain, a hydrophobic structural unit, and a structural unit that can be combined with black without compromising the effect of the present invention. Colored pigments such as pigments have different structural units that form functional groups that interact with each other, and other structural units that contain various functions (for example, structural units that have functional groups that have affinity with the dispersion medium used for the dispersion). Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles. The polymer compound can use one or more of these other structural units, and the content is calculated by mass. Relative to the total mass of the polymer compound, 0% or more and 80% or less is preferred, 10% or more and 60% The following is particularly good. The content can maintain sufficient pattern formability within the above-mentioned range.

(Physical properties of the polymer compound) The acid value of the polymer compound is preferably in the range of 0 mgKOH/g or more and 160 mgKOH/g or less, more preferably in the range of 10 mgKOH/g or more and 140 mgKOH/g or less, 20 mgKOH/g or more and 120 mgKOH The range of /g or less is more preferable. If the acid value of the polymer compound is 160 mgKOH/g or less, it is more effective to suppress pattern peeling during development when the cured film is formed. In addition, when the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability is more favorable. In addition, if the acid value of the polymer compound is 20 mgKOH/g or more, the precipitation of color pigments such as black pigments can be more suppressed, the number of coarse particles can be reduced, and the stability of the composition over time can be further improved.

The acid value of the polymer compound can be calculated from the average content of acid groups in the polymer compound, for example. In addition, it is possible to obtain a resin having a desired acid value by changing the content of the structural unit of the acid group, which is the constituent component of the polymer compound.

When the cured film is formed, the weight average molecular weight of the polymer compound is taken as a polystyrene conversion value based on the GPC (Gel Permeation Chromatography) method from the viewpoint of suppression of pattern peeling during development and developability. 4,000 or more and 300,000 or less are preferably, more preferably 5,000 or more and 200,000 or less, more preferably 6,000 or more and 100,000 or less, and particularly preferably 10,000 or more and 50,000 or less. The GPC method is based on the following method: HLC-8020GPC (manufactured by TOSOH CORPORATION), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID×15cm) as the column, and THF ( Tetrahydrofuran).

The polymer compound can be synthesized according to a known method. As a solvent used in the synthesis of polymer compound, for example, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethyl Methyl methamide, N,N-dimethyl acetamide, dimethyl sulfide, toluene, ethyl acetate, methyl lactate, ethyl lactate, etc. These solvents may be used alone or in mixture of two or more kinds.

Specific examples of polymer compounds include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., "Disperbyk-101 (polyamide amine phosphate) manufactured by BYK Chemie, 107 (carboxylate), 110 (containing Acid-based copolymer), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", EFKA 4047, 4050-4010-4165 (polyurethane series), EFKA 4330-4340 (block copolymer), 4400-4402 (modified poly Acrylate), 5010 (polyamide ester), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", Ajinomoto Fine- "AJISPER PB821, PB822, PB880, PB881" manufactured by Techno Co., Inc., "FLOREN TG-710 (urethane oligomer)" manufactured by KYOEISHA CHEMICAL Co., LTD., "Polyflow No.50E, No .300 (acrylic copolymer)", manufactured by Kusumoto Chemicals, Ltd. "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725", Kao Corporation "DEMOL RN, N (formalin naphthalenesulfonate condensation polymer), MS, C, SN-B (aromatic sulfonate formalin condensation polymer)", "HOMOGENOL L- 18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)", "ACETAMIN 86 (stearyl amine acetate)", "SOLSPERSE 5000 manufactured by The Lubrinzol corporation" (Phthalocyanine derivatives), 22000 (Azo pigment derivatives), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymers with functional parts at the end), 24000, 28000, 32000, 38500 (graft copolymer)", "Nikkor T106 (polyoxyethylene sorbitol monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikkol Chemicals CO., LTD., Kawaken Fine Ch Emicals CO., LTD. manufactures HINOAKUTO T-8000E, etc., Shin-Etsu Chemical Co., Ltd. manufactures polyorganosiloxane polymer KP341, Yusho Co Ltd manufactures "W001: cationic surfactant", polyoxygen Ethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Nonionic surfactants such as distearate and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, and W017", "EFKA-46, EFKA-47" manufactured by MORISHITA & CO., LTD. , EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" and other polymers manufactured by SAN NOPCO LIMITED Dispersant, "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION and Sanyo Chemical "Ionet (trade name) S-20" manufactured by Industries, Ltd., etc. In addition, Acrylic base FFS-6752, Acrylic base FFS-187, Akurikyua-RD-F8, and Cyclomer P can also be used. In addition, as commercial products of amphoteric resins, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, manufactured by BYK Additives & Instruments DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822 and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. etc. These polymer compounds may be used alone or in combination of two or more kinds.

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

In addition, as the dispersant, in addition to the above-mentioned polymer compounds, the graft copolymers of paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 of US2011/0124824) of JP 2010-106268 A can also be used. These contents can be cited and introduced into this manual. In addition to the above, paragraphs 0028 to 084 of JP 2011-153283 (corresponding to paragraphs 0075 to 0133 of US2011/0279759) containing side chain structures containing acidic groups bonded via linking groups can also be used. The content of the polymer compound of the constituent components can be cited and incorporated into this specification.

When the composition contains a dispersant, the content of the dispersant relative to the total solid content of the composition is preferably 0.1-50% by mass, more preferably 0.5-30% by mass. One type of dispersant may be used alone, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above-mentioned range.

In the composition, the mass ratio of the dispersant to the metal nitride-containing particles (that is, (the content of the dispersant in the composition)/(the content of the metal nitride-containing particles in the composition), Hereinafter, it is also referred to as "D/P".) It is preferably 0.05 to 0.30, more preferably 0.10 to 0.30, and even more preferably 0.12 to 0.30. If the above-mentioned D/P is 0.30 or less, the cured film formed of the above-mentioned composition has more excellent resolution. If the above D/P is 0.05 or more, the above composition has more excellent stability over time.

In the above composition, the lower limit of the mass ratio of the dispersant relative to the atom A (that is, (the content of the dispersant in the composition)/(the content of Fe atoms in the composition)) is 0.8 or more Preferably, 1.0 or more is more preferable, and 1.5 or more is even more preferable. The upper limit is preferably 270 or less, more preferably 150 or less, and even more preferably 50 or less. Since the mass ratio of the dispersant to the atom A is within the above range, the above composition has a more excellent effect of the present invention. In particular, since the above-mentioned mass ratio is in the range of 1.5-50, the above-mentioned composition has a further excellent effect of the present invention. Although the reason is not clear, it is thought that the atom A in the composition interacts with the dispersant, thereby affecting the patterning properties (curability and resolution).

In the above-mentioned composition, the lower limit of the mass ratio of the following polymerizable compound to the above-mentioned atom A (that is, (the content of the polymerizable compound in the composition)/(the content of the atom A in the composition)) is 0.7 or more is preferable, 0.85 or more is more preferable, and 1.0 or more is still more preferable. The upper limit is preferably 50 or less, more preferably 11 or less, and even more preferably 7.0 or less. When the mass ratio of the polymerizable compound to the atom A is within the above range, the composition has a more excellent effect of the present invention. When the above-mentioned content ratio is in the range of 1.0 to 7.0, the composition has more excellent effects of the present invention. Although the reason is not clear, it is thought that the atom A in the composition interacts with the polymerizable compound and thereby affects the patterning properties (curability and resolution).

[Binder Resin] The above composition preferably contains a binder resin. As the binder resin, it is preferable to use a linear organic polymer. As such linear organic polymers, known ones can be used arbitrarily. In order to realize water development or weak alkaline water development, it is better to select linear organic polymers that are soluble or swellable to water or weak alkaline water. Among them, as the binder resin, alkali-soluble resins (resins containing groups that promote alkali solubility) are particularly preferred. As a binding resin, it can contain at least one group that promotes alkali solubility from a linear organic polymer and a molecule (preferably a molecule with a (meth)acrylic copolymer or a styrene copolymer as the main chain) The alkali-soluble resin is appropriately selected. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic acid/(meth)acrylic acid resins Amine copolymer resins, epoxy resins, and polyimide resins are preferred. From the viewpoint of developability control, (meth)acrylic resin, (meth)acrylamide resin, (meth)acrylic acid /(Meth)acrylamide copolymer resin and polyimide resin are more preferable. Examples of groups that promote alkali solubility (hereinafter, also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. Among them, those that are soluble in organic solvents and can be developed by weakly alkaline aqueous solutions are preferred, and more preferred include alkali-soluble resins containing structural units derived from (meth)acrylic acid. There may be only one type of these acid groups, or two or more types.

As the binder resin, for example, a radical polymer containing a carboxylic acid group in the side chain can be cited. As a radical polymer containing a carboxylic acid group in the side chain, for example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957 No., Japanese Patent Application Publication No. 54-92723, Japanese Patent Application Publication No. 59-53836, and Japanese Patent Application Publication No. 59-71048. As a radical polymer containing a carboxylic acid group in the side chain, there can be mentioned the acid anhydride unit obtained by hydrolyzing the monomer containing the carboxylic acid group alone or by copolymerizing it, and the monomer containing acid anhydride alone or by copolymerizing it. , Semi-esterified or semi-aminated resin and epoxy acrylate modified by unsaturated monocarboxylic acid and acid anhydride. Examples of monomers containing carboxylic acid groups include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like. In addition, an acidic cellulose derivative containing a carboxylic acid group in the side chain can also be cited as an example. Examples of monomers containing acid anhydride include maleic anhydride. In addition, it is more useful to add cyclic anhydrides to polymers containing hydroxyl groups. In addition, acetal-modified polyvinyl alcohol-based binder resins containing acid groups are described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Laid-Open No. 2001-318463. The acid group-containing acetal-modified polyvinyl alcohol-based adhesive resin has an excellent balance of film strength and developability, which is preferable. Furthermore, as a water-soluble linear organic polymer, polyvinylpyrrolidone or polyethylene oxide is useful. In addition, in order to increase the strength of the cured film, polyethers, which are alcohol-soluble nylon and 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, which are the reactants, are also useful. In addition, the polyimide resin described in International Publication No. 2008/123097 is also useful.

In particular, among these, [benzyl (meth)acrylate/(meth)acrylic acid/other addition polymerizable vinyl monomers as necessary] copolymer and [(meth)allyl acrylate/(meth) ) Acrylic acid/other addition polymerizable vinyl monomers as required] The copolymer has excellent film strength, sensitivity, and developability in balance, which is preferred. As commercially available products, for example, Acrylic base FF-187, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.), Akurikiyua-RD-F8 (NIPPON SHOKUBAI CO., LTD.), and DAICEL-ALLNEX LTD. Manufacturing Cyclomer P (ACA) 230AA, etc.

In the production of the binder resin, for example, a method based on a known radical polymerization method can be applied. Those skilled in the art can easily set polymerization conditions such as the 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.

Moreover, as the binder resin, it is also preferable to use a polymer containing a structural unit containing a graft chain and a structural unit containing an acid group (alkali-soluble group). The definition of the structural unit containing the graft chain is the same as the structural unit containing the graft chain contained in the above-mentioned dispersant, and the preferred range is also the same. The acid group includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. At least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable.

