TW201806850A - Composition, method for producing composition, cured film, color filter, light-blocking film, solid-state imaging element, and image display device - Google Patents

Abstract

Provided are: a composition with which a cured film exhibiting an excellent light-blocking performance, an excellent resolution, and an excellent electrode corrosion resistance can be produced; and a method for producing the composition; a cured film; a color filter; a light-blocking film; a solid-state imaging element; and moreover an image display device. The composition contains particles containing a metal nitride that contains specific atoms, and these metal nitride-containing particles contain the nitride of a transition metal from among the transition metals of groups 3-11 excluding titanium, wherein the transition metal has an electronegativity of 1.22-2.36.

Description

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

The invention relates to a composition, a method for producing 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 in various applications, for example, for producing a light-shielding film provided in a liquid crystal display device, a solid-state imaging device, and the like. Specifically, a color filter used in a liquid crystal display device includes a light-shielding film called a black matrix in order to block light between colored pixels, improve contrast, and the like. In addition, a solid-state imaging element is also provided with a light-shielding film in order to prevent noise and improve image quality. At present, a small and thin camera module is mounted on a portable terminal of an electronic device such as a mobile phone and a PDA (Personal Digital Assistant). This type of camera module usually includes solid-state imaging elements such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors and A lens for forming a subject image on a solid-state imaging element.

In addition, in recent years, focusing on the transmittance of light of a specific wavelength, research has been conducted on black powders of metal oxynitrides that have a lower transmittance (higher light-shielding property) of using a specific wavelength of light instead of titanium nitride. For example, Patent Document 1 discloses "a blue masking black powder, which is a black powder containing one or two kinds of nitrogen oxides of vanadium or niobium, characterized by an oxygen content of 16 wt% or less and a nitrogen content of 10 wt%. As described above, in the transmission spectrum of the dispersion having a powder concentration of 50 ppm, the transmittance X at 450 nm is 10.0% or less. " [Prior Art Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent Laid-Open No. 2012-96945

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

An object of the present invention is to provide a composition capable of producing a cured film having excellent light shielding properties, excellent resolving properties, and excellent electrode corrosion resistance. Another object of the present invention is to provide a method for producing a composition, a cured film, a color filter, a light-shielding film, a solid-state imaging device, and an image display device.

The present inventors have conducted intensive research in order to solve the above-mentioned problems, and as a result, have found a composition containing metal nitride-containing particles containing a predetermined atom, and the metal nitride-containing particles containing a transition metal in groups 3 to 11 A composition of a nitride of a transition metal other than titanium and a transition metal having an electronegativity of 1.22 to 2.36 can solve the above problems, and completed the present invention. That is, it was found that the above problems can be solved by the following configuration.

[1] A composition containing metal nitride-containing particles containing atom A, wherein the metal nitride-containing particles contain a transition metal other than titanium among transition metals of Groups 3 to 11 and have an electronegativity of 1.22 A nitride of a transition metal of ~ 2.36. The atom A is an element different from the transition metal constituting the nitride of a transition metal. It is at least one selected from the group consisting of boron, aluminum, silicon, manganese, iron, nickel, and silver. One type, and the content of the atom A in the metal nitride-containing particles is 0.00005 to 10% by mass. [2] The composition according to [1], wherein the 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 average primary particle diameter of the metal nitride-containing particles is 10 to 50 nm. [4] The composition according to any one of [1] to [3], further containing 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], wherein 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], further comprising a polymerizable compound. [9] The composition according to any one of [1] to [8], further comprising a polymerization initiator. [10] The composition according to any one of [1] to [9], further containing a solvent, and having a solid content of 10 to 40% by mass. [11] The composition according to [10], wherein the solvent contains water, and the content of water is 0.1 to 1% by mass based on 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 based on the total solid content of the composition. [13] The composition according to any one of [1] to [12], further containing a dispersant, the dispersant containing a member selected from 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 according to any one of [1] to [15], which comprises a process for obtaining particles containing metal nitride by a thermoplasma method. [17] A cured film obtained using the composition according to any one of [1] to [15]. [18] A color filter containing the cured film according to [17]. [19] A light-shielding film containing the hardened film according to [17]. [20] A solid-state imaging element comprising the cured film according to [17]. [21] An image display device comprising the cured film according to [17]. [Inventive effect]