<Structural unit containing an acid group> As a structural unit containing an acid group, one or more structural units selected from the structural units derived from the monomers represented by the following general formula (vii) to general formula (ix) are more good.

[Chemical formula 7]

In general formula (vii) to general formula (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 the number of carbon atoms is 1 to 6 alkyl groups (for example, methyl, ethyl, propyl, etc.). In general formula (vii) to general formula (ix), R ²¹ , R ²² and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently is a hydrogen atom or a methyl group. good. In the 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 an oxygen atom is preferred. In addition, Y in the general formula (viii) represents a methine group or a nitrogen atom.

_{In addition, L 2 in} general formula (vii) to general formula (ix) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), 2 Valence aromatic groups (for example, aryl and substituted aryl groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imine bond (-NR ⁴¹ '-, wherein, R ^41' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and the plurality of combinations.

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

The number of carbon atoms of the divalent aromatic group is preferably 6-20, more preferably 6-15, and most preferably 6-10. In addition, 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 the heterocyclic ring. One or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed on the heterocyclic ring. In addition, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR ⁴² , where R ⁴² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

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

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

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

As a monomer represented by the general formula (vii), R ²¹ , R ²² and R ²³ are each independently a hydrogen atom or a methyl group, L ₂ is an alkylene group or a divalent linking group containing an oxyalkylene structure, and X _{A compound in which 2} is an oxygen atom or an imino group, and Z ₂ is a carboxylic acid group is preferred. In addition, as a monomer represented by the general formula (vii), a compound in which R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is a methine group is preferable. Furthermore, as a monomer represented by the general formula (ix), compounds in which R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom or a methyl group, and Z ₂ is a carboxylic acid group are preferred.

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

The above-mentioned binder resin may have one or more structural units containing acid groups. The content of the acid group-containing structural unit is calculated by mass conversion, and is preferably 5-95% relative to the total mass of the above-mentioned binder resin. From the viewpoint of suppressing damage to the image strength due to alkali development, 10-95% is Better.

The content of the binder resin in the composition is preferably 0.1 to 30% by mass, and more preferably 0.3 to 25% by mass relative to the total solid content of the composition. One type of bonding resin can be used alone, or two or more types can be used. When two or more types are used, it is preferable that the total amount falls within the above-mentioned range.

The mass ratio of the binding resin to the metal nitride-containing particles (ie, (the content of the binding resin in the composition)/(the content of the metal oxide-containing particles in the composition)) is preferably 0.3 or less, 0.25 The following is more preferable, and 0.20 or less is even more preferable. In addition, the lower limit is not particularly limited, but it is usually 0.01 or more, preferably 0.02 or more, and more preferably 0.07 or more. If the upper limit value is 0.25 or less, the composition has more excellent stability over time, and if it is 0.014 or more, the cured film obtained by using the composition has more excellent resolution.

[Polymerizable compound] The above composition preferably contains a polymerizable compound. The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bond-containing groups, more preferably two or more compounds, more preferably three or more, and more preferably five or more groups. The upper limit is, for example, 15 or less. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.

The polymerizable compound may be any of chemical forms such as monomers, prepolymers, oligomers, mixtures of these, and polymers of these, for example. Monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000, more preferably 250 to 1500. The polymerizable compound is preferably a 3 to 15 functional (meth)acrylate compound, and a 3 to 6 functional (meth)acrylate compound is more preferable. Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides. And these polymers, esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and these polymers are preferred. In addition, addition reactants of unsaturated carboxylic acid esters containing nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups, or addition reactants of amides and monofunctional or polyfunctional isocyanates or epoxy groups and the above-mentioned non- Dehydration condensation reaction product of saturated carboxylic acid ester or amides and monofunctional or polyfunctional carboxylic acid, etc. In addition, reaction products of unsaturated carboxylic acid esters or amides containing electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and mercaptans, halogen groups or toluene Unsaturated carboxylic acid esters with discrete substituents such as sulfonyl groups or reactants of amides and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, in place of the above-mentioned unsaturated carboxylic acids, styrene derivatives such as unsaturated phosphonic acid and styrene, and compound groups substituted with vinyl ethers, allyl ethers, and the like can also be used. As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP 2009-288705 A can also be suitably used in the present invention.

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

As the polymerizable compound, dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku CO., LTD.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku CO., LTD.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku CO., LTD.), dipentaerythritol hexa(meth)acrylate (as a commercial product) For sale, KAYARAD DPHA; manufactured by Nippon Kayaku CO., LTD., A-DPH-12E; manufactured by Shin-Nakamura Chemical CO., LTD), and these (meth)acrylic groups are through ethylene glycol residues and propylene glycol residues. The base structure (for example, SR454 and SR499 commercially available from Sartomer company Inc.) 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.), etc. can also be used. The state of the preferable polymerizable compound is shown below.

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

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

Regarding the polymerizable compound, a compound containing a caprolactone structure is also preferred. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. For example, it can be exemplified by using trimethylolethane, ditrimethylolethane, and trimethylolethane. Methylpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine and other polyols are obtained by esterification with (meth)acrylic acid and ε-caprolactone , Ε-caprolactone modified multifunctional (meth)acrylate. Among them, compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.

[Chemical formula 8]

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

[Chemical formula 9]

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

[Chemical formula 10]

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

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

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

[Chemical formula 11]

In general formulas (Z-4) and (Z-5), E independently represents -((CH ₂ ) _y CH ₂ O)-, or -((CH ₂ ) _y CH(CH ₃ )O)-, y each independently represents an integer of 0-10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group. In the general formula (Z-4), the total of (meth)acrylic groups is 3 or 4, m each independently represents an integer of 0-10, and the total of each m is an integer of 0-40. In general formula (Z-5), the total of (meth)acrylic groups is 5 or 6, n each independently represents an integer of 0-10, and the total of each n is an integer of 0-60.

In the general formula (Z-4), m is preferably an integer of 0-6, and more preferably an integer of 0-4. In addition, it is preferable that the total of each m is an integer of 2 to 40, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is more preferable. In general formula (Z-5), n is preferably an integer of 0-6, and more preferably an integer of 0-4. Furthermore, it is preferable that the total of each n is an integer of 3-60, the integer of 3-24 is more preferable, and the integer of 6-12 is more preferable. _{In addition, -((CH 2} ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in general formula (Z-4) or general formula (Z-5) is an oxygen atom The form in which the end of the side is bonded to X is preferred.

The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used singly, or two or more of them may be used. In particular, all the six Xs in the general formula (Z-5) are in the form of acryloyl groups, the compound in which all the six Xs in the general formula (Z-5) are acryloyl groups, and at least one of the six Xs The state of a mixture of compounds that are hydrogen atoms is preferred. With this structure, the developability can be further improved.

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

The compound represented by general formula (Z-4) or general formula (Z-5) can be synthesized by the following process, which is a conventionally known process: by ring-opening addition reaction, ethylene oxide or propylene oxide is combined with A process in which pentaerythritol or dipentaerythritol is bonded to a ring-opening skeleton; and for example, a process in which (meth)acrylic acid chloride is reacted with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acrylic acid group. Each process is a well-known process, and those skilled in the art can easily synthesize the compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by general formula (Z-4) or general formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred. Specifically, compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as "exemplary compounds (a) to (f)") can be given, and among them, the exemplified compounds (a) and (b) ), (e), (f) are better.

[Chemical formula 12]

[Chemical formula 13]

As commercially available products of polymerizable compounds represented by the general formulas (Z-4) and (Z-5), for example, SR-, a 4-functional acrylate containing 4 ethylene oxide chains manufactured by Sartomer Company Inc. can be mentioned. 494. The 6-functional acrylate containing 6 pentyleneoxy chains, namely DPCA-60, manufactured by Nippon Kayaku CO., LTD., and the trifunctional acrylate containing 3 isobutyleneoxy chains, namely TPA-330, etc. .

As a polymerizable compound, urethane acrylics described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765 Esters; amines containing ethylene oxide-based skeletons described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Carbamate compounds are also preferred. In addition, it is also possible to use JP-A 63-277653, JP-A 63-260909, and JP-A 1-105238, which contain an amine structure and/or sulfur in the molecule. Addition polymerizable compounds with ether structure to obtain a composition with very excellent photosensitive speed. Commercial products include 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-306T, UA-306I, AH-600, T-600 and AI-600 (manufactured by KYOEISHA CHEMICAL CO., LTD), etc.

In addition, the SP (Solubility Parameter) value of the polymerizable compound is preferably 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more. In addition, in this specification, the SP value is calculated by the Hoy method (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118) unless otherwise specified. In addition, the SP value is shown without the unit, but the unit is cal ^1/2 cm ^-3/2 .

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

General formula (Q3) [Chemical formula 14]

In the above general formula (Q3), Ar ¹¹ to Ar ¹⁴ each independently represent an aryl group containing a benzene ring surrounded by a dotted line. X ¹ to X ⁴ each independently represent a substituent containing 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 greater than or equal to 0, and the upper limits of e, f, g, and h are each that can be possessed ^{from Ar 11} to Ar ¹⁴ The number of substituents minus the value of a, b, c, or d. Wherein, when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the condensed rings, X ¹ to X ⁴ and R ¹ to R ⁴ may each independently be substituted with The benzene ring enclosed by the dotted line may be substituted with a ring other than the benzene ring enclosed by the dotted line.

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

In the above general formula (Q3), X ¹ to X ⁴ each independently represent a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. The ^{polymerizable group-containing substituent represented by X 1} to X ⁴ is not particularly limited, but an aliphatic group containing a polymerizable group is preferred. The aliphatic group having a ^{polymerizable group represented by X 1} to X ⁴ is not particularly limited, but an alkylene group having 1 to 12 carbon atoms other than the polymerizable group is preferred, and the number of carbon atoms is 2 The alkylene group of -10 is more preferable, and the alkylene group of 2 to 5 carbon atoms is more preferable. In addition, in ^{the aliphatic group containing the polymerizable group represented by X 1} to X ⁴ , when the aliphatic group is substituted with a hetero atom, it is replaced by -NR- (R is a substituent), an oxygen atom, and a sulfur atom. Jia, the aliphatic group of non-adjacent -CH ₂ - is substituted with an oxygen atom or a sulfur atom is more preferably the aliphatic group of non-adjacent -CH ₂ - is substituted with an oxygen atom is further preferred. The aliphatic group containing the polymerizable group represented by X ¹ to X ⁴ is preferably substituted by a heteroatom at 1 to 2 places, and it is more preferably substituted by a heteroatom at 1 place, and contains the ^{same as Ar 11} ～Ar ¹⁴ It is more preferable that one adjacent aryl group of the benzene ring surrounded by a dotted line is substituted with a heteroatom. As ^{the polymerizable group contained in the aliphatic group containing the polymerizable group represented by X 1} to X ⁴ , a polymerizable group capable of undergoing radical polymerization or cationic polymerization (hereinafter, also referred to as radical polymerizable group, respectively) Group and cationically polymerizable group) are preferred. As the radical polymerizable group, a generally known radical polymerizable group can be used. Preferably, a polymerizable group containing an ethylenically unsaturated bond capable of radical polymerization can be used. Specifically, Examples include vinyl groups, (meth)acryloxy groups, and the like. Among them, (meth)acryloxy is preferred, and acryloxy is more preferred. As the cationically polymerizable group, generally known cationically polymerizable groups can be used. Specifically, alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, and spiro Cycloorthoester group, vinyloxy group, etc. Among them, alicyclic ether groups and vinyloxy groups are preferred, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferred. The above-mentioned polymerizable groups contained in the substituents contained in Ar ¹ to Ar ^{4 are preferably radical polymerizable groups.} Ar ¹ ~ Ar ⁴ comprising two or more of the substituents containing the polymerizable group, Ar ¹ ~ Ar ⁴ is 2 to 4 comprising a substituent of the polymerizable group is preferred, Ar ¹ ~ Ar ⁴ in It is more preferable that two or three of the substituents contain a polymerizable group, and it is more preferable that two of Ar ¹ to Ar ⁴ contain a polymerizable group-containing substituent. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the condensed rings, X ¹ to X ⁴ may each independently be substituted with a benzene ring surrounded by a dotted line, or may be substituted It is a ring other than the benzene ring surrounded by a dotted line.

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

In the above general formula (Q3), R ¹ to R ⁴ each independently represent a substituent. The substituents represented by R ¹ to R ⁴ are not particularly limited. Examples include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, hydroxy groups, hydroxyalkyl groups, alkoxy groups, and aryl groups. , Heteroaryl, alicyclic, etc. The substituent represented by R ¹ to R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a phenyl group having 1 to 5 carbon atoms , Methyl, methoxy or phenyl is further preferred. In the above general formula (Q3), when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the condensed rings, R ¹ to R ⁴ may each independently be substituted with a dotted line The surrounding benzene ring may be substituted with a ring other than the benzene ring surrounded by a dotted line.

In the above general formula (Q3), e, f, g, and h each independently represent an integer of 0 or more, and the upper limit of e, f, g, and h is the number of substituents that can have ^{from Ar 11} to Ar ^{14 respectively} Subtract the value of a, b, c, or d. e, f, g, and h each independently are preferably 0-8, more preferably 0-2, 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 dotted line as one of the condensed rings, it is preferable that e, f, g, and h are 0 or 1, and 0 is more preferable.

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

The polymerizable compound containing the cardo skeleton is not limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD) and Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.).

When the composition contains a polymerizable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass relative to the total solid content of the composition. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The polymerizable compound may be one type alone, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above-mentioned range.

[Polymerization initiator] The above composition preferably contains a polymerization initiator. The polymerization initiator is not particularly limited, and can be appropriately selected from known polymerization initiators. For example, those having photosensitivity (so-called photopolymerization initiators) are preferred. When the above composition contains a photopolymerization initiator and the above polymerizable compound in addition to the metal nitride-containing particles, it is cured by irradiation with active light rays or radiation, so it is sometimes referred to as a "photosensitive composition." The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity from ultraviolet region to visible light. In addition, the polymerization initiator can be an active agent that has some effect with the photosensitizer excited by light and generates active free radicals, or it can be an initiator that initiates cationic polymerization according to the type of polymerizable compound. In addition, the photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 mol in the range of about 300 nm to 800 nm (more preferably, 330 nm to 500 nm).

As the photopolymerization initiator, for example, halogenated hydrocarbon derivatives (for example, those containing triazine skeletons, those containing oxadiazole skeletons, etc.), phosphine compounds such as phosphine oxides, hexaarylbisimidazole, Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, etc. Examples of halogenated hydrocarbon compounds containing triazine skeletons include compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in the specification of British Patent No. 1388492, and Japanese patents The compound described in Japanese Patent Publication No. 53-133428, the compound described in German Patent No. 3337024, the compound described in J. Org. Chem. based on FC Schaefer et al.; 29, 1527 (1964), and Japanese Patent Application Publication No. 62-58241 The compound described in the publication, the compound described in JP 5-281728, the compound described in JP 5-34920, the compound described in the specification of U.S. Patent No. 4212976, and the like.

Also, from the viewpoint of exposure sensitivity, it is selected from trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, Metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and Compounds in the group consisting of salts, halogenated methyl oxadiazole compounds and 3-aryl substituted coumarin compounds are preferred.

Trihalomethyl triazine compound, α-amino ketone compound, phosphine compound, phosphine oxide compound, oxime compound, triaryl imidazole dimer, onium compound, benzophenone compound or acetophenone compound are further Preferably, at least one compound selected from the group consisting of trihalomethyl triazine compound, α-amino ketone compound, oxime compound, triaryl imidazole dimer, and benzophenone compound is particularly preferred.

In particular, when producing a light-shielding film using the above-mentioned composition, it is necessary to form a fine pattern in a sharp shape. Therefore, together with the curability, it is important to develop the unexposed area without residue. From this viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when forming a fine pattern, step exposure is used in exposure for curing, but this exposure machine may be damaged by halogen, and it is also necessary to suppress the addition amount of the photopolymerization initiator to a low level. Therefore, considering these aspects, when forming a fine pattern, it is particularly preferable to use an oxime compound as a photopolymerization initiator. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP 2013-29760 A can be referred to, and this content is incorporated into the specification of this application.

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

(Oxime compound) As the photopolymerization initiator, an oxime compound (oxime-based initiator) can be more preferably used. In particular, the oxime compound has high sensitivity and high polymerization efficiency, can be cured regardless of the color material concentration, and the color material concentration can be easily designed to be high, which is preferable. As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-80068 A, or the compound described in JP 2006-342166 A can be used. As the oxime compound that can be preferably used in the present invention, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutane-2- Ketone, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane- 1-ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxy Carbonyloxyimino-1-phenylpropan-1-one and the like. In addition, JCSPerkin II (1979) pp.1653-1660), JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japan Compounds described in JP 2000-66385, JP 2000-80068, JP 2004-534797, and JP 2006-342166, compounds, etc. Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF Corporation), IRGACURE-OXE02 (manufactured by BASF Corporation), IRGACURE-OXE03 (manufactured by BASF Corporation), or IRGACURE-OXE04 (manufactured by BASF Corporation) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arkls NCI-831 and Adeka Arkls NCI-930 (manufactured by ADEKA CORPORATION) or N-1919 (containing carbazole·oxime ester skeleton light Starter (manufactured by ADEKA CORPORATION).

In addition, as oxime compounds other than those described above, there can be used: the compound described in Japanese Patent Application Publication No. 2009-519904 in which an oxime is linked to the N-position of a carbazole; and the US Patent No. The compound described in No. 7626957; the compound described in JP 2010-15025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into the pigment site; the ketone described in International Publication No. 2009-131189 An oxime compound; a compound described in US Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule; described in Japanese Patent Application Laid-Open No. 2009-221114, which has great absorption at 405 nm and good sensitivity to g-ray light sources The compound; etc. For example, it is better to refer to paragraphs 0274 to 0275 of JP 2013-29760 A, which content is incorporated into the specification of this application. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. In addition, the N-O bond of the oxime may be an oxime compound of the (E) body, or an oxime compound of the (Z) body, or a mixture of the (E) body and the (Z) body.

[Chemical formula 15]

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

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

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

[Chemical formula 16]

[Chemical formula 17]

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

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

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

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

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

Specific examples of oxime compounds that can be preferably used in the above composition are shown below.

[Chemical formula 18]

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and further preferably has a higher absorbance at 365 nm and 405 nm. Among the oxime compounds, from the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and more preferably 5,000 to 200,000. The molar absorptivity of the compound can be measured by a known method, for example, by an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), using an ethyl acetate solvent, preferably at a concentration of 0.01 g/L. The photopolymerization initiator can be used in combination of two or more types as required.

When the above composition contains a polymerization initiator, the content of the polymerization initiator relative to the total solid content in the composition is preferably 0.1-30% by mass, more preferably 1-25% by mass, and 1-10% by mass Further better. The said composition may contain only 1 type of polymerization initiator, and may contain 2 or more types. When two or more types are contained, the total amount thereof is preferably within the above-mentioned range.

[Other optional components] The above-mentioned composition may further contain the following optional components.

<Surfactant> The above-mentioned composition may contain various surfactants from the viewpoint of further improving coatability. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.

By including a fluorine-based surfactant in the above composition, the liquid characteristics (especially fluidity) when preparing the coating liquid are further improved, and the uniformity of the coating thickness and the liquid-saving property can be further improved. That is, when a film is formed using a coating liquid applied with a composition containing a fluorine-based surfactant, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is improved. The coatability to the coated surface is improved. Therefore, it is possible to better form a uniform thickness film with less uneven thickness.

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

Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, , Megafac F482, Megafac F554, Megafac F780, RS-72-K (above, manufactured by DIC CORPORATION), Fluorado FC430, Fluorado FC431, Fluorado FC171 (above, manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD. ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTIONS INC.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A can also be used. As the fluorine-based surfactant, a block polymer can also be used. As a specific example, for example, a compound described in JP 2011-89090 A can be cited. Fluorine-based surfactants can also preferably use the following fluorine-containing polymer compounds, which contain repeating units derived from (meth)acrylate compounds containing fluorine atoms and two or more (5 or more are preferred) ) Repeating units of (meth)acrylate compounds of alkoxyl groups (ethyleneoxy and propyleneoxy are preferred), and the following compounds are also exemplified as fluorine-based surfactants that can be used in the present invention.

[Chemical formula 19]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In addition, a fluorine-containing polymer containing an ethylenically unsaturated group in the side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965 A, such as Megafac RS-101, RS-102, RS-718K, RS-72 manufactured by DIC CORPORATION -K etc.

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

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

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

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

Surfactant may use only 1 type, and may combine 2 or more types. The content of the surfactant relative to the total solid content of the composition of the present invention is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass.

<Coloring agent> The above-mentioned composition may contain a coloring agent other than the metal nitride-containing particles (hereinafter, also simply referred to as "coloring agent"). The colorant is used, for example, to adjust the chromaticity of the composition, and it is possible to replace part of the metal nitride-containing particles with the colorant within a range where the OD (Optical Density) value does not decrease. Examples of such coloring agents include pigments (black organic pigments, colored organic pigments, and inorganic pigments), dyes, and the like.

(Pigment) There is no restriction|limiting in particular as a pigment, A well-known pigment can be used. Examples of color organic pigments include: Dye Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24 , 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77 , 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 , 126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171 , 172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 etc.; CI Pigment Orange 2,5,13,16,17 : 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 etc.; CI Pigment Red 1, 2, 3, 4 ,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2 , 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112 , 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200 , 202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279 etc.; CI Pigment Green 7,10,36,37,58 ,59 etc.; CI Pigment Violet 1,19,23,27,32,37,42 etc.; CI Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6 , 16, 22, 60, 64, 66, 79, 80 etc.

In addition, as a green pigment, it is also possible to use a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in the molecule. As a specific example, the compound described in International Publication No. 2015/118720 can be mentioned. These organic pigments can be used alone or in combination of plural kinds in order to improve color purity.