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

Hereinafter, the composition will be described in detail for each component constituting the composition. In the present specification, a numerical range indicated by “～” means a range including numerical values described before and after “～” as a lower limit value and an upper limit value. In addition, in the description of the group (atomic group) in the present specification, the expressions that do not describe substitution and unsubstituted refer to those that do not include substituents and those that contain substituents. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) without a substituent, but also an alkyl group (substituted alkyl group) with a substituent. In this specification, "active light" or "radiation" means, for example, a bright line spectrum of a mercury lamp and an extreme ultraviolet (EUV: Extreme ultraviolet lithography light), an X-ray, an electron beam, and the like, represented by an excimer laser. In this specification, "light" means active light or radiation. Regarding "exposure" in this specification, unless otherwise specified, it is not limited to exposure based on the bright line spectrum of a mercury lamp, far-ultraviolet rays, X-rays, and EUV light represented by an excimer laser, and electron beam and ion beam. The depiction of the particle beam is also included in the exposure. In addition, in this specification, "(meth) acrylate" means an acrylate and a methacrylate. In addition, in this specification, "(meth) acrylic acid" means acrylic acid and methacrylic acid. In addition, in this specification, "(meth) acrylfluorenyl" means acrylfluorenyl and methacrylfluorenyl. In addition, in this specification, "(meth) acrylamide" means acrylamide and methacrylamide. In addition, in this specification, "monomer" and "monomer" have the same meaning. A monomer is different from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. A polymerizable group refers to a group that participates in a polymerization reaction. [Composition] The above composition is a composition containing metal nitride-containing particles containing atom A, wherein the metal nitride-containing particles contain a transition metal other than titanium among the transition metals of Groups 3 to 11 and are electrically negatively charged. A nitride of a transition metal having a property of 1.22 to 2.36, the atom A is an element different from the above transition metal, and is at least one 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 particles is 0.00005 to 10% by mass. Although the reason why the above composition has the effect of the present invention is not clear, the inventors and others have estimated the following. In addition, the mechanism by which the above-mentioned composition exerts the effects of the present invention is not limited based on the following estimation.

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

[Metal nitride-containing particle] The metal nitride-containing particle is a metal nitride-containing particle containing atom A. The form in which the metal nitride-containing particles contain atom A is not particularly limited, and may be ions, metal compounds (also containing complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, Included in any form such as nitrogen oxides, sulfides, and sulfur oxides. In addition, the atom A contained in the metal nitride-containing particle may exist as an impurity at an inter-lattice position, or may exist as an impurity in an amorphous state at a grain boundary.

<Atom A> The atom A is contained in a metal nitride-containing particle. 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, at least one selected from the group consisting of aluminum, silicon, iron, nickel, and silver is preferable from the viewpoint that the composition has more excellent effects of the present invention, and is selected from the group consisting of iron, silicon, and nickel. More preferably, at least one of the groups is composed. Atom A may be used alone or in combination of two or more.

The content of the atom A in the metal nitride-containing particles is 0.00005 to 10% by mass. If the content of the atom A is less than the lower limit value, the resolution of the cured film obtainable from the composition is poor. If the content of the atom A exceeds the upper limit, the light-shielding property of the cured film obtainable from the composition and the corrosion resistance of the electrode are poor. Among them, from the viewpoint that the cured film obtainable 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 the better. Moreover, if it is 0.00005 mass% or more and less than 10 mass%, the cured film obtainable by the said composition will have more excellent light-shielding property. Among them, the content of atom A in the metal nitride-containing particles was measured by an ICP (Inductively Coupled Plasma) emission spectroscopic analysis method.

<Nitride of transition metal> The above-mentioned metal nitride-containing particle contains a transition metal other than titanium among transition metals of Groups 3 to 11 and a transition metal nitride having an electronegativity of 1.22 to 2.36. Examples of the transition metal (electronegativity in parentheses) include Sc (1.36), Dy (1.22), Ho (1.23), Er (1.24), Tm (1.25), Lu (1.27) ), 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) for Group 4; V (1.63), Nb (1.6), Ta (for Group 5) 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 standpoint that the composition has 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 are more preferred, V, Cr, Y, Zr, Nb, Hf, Ta, W, or Re are further preferred, V, Cr, Y, Nb, Ta, W, or Re are particularly preferred, V or Nb Especially preferred is Nb.