As the black pigment, various well-known black pigments can be used. For example, carbon black and/or black metal-containing organic pigments shown below can be cited. Examples of black metal-containing organic pigments include those containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Metal oxide. These can be used only 1 type, and can also be used as a mixture of 2 or more types. In addition, it can be prepared to have desired light-shielding properties by further combining inorganic pigments of other colors with black pigments. Examples of specific inorganic pigments that can be used in combination include zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitating barium sulfate and barite powder, lead red, oxide Iron red, chrome yellow, zinc yellow (1 zinc yellow, 2 zinc yellow), ultramarine blue, Prussian blue (potassium ferrocyanide) zircon gray, yellow yellow, chrome titanium yellow, chrome green, peacock, Victoria Green, iron blue (not related to Prussian blue), vanadium zirconium blue, chrome tin red, manganese red, orange red, etc. In particular, in order to express light-shielding properties in a wide wavelength range from ultraviolet to infrared, not only these black pigments or other colors can be used alone, but also plural kinds of pigments can be mixed and used.

The average primary particle size of the black pigment is preferably 5 nm or more, and more preferably 10 nm or more. From the same viewpoint, as the upper limit, 10 μm or less is preferable, 1 μm or less is more preferable, and 100 nm or less is more preferable. The average primary particle size of the black pigment means the average primary particle size measured by the same method as the average primary particle size of the metal nitride-containing particles.

(Dyes) As dyes, for example, Japanese Patent Application Publication No. 64-90403, Japanese Patent Application Publication No. 64-91102, Japanese Patent Application Publication No. 1-94301, Japanese Patent Application Publication No. 6-11614, Japanese Patent Publication No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5,669,920, U.S. Patent No. 505,950, Japanese Patent Application Publication No. 5-333207, Japanese Patent Application Publication No. 6-35183, Japanese Patent Application Publication No. 6-51115, and Japanese Patent The pigment disclosed in Kaihei 6-194828 Bulletin. If distinguished as a chemical structure, pyrazole azo compounds, pyrrole methylene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazole compounds can be used Azolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. In addition, as the dye, a dye multimer can be used. Examples of the dye multimer include compounds described in Japanese Patent Application Publication No. 2011-213925 and Japanese Patent Application Publication No. 2013-041097.

The above-mentioned composition may contain extender pigments as needed in addition to the colorant. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, hydrotalcite, and the like. These extender pigments can be used alone or in mixture of two or more kinds. The use amount of the extender pigment is usually 0-100 parts by mass relative to 100 parts by mass of the colorant, preferably 5-50 parts by mass, and more preferably 10-40 parts by mass. Colorants and extender pigments can be used by modifying their surfaces with polymers.

The coloring agent may be used singly, or two or more kinds may be used. As a coloring agent, coloring organic pigments, such as red, blue, yellow, green, and purple, can be contained. When using light-shielding pigments (specifically, metal nitride-containing particles) and coloring organic pigments, it is preferable to use 1-40% by mass of the coloring organic pigments relative to the light-shielding pigments. From the viewpoint of adjusting the color tone, a red pigment and a light-shielding pigment are preferable. Although not particularly limited, as the red pigment, Pigment Red 254 is preferable. In addition, from the viewpoint of improving light-shielding properties, yellow pigments and light-shielding pigments are preferred. Although not particularly limited, as the yellow pigment, Pigment Yellow 150 is preferred.

When the composition contains a coloring agent, the content of the coloring agent relative to the total solid content of the composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and more preferably 35 to 60% by mass.

<Pigment Derivatives> The above-mentioned composition can contain a pigment derivative. As the pigment derivative, for example, a compound having a structure in which a part of an organic pigment is substituted by an acidic group, a basic group, or a phthalic iminomethyl group. Examples of organic pigments used to form pigment derivatives include dioxopyrrolopyrrole-based pigments, azo-based pigments, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, and dioxazine-based pigments. , Perylene pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, Shilin pigments, metal complex pigments, etc. In addition, as the acidic group contained in the pigment derivative, a sulfonic acid group, a carboxylic acid group, and a quaternary ammonium salt group thereof are preferable, the carboxylic acid group and the sulfonic acid group are more preferable, and the sulfonic acid group is particularly preferable. As the basic group contained in the pigment derivative, an amine group is preferred, and a tertiary amine group is more preferred. As a specific example of a pigment derivative, the following compounds can be mentioned, for example. In addition, the description of paragraphs 0162 to 0183 of JP 2011-252065 A can be referred to, and this content is incorporated into this specification.

[Chemical formula 20]

When the above composition contains a pigment derivative, the content of the pigment derivative relative to the total mass of the colorant is preferably 1-30% by mass, and more preferably 3-20% by mass. The above-mentioned composition may contain only one type of pigment derivative, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably in the above-mentioned range.

<Silane coupling agent> Silane coupling agent refers to a compound containing a hydrolyzable group and other functional groups in the molecule. In addition, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond through a hydrolysis reaction and/or condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an alkoxy group, and an alkenoxy group. When the hydrolyzable group contains carbon atoms, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. An alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is particularly preferred. In addition, when the cured film is formed on the substrate, in order to improve the adhesion between the substrate and the cured film, the silane coupling agent does not contain fluorine atoms and silicon atoms (except for the silicon atoms bonded by hydrolyzable groups). Preferably, it does not contain fluorine atoms, silicon atoms (excluding silicon atoms bonded by hydrolyzable groups), alkylene groups substituted by silicon atoms, straight-chain alkyl groups with 8 or more carbon atoms, and 3 or more carbon atoms The branched alkyl group is preferred.

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

The silane coupling agent preferably contains one or more curable functional groups selected from the group consisting of (meth)acryloxy groups, epoxy groups, and oxetanyl groups. The hardenable functional group can be directly bonded to the silicon atom, or can be bonded to the silicon atom via a linking group. Moreover, as a preferable aspect of the curable functional group contained in the said silane coupling agent, a radical polymerizable group can also be mentioned.

The molecular weight of the silane coupling agent is not particularly limited. From the viewpoint of operability, it is often 100 to 1,000, preferably 270 or more, and more preferably 270 to 1,000.

As one of the preferred aspects of the silane coupling agent, a silane coupling agent X represented by the formula (W) can be cited. Formula (W) R _Z2 -Lz-Si-(R _Z1 ) ₃ R _z1 represents a hydrolyzable group, and is defined as described above. R _z2 represents a curable functional group, which is defined as described above, and the preferred range is also the same as described above. Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include an alkylene group substituted with a halogen atom, an aryl group substituted with a halogen atom, -NR ¹² -, -CONR ¹² -, -CO- , -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, -SO ₂ -or a combination of these. Among them, at least one selected from the group consisting of an alkylene group substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group substituted with a halogen atom having 6 to 12 carbon atoms, or includes these Group and at least 1 selected from the group consisting of -NR ¹² -, -CONR ¹² -, _{-CO-, -CO 2} -, SO ₂ NR ¹² -, -O-, -S- and SO _2- Combinations of these groups are preferred, including alkylene groups that can be substituted with a halogen atom having 2 to 10 carbon atoms, -CO ₂ -, -O- ^{, -CO-, -CONR 12} -or these groups The combination of groups is more preferable. Here, the above-mentioned R ¹² represents a hydrogen atom or a methyl group.

Examples of the silane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N -β-aminoethyl-γ-aminopropyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-tri Ethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd.) , Ltd. manufactures trade name KBM-503) and glycidoxy octyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd. manufactures trade name KBM-4803) and so on.

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

Silane coupling agent Y has at least one nitrogen atom in the molecule. The nitrogen atom is preferably in the form of a secondary or tertiary amino group, that is, the nitrogen atom contains at least one organic group as a substituent. Group is better. In addition, the structure of the amino group may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocyclic ring, or may exist as a substituted amino group such as aniline. Among them, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination of these. These may further have substituents. Examples of the substituents that can be introduced include silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, amino groups, and halogen atoms. , Sulfonamide group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkoxy ammonium group, alkyl ammonium group, carboxylic acid group or its salt, sulfo group, etc. In addition, the nitrogen atom is preferably bonded to the curable functional group via any organic linking group. As a preferable organic linking group, the substituent which can be introduced into the above-mentioned nitrogen atom and the organic group bonded to it can be mentioned.

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

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

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

The above composition may contain one type of silane coupling agent alone, or two or more types. When the composition contains two or more types of silane coupling agents, the total of them should be within the above-mentioned range.

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

<Polymerization inhibitor> The above-mentioned composition may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, tertiary butylcatechol, p-benzoquinone, 4, 4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), N-nitroso Phenylhydroxylamine cerium salt and the like. The content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition. The said composition may contain only 1 type of polymerization inhibitor, and may contain 2 or more types. When two or more types are contained, the total amount thereof is preferably in the above-mentioned range. In addition, if necessary, in order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid and/or behenic acid amide can be added to make it locally present in the coating film during the drying process after coating. surface. The content of the higher fatty acid derivative is preferably 0.5 to 10% by mass relative to the total solid content of the composition.

In addition to the above-mentioned components, the following components may be further added to the above-mentioned composition. For example, sensitizers, co-sensitizers, crosslinking agents, hardening accelerators, fillers, thermal hardening accelerators, plasticizers, diluents, and fat-sensitizing agents, etc. can be mentioned. Moreover, it can be added as needed. Adhesion promoters and other auxiliary agents on the substrate surface (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, antioxidants, fragrances, interfacial tension regulators, and chain transfer agents Etc.) and other well-known additives. For these components, refer to paragraphs 0183 to 0228 of Japanese Patent Application Publication No. 2012-003225 (corresponding to <0237> to <0309> of the specification of US Patent Application Publication No. 2013/0034812) and Japanese Patent Application Publication No. 2008-250074 The descriptions of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP 2013-195480 A are incorporated into the specification of this application.

[Method for manufacturing composition] The method for manufacturing the above composition includes the following mixing and dispersion processes. In addition, it is more preferable to include a standing process and/or a filtration process. Hereinafter, the preferred aspects of each manufacturing process will be described in detail.

<Mixing and Dispersion Process> The mixing and dispersion process is a process in which the above-mentioned components are mixed by a known mixing method (for example, agitator, homogenizer, high-pressure emulsification device, wet grinder, and wet disperser) to obtain a composition. In the mixing and dispersing process, the components of the composition can be mixed together, or they can be mixed in sequence after dissolving or dispersing the components in an organic solvent. In addition, the order of input and working conditions at the time of cooperation are not particularly limited. In addition, the mixing and dispersion process may include a process for preparing a dispersion.

(Process for making dispersion) The process for making dispersion is a process of mixing metal nitride-containing particles, dispersant and solvent, and dispersing the metal nitride-containing particles by the above-mentioned method to make a dispersion. The remaining components can be mixed with the prepared dispersion to produce a composition. In the process of preparing the above dispersion, as the mechanical force used for the dispersion of the pigment, compression, squeezing, impact, cutting, or cavitation can be mentioned. Specific examples of these processes include bead milling, sand milling, roll milling, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, it is possible to appropriately use the "Dispersion Technology Encyclopedia, issued by the Information Agency Co., Ltd., July 15, 2005" and "suspension (solid/liquid dispersion system)-centered dispersion technology and actual comprehensive data on industrial applications. The production process and dispersing machine recorded in the publishing department of the Collection and Management Development Center r, October 10, 1978. In addition, in the process of preparing the above-mentioned dispersion liquid, the miniaturization treatment of the pigment based on the salt milling process can be performed. The raw materials, equipment, and processing conditions used in the salt milling process can be those described in Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629, for example. In addition, it is preferable that the manufacturing method of the above-mentioned composition includes a process of obtaining the above-mentioned metal nitride-containing particles by a thermoplasma method. The process of obtaining metal nitride-containing particles is carried out before mixing the above-mentioned components. The specific manufacturing process of the metal nitride-containing particles based on the thermoplasma method is as described above.