The content of the "transition metal constituting a nitride of a 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 preferred. The content of the "transition metal constituting a nitride of a transition metal" in the metal nitride-containing particles can be analyzed by an ICP (Inductively Coupled Plasma) emission spectroscopic analysis method. The content of nitrogen atoms (N atoms) in the metal nitride-containing particles is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, and 10 to 40% by mass relative to the total mass of the metal nitride-containing particles. % Is further preferred. The nitrogen atom content can be analyzed by an inert gas fusion thermal conductivity method. The metal nitride-containing particles contain metal nitride as a main component, and may contain a part of oxygen atoms by oxidation of the particle surface or the like. The oxidation of the particle surface becomes more pronounced, for example, when oxygen is mixed during the synthesis of a metal nitride or when the particle diameter is small. The content of oxygen atoms in the metal nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass, and 5 to 30% by mass relative to the total mass of the metal nitride-containing particles. good. The content of oxygen atoms can be analyzed by an inert gas melting 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 determined by the BET (Brunauer, Emmett, Teller) method.

The metal nitride-containing particles may be composite particles containing metal nitride-containing particles and metal particles. Composite particles refer to particles in which metal nitride-containing particles and metal particles are composited or in a highly dispersed state. Among them, "combination" indicates that the particles are composed of two components of metal nitride and metal, and "highly dispersed state" indicates that metal nitride-containing particles and metal particles exist separately, and particles with a small amount of components are not Agglomerated and uniformly dispersed. The metal fine particles are not particularly limited, and examples thereof include 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 the group consisting of copper, gold, platinum, palladium, tin, cobalt, rhodium, and iridium, and these alloys is preferable, and at least one selected from the group consisting of copper, gold, platinum, tin, and these alloys 1 type is more preferable. 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, and specifically, an electric furnace method and a thermo-plasma method are used. Among these production methods, a thermoplasma method is preferred from the viewpoints of a small amount of impurities, a point of easy particle size consistency, and a point of high productivity. As a specific manufacturing method of the metal nitride-containing particle by the pyroplasma method, for example, a person using a metal particle manufacturing apparatus can be mentioned. The metal particle manufacturing device includes, for example, a plasma torch that generates a thermal plasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber containing a cooling function, a cyclone that classifies the generated metal particles, and recovery. The collection part of the metal fine particles. In addition, in this specification, a metal fine particle means the particle | grains which have a primary particle diameter containing a metal element of 20 nm-40 micrometers.

The method for producing metal nitride-containing particles using a metal particle production apparatus is not particularly limited, and a known method can be used. Among them, from the viewpoint of improving the yield of the metal nitride-containing particles having a predetermined average primary particle diameter as described below, it is preferable that the method for producing metal nitride-containing particles using a metal particle manufacturing apparatus includes a process shown below. . Process A: A process of supplying a plasma plasma torch without an inert gas containing nitrogen as a plasma gas to generate a thermal plasma flame. Process B: A process of supplying a metal raw material powder containing a transition metal to a thermoplasma flame in a plasma torch, and evaporating the metal raw material powder to obtain a raw material metal in a gas phase. Process C: a process of cooling the raw metal in the gas phase to obtain metal particles containing a transition metal. Process D: The process of supplying a plasma gas with an inert gas containing nitrogen as a plasma gas to generate a thermoplasma flame. Process E: A process of supplying metal particles containing a transition metal to a thermoplasma flame in a plasma torch, and evaporating the metal particles to obtain a raw material metal in a gas phase. Process F: a process of cooling the raw metal in the gas phase to obtain metal nitride-containing particles. In addition, the method for producing a metal nitride-containing particle may include the following process G as required after the above-mentioned process C and / or process F. Process G: a process of grading the obtained particles. Furthermore, 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 in which atom A is mixed into a metal raw material powder containing a transition metal. In addition, the following processes A3-1 to A3-3 may be included before the aforementioned process A2. Process A3-1: Supplying an inert gas containing no nitrogen to the plasma torch as a plasma gas to generate a thermoplasma flame. Process A3-2: Supply the raw material powder containing atom A to the thermoplasma flame in the plasma torch. Process A3-3 for evaporating the raw material powder to obtain atom A in the gas phase: process for cooling atom A in the gas phase to obtain atomized A in micronized state In addition, process G may be included after process A3-3 . In addition, in this specification, atomized atom A means particles containing atom A having a primary particle diameter of 20 nm to 40 μm.

In addition, it is preferable that the method for producing the metal nitride-containing particles 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 metal nitride-containing particles obtained in process F (or process G) are subjected to a nitriding treatment by exposing them to a mixed atmosphere of water vapor and nitrogen. In addition, if necessary, the method for producing the metal nitride-containing particles may further include a process G after the process H. Hereinafter, a preferred embodiment of each process will be described in detail.

・ Process A Process A is a process of supplying a plasma torch with an inert gas that does not contain nitrogen as the plasma gas to generate a plasma flame. The method for generating the pyroplasma flame is not particularly limited, and examples thereof include a DC arc discharge method, a multi-phase arc discharge method, a high-frequency plasma method, and a hybrid plasma method. The plasma method is preferred. There is no particular limitation on the method for generating the pyroplasma flame by the high-frequency plasma method. For example, a plasma gas is supplied into a plasma torch containing a coil for high-frequency oscillation and a quartz tube, and the high-frequency oscillation A method of applying a high-frequency current with a coil to obtain a pyroplasmic flame. As the plasma gas in the process A, an inert gas containing no nitrogen can be used. Examples of the inert gas that does not contain nitrogen include argon and hydrogen. Inert gas containing no nitrogen can be used alone or in combination of two or more.

・ Process A2 Process A2 is a process of mixing atom A into a metal raw material powder containing a transition metal. The method for mixing the raw metal powder and the atom A is not particularly limited, and a known method can be used. For example, the above-mentioned material supply device for supplying the metal raw material powder into the plasma torch may include a mixing and dispersing function. 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 for producing a metal nitride-containing particle, the following processes A3-1 to A3-3 may be included before the process A2.

・ Process B Process B is a process of supplying a metal raw material powder containing a transition metal to a thermoplasma flame in a plasma torch, and evaporating the metal raw material powder to obtain a raw material metal in a gas phase. As a method for supplying the metal raw material powder to the pyroplasma flame in the plasma torch, there is no particular limitation. From the standpoint that the obtained raw material metal in the gas phase becomes more uniform, it is preferable to use a carrier gas spray. In addition, as the carrier gas, an inert gas containing no nitrogen is preferably used. The state of the inert gas not containing nitrogen is as described above. In addition, when the method for producing metal nitride-containing particles contains the above-mentioned process A2, it is preferable that the metal raw material powder is maintained in a uniformly dispersed state between the time when the metal raw material powder is supplied into the plasma torch.

・ Process C Process C is a process of cooling raw material metals 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 metal in the gas phase obtained in the above-mentioned process B is introduced into a chamber containing the above-mentioned cooling function, and rapidly cooled in the chamber, thereby being able to generate metal particles having a desired particle size as described below. The generated metal fine particles are recovered, for example, by the recovery unit. The atmosphere in the chamber is preferably an inert gas that does not contain nitrogen. The state of the inert gas not containing nitrogen is as described above. In addition, metal particles containing a transition metal can be obtained by the processes A to C described above. Metal particles containing transition metals are easily evaporated in Process E. In addition, when the metal raw material powder contains impurities, the impurities can be removed by going through the processes A to C described above.

・ Process D Process D is a process of supplying a plasma torch with an inert gas containing nitrogen as a plasma gas to generate a thermoplasma flame. Examples of the nitrogen-containing inert gas include nitrogen and nitrogen containing an inert gas. Examples of the inert gas include argon and hydrogen. The nitrogen containing the inert gas is not particularly limited, and the content of nitrogen is usually about 10 to 90 mol%, and preferably about 30 to 60 mol%. Other states are the same as in Process A.

・ Process E Process E is a process of supplying metal particles containing a transition metal to a thermoplasma flame in a plasma torch, and evaporating the metal particles to obtain a raw material metal in a gas phase. As a method for supplying the metal particles to the pyroplasma 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 metal that becomes the metal particles in the process A to the process C is supplied to the pyroplasma flame, so the raw metal in the gas phase is easily obtained, and the state of the raw metal in the gas phase becomes more uniform.

• Process F Process F is a process of cooling the raw metal in the gas phase to obtain metal nitride-containing particles containing a transition metal nitride. 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. A preferred aspect of the inert gas containing nitrogen is as described above.

・ Process G Process G is a process for classifying the obtained metal fine particles and / or metal nitride-containing particles. The classification method is not particularly limited, and for example, a cyclone can be used. The cyclone separator has a container on a cone, and has the function of generating a swirling flow in the container and using centrifugal force to classify particles. The classification is preferably performed in an inert gas atmosphere. 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 to perform a nitriding treatment. By going through this process, the content of metal nitrides in the metal nitride-containing particles can be increased. The method for exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen is not particularly limited, and examples thereof include introducing the metal nitride-containing particles into a constant temperature filled with a gas mixed with water vapor and nitrogen. In the tank, the method of standing or stirring for a predetermined period of time is preferable from the standpoint that the surfaces and grain boundaries of the metal nitride-containing particles are more stable. In addition, as a mixing ratio of water vapor and nitrogen, if the relative humidity is 25 to 95% in the atmosphere, it is preferable. 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.