<Standing Process> The above-mentioned metal nitride-containing particles are preferably subjected to the following standing process before being supplied to the mixing and dispersion process or the process of preparing a dispersion. The static process is to make the metal nitride-containing particles obtained by the thermoplasma method not be exposed to the atmosphere after its manufacture, but placed in a sealed container with controlled oxygen concentration for a predetermined time (12 to 72 hours is Preferably, 12 to 48 hours is more preferable, and 12 to 24 hours is further preferable). At this time, it is better to control the moisture content in the sealed container.

At this time, the oxygen (O ₂ ) concentration and the moisture content in the sealed container are preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. The oxygen (O ₂ ) concentration and moisture content in the sealed container can be adjusted by adjusting the oxygen concentration and moisture content in the inert gas supplied into the sealed container. As the inert gas, nitrogen and argon are preferable, and among them, nitrogen is more preferable. After the above-mentioned standing process, the surface and grain boundary of the metal nitride-containing particles become stable. Thereby, it is possible to suppress the occurrence of pinholes in the cured film obtained by using the composition. In addition, the above-mentioned standing process can be replaced by the process H described in the method for producing metal nitride-containing particles. From the viewpoint of the composition having a more excellent effect of the present invention, it is better to replace it by the process H.

<Filtration process> The filtration process is a process in which the composition manufactured by the above mixing and dispersion process is filtered through a filter. During the filtration process, foreign matter can be removed from the composition and/or defects can be reduced. As the filter, as long as it has been used for filtering purposes, etc., it can be used without particular limitation. For example, fluororesins such as PTFE (polytetrafluoroethylene: polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP), etc. can be mentioned. filter. Among these raw materials, polypropylene (containing high-density polypropylene) and nylon are preferred. The pore size of the filter is preferably about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and even more preferably 0.3 to 0.7 μm. By setting it as this range, the filter clogging of the pigment can be suppressed, and fine foreign substances such as impurities and aggregates contained in the pigment can be reliably removed. When using filters, different filters can be combined. At this time, the filtration by the first filter may be performed only once, or may be performed two or more times. When combining different filters to perform filtration more than two times, it is preferable that the pore size after the second filtration is the same or larger than the pore size of the first filtration. In addition, it is also possible to combine first filters with different pore diameters within the above-mentioned range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., Toyo Roshi Kaisha, Ltd., Nihon Entegris K.K. (formerly Mykrolis Corpration), KITZ MICROFILTER CORPORATION, and the like. The second filter can be formed of the same material as the above-mentioned first filter. The pore size of the second filter is preferably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

[Cured film (light-shielding film)] The cured film is obtained using the composition described above. The cured film contains metal nitride-containing particles. The above-mentioned cured film is suitable as a light-shielding film, and specifically, it is suitable for light-shielding the peripheral part of the light-receiving part of an image sensor. Hereinafter, as an example, a case where the cured film is used as a light-shielding film in the peripheral portion of the light-receiving portion of an image sensor will be described. The said light-shielding film is formed using the said composition (especially, the said photosensitive composition). The light-shielding film obtained by using the above composition is excellent in resolution and corrosion resistance of the electrode.

The film thickness of the light-shielding film is not particularly limited. From the viewpoint that the light-shielding film has more excellent effects of the present invention, in terms of the film thickness after drying, 0.2 μm or more and 50 μm or less is preferred, 0.3 μm or more and 10 μm The following are more preferable, and 0.3 μm or more and 5 μm or less are more preferable. The above-mentioned composition has a high optical density per unit volume (high light-shielding property), and therefore, it is possible to further reduce the film thickness compared to a composition using a black pigment in the past. As for the size of the light-shielding film (the length of one side of the light-shielding film provided on the periphery of the light-receiving part of the sensor), from the viewpoint that the light-shielding film has more excellent effects of the present invention, 0.001mm or more and 10mm or less is preferable, 0.05mm The above and 7 mm or less are more preferable, and the 0.1 mm or more and 3.5 mm or less are more preferable. The above-mentioned composition has a high optical density per unit volume, so it is advantageous for microfabrication by reducing the coating amount, etc., and is excellent in resolution and electrode corrosion resistance, so it can be used particularly preferably within the above-mentioned range.

[Method of Manufacturing Cured Film] Next, the method of manufacturing the above-mentioned cured film (light-shielding film) will be described as an example of a method of manufacturing a black matrix-containing color filter. The color filter containing the above-mentioned black matrix contains a cured film (black matrix) obtained by using the above-mentioned composition on a substrate. Hereinafter, the manufacturing method of the color filter containing the above-mentioned black matrix will be described in detail for each process.

The manufacturing method of the color filter containing the above-mentioned black matrix includes the following composition layer forming process, exposure process, and development process. Composition layer formation process: a process of coating the above composition on a substrate to form a composition layer (coating film). Exposure process: The process of exposing the above-mentioned composition layer through a photomask (hereinafter, also simply referred to as "mask".). Development process: the process of developing the exposed composition layer to form a patterned hardened film (light-shielding film).

Specifically, directly or through other layers, the above-mentioned composition is coated on the substrate to form a composition layer (composition layer formation process), and exposure is performed through a predetermined mask pattern, so that only the part of the coating film irradiated by light is exposed Hardening (exposure process), and developing with a developer (development process), whereby the color filter of the present invention can be manufactured. Hereinafter, each process in the manufacturing method of the color filter containing the above-mentioned black matrix will be described.

<Composition layer formation process> The composition layer formation process is a process of applying the above-mentioned composition on a substrate to form a composition layer (coating film). As the substrate, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, and photoelectric conversion element substrates used for solid-state imaging devices, etc. ( For example, silicone substrates, etc.), CCD (Charge Coupled Device) substrates, and CMOS (Complementary Metal-Oxide Semiconductor (Complementary Metal-Oxide Semiconductor)) substrates. In addition, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface of the substrate, a primer layer can be provided on these substrates as needed.

As a coating method for coating the above-mentioned composition on a substrate, various coating methods such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, and a screen printing method can be applied.

When manufacturing a black matrix-containing color filter for solid-state imaging devices, the coating film thickness of the composition is preferably 0.35 μm or more and 1.5 μm or less from the viewpoint of resolution, and 0.40 μm or more and 1.0 μm or less For better.

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

<Exposure process> The exposure process is a process in which the composition layer (coating film) formed in the composition layer formation process is exposed through a mask, and only the part of the coating film irradiated by light is hardened. The exposure is preferably carried out by irradiation of active light or radiation. In particular, ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably used, and a high-pressure mercury lamp is more preferred. The irradiation intensity is preferably 5 to 1500 mJ/cm ^{2 and more} preferably 10 to 1000 mJ/cm ² . In addition, from the viewpoint of improving the resolution, in the formation of the light-shielding film for solid-state imaging devices, exposure by an i-ray stepper is preferable.

<Development process> After the exposure process, an alkali development process (development process) is performed, so that the light unirradiated part in the exposure process is dissolved in the alkali aqueous solution. Thereby, only the light-hardened part (the part of the coating film irradiated by light) remains. As the developer, an organic alkali developer that does not cause damage to the circuit of the substrate and the like when producing a black matrix-containing light-shielding color filter for a solid-state imaging element is preferable. The development temperature is usually 20 to 30°C, and the development time is 20 to 90 seconds.

As an alkaline aqueous solution, an inorganic type developer and an organic type developer are mentioned, for example. As an inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, or sodium metasilicate, dissolved in a concentration of 0.001-10% by mass, preferably 0.01- 1% by mass alkaline aqueous solution. Examples of organic developers include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8- An organic basic compound such as diazabicyclo-[5.4.0]-7-undecene is dissolved into an alkaline aqueous solution with a concentration of 0.001-10% by mass, preferably 0.01-1% by mass. In the alkaline aqueous solution, for example, an appropriate amount of water-soluble organic solvents such as methanol and ethanol and/or surfactants can be added. In addition, when a developer containing such an alkaline aqueous solution is used, it is generally preferable to wash (rinse) with pure water after development.

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

In addition, the manufacturing method of the color filter containing the cured film (black matrix) may include a curing process of curing the cured film by heating and/or exposure after the development process.

The color filter containing the above-mentioned cured film (black matrix) has excellent resolution and electrode corrosion resistance. Thereby, the color filter containing the above-mentioned cured film (black matrix) is suitable for solid-state imaging devices such as CCD image sensors and/or CMOS image sensors. Especially suitable for high resolution CCD image sensor and/or CMOS image sensor with over 1 million pixels. That is, the color filter containing the above-mentioned cured film is suitable for solid-state imaging devices. In addition, the color filter may include a structure in which, for example, a space divided into a grid shape by a partition wall is embedded with a cured film forming pixels of each color. The above-mentioned cured film (black matrix) is arranged, for example, between the light-receiving portion of each pixel constituting the CCD image sensor and/or the CMOS image sensor and the microlens for condensing light.

[Solid-state imaging element] The solid-state imaging element includes the cured film (black matrix). The solid-state imaging device described above preferably has a color filter including a black matrix and a patterned film including pixels of other colors (three colors or four colors) as necessary. The solid-state imaging device described above is not particularly limited as long as it contains the black matrix and functions as a solid-state imaging device. For example, it can be mentioned that the solid-state imaging device (CCD image sensor and CMOS image sensor) is included on the substrate. A plurality of photodiodes, polysilicon and other light-receiving elements in the light-receiving area of the light-receiving area of the substrate include the above-mentioned black matrix solid-state imaging element on the surface opposite to the light-receiving element forming surface of the substrate. In addition, the color filter may have a structure in which a cured film forming pixels of each color is buried in a space divided into a grid shape by a partition wall, for example. In this case, it is preferable that the partition wall has a low refractive index with respect to each color pixel. As an example of an imaging element including such a structure, solid-state imaging elements described in Japanese Patent Application Publication No. 2012-227478 and Japanese Patent Application Publication No. 2014-179577 can be cited.

[Image Display Device] The cured film described above is suitable for image display devices such as liquid crystal display devices and organic electroluminescence display devices.

The definition of image display devices and the details of each image display device are described in, for example, "Electronic Display Devices (by Akio Sasaki, published by Kogyo Chosakai Publishing CO., LTD. 1990)" and "Display Devices (Junaki Ibuki) "Industrial Books (published in the first year of Heisei)" etc. In addition, the liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing CO., LTD. in 1994)". The above-mentioned cured film is suitable for, for example, a liquid crystal display device of the method described in the above-mentioned "Second Generation Liquid Crystal Display Technology".

As one aspect of the liquid crystal display device containing the above-mentioned cured film, for example, at least one of a pair of light-transmissive substrates contains at least a color filter, a liquid crystal layer, and a liquid crystal drive mechanism (including a simple matrix drive method and active Matrix drive mode) liquid crystal display device. The liquid crystal display device includes a plurality of pixel groups, and each pixel constituting the pixel group includes color filters separated from each other by the cured film (black matrix).

In addition, as another aspect of the above-mentioned liquid crystal display device, at least one system includes at least a color filter, a liquid crystal layer, and a liquid crystal drive mechanism between a pair of light-transmitting substrates, and the liquid crystal drive mechanism includes an active element (for example, TFT ( Thin Film Transistor (thin film transistor)), and each active element contains a color filter containing the above-mentioned cured film (black matrix).

The color filter containing the above-mentioned cured film is suitable for 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. issued in 1996)." Moreover, the above-mentioned color filter is also suitable for: IPS (In Plane Switching) and other horizontal electric field driving methods; MVA (Multi-domain Vertical Alignment) and other pixel division methods; and the viewing angle is enlarged Liquid crystal display device, STN (Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer) Interval), FFS (fringe field switching) and R-OCB (Reflective Optically Compensated Bend) etc.

The above-mentioned color filter is suitable for a bright and high-definition COA (Color-filter "On" Array (color filter array)) liquid crystal display device. Regarding the liquid crystal display device of the COA method, in addition to the usual required characteristics of the color filter, the required characteristics of the interlayer insulation film, that is, low dielectric constant and peeling liquid resistance, are sometimes required. The COA type liquid crystal display device containing the above-mentioned color filter has more excellent resolution, or has more excellent durability. In addition, in order to meet the required characteristics of low dielectric constant, a resin coating film may be further included on the color filter layer.

These image display methods are described, for example, on page 43 of "EL, PDP, LCD Display-Latest Trends in Technology and Market-(issued by TORAY Research Center, Inc. in 2001)". In addition, in the above, EL represents the abbreviation of Electroluminescence, PDP represents the abbreviation of Plasma Display Panel, and LCD represents the abbreviation of liquid crystal display (liquid crystal display).

The above-mentioned liquid crystal display device may be constituted by various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle protective film in addition to the above-mentioned color filter. The above-mentioned color filter can be applied to a liquid crystal display device composed of these known members. These components are described in, for example, "'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Shima Kentaro CMC-Group. Issued in 1994)" and "2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)" (Table Ryoshi Fuji) Chimera Research Institute, Inc., issued in 2003)”. The backlight is described in SID meeting Digest 1380 (2005) (A.Konno et.al), pages 18-24 of the December 2005 issue of the monthly display (Yoshihiro Shima), and pages 25-30 of the December 2005 issue of the monthly display (Yagi Takaaki) and so on.

In addition, the above-mentioned cured film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multifunction printers and scanners; surveillance cameras, barcode readers And automatic teller machine (ATM: automated teller machine), high-speed camera, and personal authentication using facial image authentication, and other industrial equipment; automotive camera equipment; medical cameras such as endoscopes, capsule endoscopes, and catheters Equipment; biological sensors, biological sensors (Biosensor), military reconnaissance cameras, stereo map cameras, meteorological and ocean observation cameras, terrestrial resources reconnaissance cameras, and exploration cameras for astronomical and deep space targets in the universe. The light-shielding members and light-shielding layers of optical filters and modules used in equipment, etc. are further suitable for anti-reflection members and anti-reflection layers.

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

The above-mentioned cured film is suitable as an optical filter and an optical film used in a quantum dot display. In addition, it is suitable as a member that provides a light-shielding function and an anti-reflection function. As examples of quantum dot displays, U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960 Recorder. [Example]

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

[Production of metal nitride-containing particle P-1] The metal nitride-containing particle P-1 was produced by the following method. First, prepare niobium (powder) <100-325 mesh> manufactured by Mituwa Chemistry. which contains niobium as a transition metal as a raw material (hereinafter, also referred to as "metal raw material powder"). Next, the content of impurities contained in the metal raw material powder was analyzed by ICP emission spectrometry. In addition, in the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analysis device "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used.

Next, the above-mentioned metal raw material powder was subjected to plasma treatment in Ar gas (treatment conditions were based on the following plasma treatment (1)) to perform metal microparticulation. The average primary particle size of the obtained metal fine particles was measured. As a result, it was 80 nm. In addition, the average primary particle size is calculated by the following method. Sample: The dispersion was prepared by the same method as [Preparation of metal nitride-containing particle dispersion] described later (metal fine particles 25% by mass, the following dispersant A7.5% by mass, PGMEA; propylene glycol monomethyl ether acetic acid Ester solvent 67.5% by mass), after diluting the obtained dispersion 100 times with PGMEA, dropping it on the carbon foil and drying it. An image was obtained by observing the sample with a transmission electron microscope (TEM: Transmission Electron Microscope) at a magnification of 20,000 times. The area of the metal particles in the obtained image is calculated by image processing. Next, calculate the diameter when converting the obtained area into a circle. This operation was performed for a total of 400 metal particles (approximately 3,000 metal particles were confirmed in each field of view) with 4 fields of view, and the circle-evaluated diameter converted to arithmetic average was used as the average primary particle size of the metal particles.

In addition, the impurities contained in the metal fine particles were measured by the above-mentioned method, and as a result, no impurities were detected. In addition, no impurities detected by the above method means that the content of impurities is less than 20 ppm relative to the total mass of the metal fine particles.

<Plasma treatment (1)> Plasma treatment (1) was performed by the following method. That is, an apparatus based on the black composite particle manufacturing apparatus described in Fig. 1 of International Publication No. 2010/147098 pamphlet was used as a metal particle manufacturing apparatus, and plasma treatment was performed under the following conditions (1).・High-frequency voltage applied to the high-frequency oscillation coil: frequency, about 4MHz, voltage, about 80kVA ・Plasma gas: argon (supply amount 100L/min) ・Carrier gas: argon (supply amount 10L/min) ・Chamber atmosphere: argon gas (supply rate 1000L/min, chamber flow rate 5m/sec) · Cyclone atmosphere: argon gas, internal pressure: 50kPa · Material supply speed from the chamber to the cyclone separator: 10m/s (average value)

Next, as a raw material powder containing atom A, Fe powder was prepared JIP "270M manufactured by JFE STEEL CORPORATION, and plasma treatment was performed according to the conditions of the above-mentioned plasma treatment (1) to atomize atom A. At this time, the impurities contained in the obtained microparticles were measured by the same method as described above, and as a result, no impurities were detected.

Next, the metal fine particles obtained as described above and the atomized atom A are mixed to obtain raw metal powder. The raw metal powder was subjected to plasma treatment in nitrogen (treatment conditions were based on the plasma treatment (2) described below) to obtain metal nitride-containing particles.

<Plasma treatment (2)> Plasma treatment (2) was performed by the following method. In addition, the equipment used is the same as the plasma treatment (1).・High-frequency voltage applied to the high-frequency oscillation coil: frequency, about 4MHz, voltage, about 80kVA ・Plasma gas: argon and nitrogen (supply volume of 50L/min) ・Carrier gas: nitrogen (supply volume 10L/ min) ・The atmosphere in the chamber: Nitrogen (supply amount 1000L/min, the flow rate in the chamber is 5m/sec) ・The atmosphere in the cyclone: nitrogen, internal pressure 50kPa ・The speed of feeding material from the chamber to the cyclone: 10m/s (average value)

Using Ar gas, the metal nitride-containing particles after the plasma treatment (2) are completed, and the shunt type humidity supply device SRH manufactured by NIHON SHINTECH CO., LTD. becomes 95% relative humidity in the atmosphere. Introduce nitrogen at 20°C under the conditions, and let it stand for 24 hours. After that, a TTSP separator manufactured by Hosokawa Micron Group was used to classify the obtained metal nitride-containing particles under the condition that the yield was 10%, thereby obtaining metal nitride-containing particles P-1 powder. In addition, nitrogen gas was supplied to the separator.

The average primary particle diameter of the metal nitride-containing particle P-1 was measured, and as a result, it was 12 nm. In addition, the electrical conductivity of the metal nitride-containing particle P-1 was measured. As a result, it was 180×10 ⁴ S/m. In addition, the average primary particle size is the average primary particle size measured by the above-mentioned method. In addition, the above-mentioned electrical conductivity is the electrical conductivity measured by the following method. The electrical conductivity was measured by the following method using the powder resistance measurement system MCP-PD51 manufactured by Mitsubishi Chemical Analytech CO., LTD. First, 1g of metal nitride-containing particles was put into the measuring container of φ20mm of the above measuring device, then pressurization was started, and the pressure was changed to 0kN, 1kN, 5kN, 10kN, 20kN to measure the volume resistivity (ρ) of the particles . The saturated volume resistivity under the condition that the volume resistivity is not affected by pressure is obtained from the measurement results, and the conductivity (σ) is calculated by the relational expression of σ=1/ρ using the obtained saturated volume resistivity. In addition, the above-mentioned test was carried out at room temperature.

[Production of metal nitride-containing particles P-2 to P-7, P-C1, and P-C5] The content of atom A was set as shown in Table 1. In addition, by combining with metal nitride-containing particles The particles P-2 to P-7, P-C1, and P-C5 containing metal nitrides were produced in the same manner as the particle P-1. In addition, the average primary particle size of the metal fine particles, the average primary particle size and the electrical conductivity of the metal nitride-containing particles in the production of the metal nitride-containing particles are shown in Table 1 in a comprehensive manner.

[Preparation of metal nitride-containing particle P-C2] Except that atom A was not added to the transition metal raw material, the metal nitride-containing particle P was produced by the same method as the metal nitride-containing particle P-1 -C2. In addition, the average primary particle size of the metal fine particles, the average primary particle size and the electrical conductivity of the metal nitride-containing particles in the production of the metal nitride-containing particles are shown in Table 1 in a comprehensive manner.

[Production of metal nitride-containing particles P-8 to P-15] The transition metal raw materials shown in Table 1 were used, and the content of atom A was set as described in Table 1. In addition, by combining with metal nitrogen The metal nitride-containing particles P-8 to P-15 were produced in the same manner as the particles P-1 of the compound. In addition, the average primary particle size of the metal fine particles, the average primary particle size and the electrical conductivity of the metal nitride-containing particles in the production of the metal nitride-containing particles are shown in Table 1 in a comprehensive manner.

[Preparation of metal nitride-containing particles P-C3 and P-C4] Instead of transition metal raw materials, the raw materials shown in Table 1 were used, and atom A was not added. In addition, by combining with metal nitride-containing particles P- 1 The metal nitride-containing particles P-C3 and P-C4 were produced in the same way. In addition, the average primary particle size of the metal fine particles, the average primary particle size and the electrical conductivity of the metal nitride-containing particles in the production of the metal nitride-containing particles are shown in Table 1 in a comprehensive manner.

The symbols of the transition metal raw materials and the raw materials of atom A in Table 1 are as follows.

・Nb powder: Niobium (powder) manufactured by Mituwa Chemistry. <100-325mesh> ・V powder: Metal vanadium powder VHO manufactured by TAIYO KOKO Co., LTD. ・Zr powder: Zirconium powder manufactured by Wako Pure Chemical Industries, Ltd.・Tantalum Nodular: Tantalum Nodular manufactured by Global Advanced Metal ・Hf powder: Hafnium powder manufactured by Furuchi Chemical Corporation ・Y powder: Yttrium powder manufactured by NIPPON YTTRIUM CO., LTD. ・Cr powder: manufactured by Copyright Kosei Pharmaceutical CO., LTD. Degassed electrolytic metal chromium powder ・Re powder: Rhenium powder manufactured by Rhenium Alloys, Inc. ・W powder: Tungsten powder AW3110 manufactured by Eurotungsten ・Al powder: Aluminum powder No.22000 ・Si manufactured by METAL POWDER CO., LTD. Powder: Silicon powder manufactured by Furuuchi Chemical Corporation ・Fe powder: Fe powder JIP　270M manufactured by JFE STEEL CORPORATION ・Ni powder: Ni powder 300nm product manufactured by Toho Titanium Corporation ・Ag powder: Ag powder Mitsui Mining & Smelting Co., SPQ03R manufactured by Ltd.

In addition, "ppm" in Table 1 below means ppm by mass. In addition, in the table, "not detected" means that no impurities are detected as a result of the measurement by the above-mentioned measuring method, and specifically means that it is less than 20 mass ppm. In addition, "not added" means that the atom A is added, and "not measured" means that the above-mentioned atom A is not added, and therefore the measurement is not performed. By this, "not measured" means that it is actually less than 20 mass ppm (calculated as less than 5 mass ppm).

[Table 1]

<Dispersant> As dispersants, dispersants A to C of the following structures were used. In dispersant A and C, the numerical value described in each structural unit represents the mass% of each structural unit with respect to all structural units. In dispersant B, the characters described in each structural unit indicate the mol% of each structural unit with respect to all structural units.

・Dispersant A [Chemical formula 21]

・Dispersant B [Chemical formula 22]

・Dispersant C [Chemical formula 23]

<Binder Resin> As the binder resin, the following resin A and resin B were used. Hereinafter, the structures of resin A and resin B are shown respectively. In resin A and resin B, the number described in each structural unit represents the mol% of each structural unit with respect to all structural units.

・Resin A: Akurikiyua RD-F8 (trade name, manufactured by NIPPON SHOKUBAI CO., LTD.) [Chemical formula 24]

・Resin B [Chemical formula 25]

In the formula of the resin B, each abbreviation indicates the following. BzMA: Benzyl methacrylate MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate

<Polymerizable compound> ・Polymerizable compound M1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku CO., LTD., trade name "KAYARAD", see the following formula) [Chemical formula 26]

・Polymerizable compound M2: PET-30 (pentaerythritol triacrylate, manufactured by Nippon Kayaku CO., LTD.)

<Polymerization initiator> ・OXE-02: Irgacure　OXE02 (trade name, manufactured by BASF Japan Ltd)

<Polymerization inhibitor> ・PMF: p-methoxyphenol

<Surface active agent> ・F-556: Megafac F-556 (manufactured by DIC CORPORATION)

<Organic solvent> ・PGMEA: Propylene glycol monomethyl ether acetate ・CPN: Cyclopentanone ・Bu acetate: butyl acetate

[Preparation of metal nitride-containing particle dispersion] First, with a blender (EUROSTAR manufactured by IKA Works GmbH & CO. KG), the metal nitride-containing particles, dispersant, and organic solvent were mixed for 15 minutes to obtain the above components的mixture. Next, using NPM-Pilot manufactured by SHINMARU ENTERPRISES CORPORATION, the obtained mixed liquid was subjected to dispersion treatment under the following conditions to obtain a metal nitride-containing particle dispersion liquid. In addition, it was added so that the mass ratio (D/P) of the dispersant to the metal nitride-containing particles became the values shown in the Examples and Comparative Examples in Table 3.

<Dispersion conditions> ・Bead diameter: φ0.05mm, (Zirconium oxide beads, YTZ manufactured by NIKKATO CORPORATION) ・Bead filling rate: 65% by volume ・Grinding peripheral speed: 10m/sec ・Separator peripheral speed: 13m/s ・Mixed liquid volume for dispersion treatment: 15kg ・Circulation flow rate (pump supply volume): 90kg/hour ・Processing liquid temperature: 19～21℃ ・Cooling water: water ・Treatment time: about 22 hours

[Preparation of composition] Next, the above-mentioned metal nitride-containing particle dispersion, binder resin, polymerizable compound, polymerization initiator, polymerization inhibitor, and surfactant were mixed and stirred to obtain the following Tables 2 and 3 The compositions of the examples and comparative examples are shown. In addition, the content of each component in Table 2 is mass %.

[Table 2]

<Measurement of the moisture content in the composition> The moisture content of each composition in the examples and comparative examples was measured by MKV-710 (trade name, manufactured by KYOTO ELECTRONICS INDUSTRY CO., LTD.) based on the Karl Fischer method. ) Was measured. The results are shown in Table 3.

[Evaluation Test] The following evaluation tests were performed on each composition of the Examples and Comparative Examples. The results are summarized in Table 3.

[OD value] On a square glass plate (EagleXG, manufactured by Corning Incorporated) with a thickness of 0.7 mm and 10 cm, each composition was used to form a coating film by spin coating. At this time, in accordance with the solid content concentration of each composition, the rotation speed was adjusted so that the film thickness became 1.5 μm. The formed coating film was dried by a heat treatment at 100°C for 2 minutes on a hot plate to obtain a cured film. For the substrate containing the obtained cured film, the OD value was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The greater the OD value, the more excellent the light-shielding property of the cured film is. In addition, evaluation was performed based on the following criteria. In actual use, "C" or higher is preferred. A: OD value exceeds 4 B: OD value exceeds 3 and is 4 or less C: OD value exceeds 2 and is 3 or less D: OD value is 2 or less

[Stability with time] To a container having a diameter of 50 mm and a capacity of 100 mL, 100 mL of the metal nitride-containing particle dispersion was added, and the mixture was allowed to stand at room temperature for 9 minutes. After standing still, 1 cm of the supernatant liquid was extracted from the metal nitride-containing particle dispersion liquid, and the solid content concentration was measured by evaporation to dryness. The rate of change in the solid content of the metal nitride-containing particle dispersion before and after the standing was calculated by the following formula, and the value was evaluated by the following criteria. In actual use, "C" or higher is preferred. (Formula) Solid content change rate = (initial solid content concentration)-(solid content concentration of 1 cm of supernatant) A: The solid content change rate is less than 3% B: The solid content change rate is 3% or more and less than 7% C : The rate of change of solid content is 7% or more and less than 12% D: The rate of change of solid content is 12% or more

[Number of particles] A sample solution was prepared by diluting the above composition 500 times by PGMEA, and measured by a flow-type particle image analyzer (trade name "FPIA", manufactured by Malvern Instruments Ltd), and the sample solution contained in 10 ml The number of metal nitride-containing particles with a size of 10μm or more. The evaluation was performed based on the following criteria. In actual use, "C" or higher is preferred. A: The number of particles is 3 or less B: The number of particles is 4-10 C: The number of particles is 11-20 D: The number of particles is 21 or more

[Resolution] The above composition was applied on an 8-inch silicon substrate to produce a coating film. The coating film was produced using Coater Developer ACT8 manufactured by Tokyo Electron Limited, and the rotation speed was adjusted so that the film thickness became 1.5 μm in accordance with the solid content concentration of each composition. The obtained coating film was subjected to a heat treatment at 100°C for 2 minutes on a hot plate as a pre-baking treatment. The pre-baked substrate with a coating film was exposed (negatively) by using an i-ray stepper (FPA3000i5+ manufactured by Canon Inc.) through a mask formed with an island pattern with a width of 10 μm. For the exposed coating film, use Coater Developer ACT8 manufactured by Tokyo Electron Limited and CD-2060 (manufactured by FUJIFILM Electronic Materials CO., LTD.) as a developer. Perform spin immersion development for 30 seconds. The pure water was rinsed. Post-baking the developed coating film (temperature: 220°C, time: 10 minutes). The pattern shape of the post-baked coating film was measured by SEM (Scanning Electron Microscope). Specifically, the width of the island shape was measured and evaluated based on the following criteria. In actual use, "C" or higher is preferred. A: The width of the island shape is 9.5 μm to 10.5 μm B: The width of the island shape is 8 μm or more and less than 9.5 μm, or more than 10.5 μm and 12 μm or less C: The width of the island shape is less than 8 μm or more than 12 μm D: Pattern peeling Or the islands are not formed due to insufficient development.

[Corrosion resistance of electrode] Using the composition, a coating film was formed on the substrate of the image sensor device by spin coating. The coated film was pre-baked on a hot plate at 100°C for 2 minutes. For the pre-baked substrate, an i-ray exposure device (FPA3000i5+, manufactured by Canon Inc.) was used to form a cutting line and a light shielding layer other than the coated electrode on the outer periphery of the light-receiving part on the substrate. Moreover, the heating plate was used for heating treatment (post-baking process) at 220°C for 5 minutes. After the light-shielding film formation process, the substrate was exposed to conditions of 130° C. and a relative humidity of 90% for 7 days, and then wiring was formed by bonding wires. The occurrence of wire breakage was evaluated by a bonding wire inspection device manufactured by Canon Machinery Inc. The number of chips evaluated was 50, and the number of wires per chip was 40. The evaluation was performed based on the following criteria. In actual use, "C" or higher is preferred. A: The number of broken wires is less than 1 B: The number of broken wires is more than 2 and less than 5 C: The broken wires are more than 5 and less than 10 D: The broken wires are more than 10

[table 3]

From the results shown in Table 3, it can be seen that the particles containing metal nitrides contain transition metals other than titanium among the transition metals of groups 3 to 11 and have an electronegativity of 1.22 to 2.36 in Example 1 The cured film (light-shielding film) made from the composition of ~32 has excellent light-shielding properties, excellent resolution, and excellent electrode corrosion resistance. On the other hand, the cured film (light-shielding film) produced using the compositions of Comparative Examples 1 to 5 did not achieve the desired effect. In addition, the cured film (light-shielding film) produced by using the composition of Examples 3, 8, 10, 12, 13, 14 and 15 of the transition metal-based niobium, vanadium, tantalum, yttrium, chromium, rhenium or tungsten, respectively The cured film (light-shielding film) produced using the composition of Example 9 or 11 of transition metal-based zirconium or hafnium has a more excellent OD value (light-shielding property). Among them, the cured film (light-shielding film) produced using the composition of Examples 3 or 8 in which the transition metal is niobium or vanadium, respectively, has a further excellent OD value. In addition, the composition of Example 21 having a solid content of 10 to 40% by mass has a smaller number of particles than the composition of Example 22 having a solid content of more than 40% by mass. In addition, the composition of Example 23 having a water content of 0.1 to 1% by mass has a smaller number of particles than the composition of Example 24 having a water content of more than 1% by mass. In addition, the composition of Example 2 in which the content of metal nitride-containing particles is 20 to 70% by mass relative to the total solid content of the composition is more excellent than the composition of Example 29, which is less than 20% by mass. Stability over time. In addition, the composition of Example 2 described above has fewer particles than the composition of Example 28 that exceeds 70% by mass, and the cured film (light-shielding film) obtained has more excellent resolution. In addition, the composition of Example 2 in which the mass ratio of the dispersant to the metal nitride-containing particles is 0.05 to 0.30 has better stability over time than the composition of Example 32 in which the mass ratio is less than 0.05. . In addition, the cured film (light-shielding film) produced using the composition of Example 2 has better resolution than the cured film (light-shielding film) produced using the composition of Example 18.

[Preparation and evaluation of metal nitride-containing particle P-1 (A)] The metal nitride-containing particle P-1 (A) was prepared by the following method, and the metal nitride-containing particle P-1 (A) It is obtained by coating the surface of the metal nitride-containing particle P-1 produced by the above method with aluminum hydroxide. First, 100 g of metal nitride-containing particles P-1 was weighed, and added to 750 mL of pure water, and dispersed well to obtain a slurry. Next, to a solution prepared by dissolving 220 g of an aluminum chloride aqueous solution with a concentration of 10% by mass of aluminum oxide and 160 g of urea in 500 mL of water, the slurry was added and uniformly mixed to obtain a mixture. The mixture was heated at 90°C for 8 hours and cooled to room temperature. The cooled mixture was filtered, washed with water, dried at 110°C for 24 hours, and then fired at 600°C for 5 hours to obtain a metal nitride-containing particle P-1 whose surface was coated with aluminum hydroxide. Metal nitride particles P-1 (A). The average primary particle diameter of the metal nitride-containing particle P-1 (A) was 13 nm, and the electrical conductivity was 100 S/m. Next, using the metal nitride-containing particles P-1 (A), the dispersion and composition were prepared by the same method as in Example 1 above, and the OD value, resolution, corrosion resistance of the electrode, and time-dependent The stability and particles were evaluated. As a result, the results were the same as those of Example 1 using metal nitride-containing particles P-1.

[Preparation and evaluation of metal nitride-containing particles P-2(A) to P-15(A)] By the same method as the above-mentioned metal nitride-containing particle P-1(A), metal-containing nitride was used Particles P-2 to P-15 of, and metal nitride-containing particles P-2(A) to P-15(A) were produced. Table 4 shows each average primary particle size and conductivity. Next, using metal nitride-containing particles P-2 (A) to P-15 (A), the dispersion and composition were prepared by the same method as in Examples 2 to 32 above, and the OD value and resolution The corrosion resistance, stability over time, and particles of the electrode were evaluated. The results were the same as the results of Examples 2 to 32 using metal nitride-containing particles P-2 to P-15, respectively.

[Table 4]

In Example 1, the polymerization initiator was replaced with Irgacure OXE03 (trade name, manufactured by BASF Corporation) from OXE-02. Except for this, the same method was used for evaluation. As a result, it was found that 1 The same result. Moreover, compared with Example 1, the robustness with respect to the exposure amount is wider, and the resolution can be maintained even when the exposure amount is reduced.

In Example 1, the polymerization initiator was replaced from OXE-02 to Adeka Arkls NCI-831 (manufactured by ADEKA CORPORATION). Except for this, the evaluation was carried out by the same method. As a result, it was found that the same as in the examples can be obtained. 1 The same result. Moreover, compared with Example 1, the robustness with respect to the exposure amount is wider, and the visibility can be maintained even when the exposure amount is reduced.

In Example 1, the polymerizable compound was replaced from the polymerizable compound M1 to the polymerizable compound M2, and the evaluation was performed by the same method except for this. As a result, it was found that the same results as in Example 1 were obtained.

In Example 1, the polymerizable compound was changed from the polymerizable compound M1 to a mixture of polymerizable compounds M1 and M2 (mass ratio 1:1 without changing the content of the polymerizable compound relative to all the components). Except for this, the evaluation was carried out by the same method, and as a result, it was found that the same result as in Example 1 was obtained.

In Example 1, PGMEA was used instead of the solvent CPN, and the evaluation was carried out by the same method except for this. As a result, it was found that the same results as in Example 1 were obtained.

In Example 1, PGMEA was used instead of the solvent CPN and Bu acetic acid, and the evaluation was performed by the same method. As a result, it was found that the same results as in Example 1 were obtained.

In Example 1, the surfactant F-556 was not used, and the evaluation was performed by the same method except that. As a result of the evaluation, it was found that the same results as in Example 1 were obtained.

In Example 1, the polymerization inhibitor PMF was not used, and the evaluation was performed by the same method except that. As a result of the evaluation, it was found that the same results as in Example 1 were obtained.

<Preparation of Carbon Black Dispersion (CB Dispersion)> In the preparation of the above-mentioned pigment dispersion, instead of metal nitride-containing particles, carbon black (trade name "Color Black S170", manufactured by Degussa-Hüls AG, average one time) was used. A particle size of 17 nm, a BET specific surface area of 200 m ² /g, and carbon black produced by a gas black method), except that the dispersion was prepared by the same method as above to obtain a carbon black dispersion.

In the preparation of the composition of Example 1, instead of the metal nitride-containing particle dispersion added to contain 21% by mass of the metal nitride-containing particles P-1 in the composition, a metal-containing nitride-containing particle dispersion was used. A mixture of the metal nitride-containing particle dispersion liquid of the particles P-1 and the above-mentioned CB dispersion liquid [metal nitride-containing particle P-1 in the composition: carbon black of the composition=5:2 (mass ratio). The total content of the metal nitride-containing particles P-1 and carbon black in the composition was 21% by mass. ], other than that, the composition was produced by the same method and evaluated. As a result of the evaluation, the OD value was the same as that of Example 1, and it was found that the same light shielding property as that of Example 1 was obtained.

<Preparation of color pigment dispersion (PY dispersion)> In the preparation of the metal nitride-containing particle dispersion, instead of metal nitride-containing particles, Pigment Yellow 150 (Hangzhou Star-up Pigment Co., Ltd. Product, trade name 6150 Pigment Yellow 5GN), except for this, a color pigment dispersion (PY dispersion) was obtained by the same method.

In the preparation of the composition of Example 1, instead of the metal nitride-containing particle dispersion added so that the composition contained 21% by mass of the metal nitride-containing particles P-1, a metal-containing nitride-containing particle dispersion was used A mixture of the pigment dispersion of the particle P-1 and the above-mentioned PY dispersion [the metal nitride-containing particle P-1 in the composition: the pigment yellow in the composition 150=6:1 (mass ratio). The total content of the metal nitride-containing particles P-1 and Pigment Yellow 150 in the composition was 21% by mass. ], except for this, the composition was prepared by the same method, and the composition was evaluated. As a result of the evaluation, the OD value was the same as that of Example 1, and it was found that the same light shielding property as that of Example 1 was obtained, and a darker black film was obtained.

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Claims (22)

A composition containing a metal nitride-containing particle containing atom A. The aforementioned metal-nitride-containing particle contains a transition metal other than titanium among the transition metals of groups 3 to 11 and has an electronegativity of 1.22 to 2.36. Nitride of the metal, the atom A is an element different from the transition metal constituting the nitride of the transition metal, and is at least 1 selected from the group consisting of boron, aluminum, silicon, manganese, iron, nickel, and silver The content of the atom A in the metal nitride-containing particle is 0.00005 to 10% by mass. The composition described in item 1 of the scope of patent application, wherein the conductivity of the aforementioned metal nitride-containing particles is 100×10 ⁴ to 600×10 ⁴ S/m. The composition described in item 1 or item 2 of the scope of patent application, wherein the average primary particle size of the aforementioned metal nitride-containing particles is 10-50nm. Such as the composition described in item 1 or item 2 of the scope of patent application, it also contains a binding resin. The composition according to item 4 of the scope of patent application, wherein the mass ratio of the aforementioned binder resin to the aforementioned metal nitride-containing particles is 0.3 or less. The composition described in item 1 or item 2 of the scope of patent application, wherein the aforementioned transition metal is at least 1 selected from the group consisting of V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re Kind. The composition described in item 1 or item 2 of the scope of patent application, wherein the aforementioned transition metal is at least one selected from the group consisting of V and Nb. The composition described in item 1 or item 2 of the scope of the patent application further contains a polymerizable compound. The composition described in item 1 or item 2 of the scope of the patent application further contains a polymerization initiator. The composition described in item 1 or item 2 of the scope of the patent application further contains a solvent and has a solid content of 10-40% by mass. The composition described in item 10 of the scope of patent application, wherein the solvent contains water, and the content of the water is 0.1 to 1% by mass relative to the total mass of the composition. The composition described in item 1 or item 2 of the scope of patent application, wherein the content of the metal nitride-containing particles is 20 to 70% by mass relative to the total solid content of the composition. The composition described in item 1 or item 2 of the scope of the patent application further contains a dispersant, and the aforementioned dispersant contains polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyesters. At least one structure in the group. The composition described in item 13 of the scope of patent application, wherein the mass ratio of the dispersant to the metal nitride-containing particles is 0.05 to 0.30. The composition according to item 1 or item 2 of the scope of patent application, wherein the aforementioned metal nitride-containing particles are metal nitride-containing particles coated with an inorganic compound containing aluminum hydroxide. The composition described in item 1 or item 2 of the scope of the patent application, wherein the content of the atom A in the metal nitride-containing particles is 0.005-10% by mass. A method for manufacturing a composition, which is a method for manufacturing the composition described in any one of items 1 to 16 in the scope of the patent application, It includes a process for obtaining the aforementioned metal nitride-containing particles by the thermoplasma method, and the aforementioned process for obtaining the aforementioned metal nitride-containing particles by the thermoplasma method sequentially includes the following process A, process B, process C, and process A3- 1. Process A3-2, Process A3-3, Process A2, Process D, Process E, and Process F. Among the following series of processes, the aforementioned processes A~C and the aforementioned processes A3-1~A3-3 can be replaced The sequence of process A: the process of supplying the plasma torch with an inert gas that does not contain nitrogen as the plasma gas to generate a thermoplasma flame; Process B: the process of supplying the thermal plasma flame in the plasma torch with the transition metal Metal raw material powder, the process of evaporating the raw material metal powder to obtain the raw material metal in the gas phase; Process C: The process of cooling the raw material metal in the gas phase to obtain metal particles containing the transition metal; Process A3-1: To plasma A process in which inert gas without nitrogen is supplied as a plasma gas in the torch to generate a thermoplasma flame; Process A3-2: the raw material powder containing the atom A is supplied to the thermoplasma flame in the plasma torch to make the raw material powder The process of evaporation to obtain the atom A in the gas phase; Process A3-3: The process of cooling the atom A in the gas phase to obtain the atom A that is atomized; Process A2: The atom A that is atomized is mixed with the metal particles Process; Process D: Supply an inert gas containing nitrogen as a plasma gas to the plasma torch to generate a thermoplasma flame; Process E: Supply the thermoplasma flame in the plasma torch with the result obtained in Process A2. The aforementioned metal particles, the process of evaporating the aforementioned metal particles to obtain the raw material metal in the gas phase; Process F: A process of cooling the raw material metal in the gas phase to obtain the metal nitride-containing particles. A cured film obtained by using the composition described in any one of items 1 to 16 in the scope of the patent application. A color filter containing the cured film described in item 18 of the scope of patent application. A light-shielding film containing the cured film described in item 18 of the scope of patent application. A solid-state imaging element containing the cured film described in item 18 of the scope of patent application. An image display device containing the cured film described in item 18 of the scope of patent application.