・ Process A3-1 ～ A3-3 Process A3-1 ～ A3-3 is a process (A3-1) of supplying a plasma plasma torch without an inert gas containing nitrogen as a plasma gas to generate a thermal plasma flame, The thermo-plasma flame in the torch supplies a raw material powder containing atom A and vaporizes the raw material powder to obtain atom A in the gas phase (A3-2), and cools atom A in the gas phase to obtain particles containing atom A. Process (A3-3). The states in each process are as follows: in the above process A, process B (instead of the metal raw material powder containing the transition metal, using the raw material powder containing the atom A), and process C (instead of the metal particles containing the transition metal, the atomized atom is obtained A.). In addition, by going through the above process, the atom A is atomized, and the atom A is easily evaporated in the process E. In addition, by the above-described 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 a metal nitride-containing particle containing atom A) As a preferred aspect of the method for producing a metal nitride-containing particle containing atom A, a method having Method for producing metal nitride-containing particles containing atom A in the following process.・ Process A: A process of supplying a plasma plasma torch without an inert gas containing nitrogen as a plasma gas to generate a thermoplasma flame. • Process B: A process of supplying a metal raw material powder containing a transition metal to a thermoplasma flame in a plasma torch, and evaporating the raw metal powder to obtain a raw metal in a gas phase. • Process C: a process of cooling the raw metal in the gas phase to obtain metal particles containing a transition metal.・ Process G: The process of classifying the obtained particles.・ Process A3-1: A process of supplying a plasma plasma torch containing an inert gas containing no nitrogen as a plasma gas to generate a thermoplasma flame. Process A3-2: Supplying a raw material containing atom A to the plasma plasma torch Powder, the process of evaporating the raw material powder to obtain the atom A of the gas phase, process A3-3: the process of cooling the atom A of the gas phase to obtain the atomized atom A, process G: classifying the obtained particles The process. • Process A2: A process of mixing atom A (in this case, atomized A) into a metal raw material powder (in this case, metal particles) containing a transition metal. • Process D: A process of supplying a plasma gas to an inert gas containing nitrogen as a plasma gas to generate a thermoplasma flame.・ Process E: A process of supplying metal particles containing a transition metal to a thermoplasma flame in a plasma torch, and evaporating the metal particles to obtain a raw material metal in a gas phase. • Process F: a process of cooling the raw 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 metal nitride-containing particles obtained in process G are exposed to a mixed atmosphere of water vapor and nitrogen to perform a nitriding treatment. In addition, in the above series of processes, the order of processes A to C and processes A3-1 to A3-3 can be replaced. That is, the processes A to C can be performed after the processes A3-1 to A3-3.

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

(Purification of raw metal powder and raw material powder) As raw metal powder containing transition metals (hereinafter, simply referred to as "metal raw material powder") and raw material powder containing atom A (hereinafter, simple It is called "raw material powder".), And is not particularly limited, and high purity is preferred. The content of the transition metal in the metal raw material powder is not particularly limited, and is preferably 99.99% or more, and more preferably 99.999% or more. The content of the atom A in the raw material powder is also the same.

The metal raw material powder and / or raw material powder may contain a 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. Examples of the impurities contained in the raw material powder include metal elements.

In the above composition, the effect of the present invention is exhibited by setting the content of the atom A in the metal nitride-containing particles to 0.00005 to 10% by mass. Therefore, if the metal raw material powder and / or the raw material powder contains the above-mentioned impurities unexpectedly, it is difficult to control the content of the atom A to a predetermined range, so that it is 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, 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 (separation and purification method) of removing impurities from the raw metal powder and / or raw material powder is not particularly limited. For example, for niobium, paragraph 0013 of JP 2012-211048 can be used The method described in ~ 0030 can also be used for other raw material metal powders and / or raw material powders.

(Coating of metal nitride-containing particles) The metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, the metal nitride-containing particle may be a metal nitride-containing particle having a coating layer formed of an inorganic compound and having a metal nitride-containing particle and a metal nitride-containing particle. The above-mentioned composition containing metal nitride-containing particles coated with an inorganic compound has more excellent dispersion stability. The inorganic compound is not particularly limited, and examples thereof include 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 easily forming a thinner film and easily forming a film with a higher coverage. When the refractive index of the metal nitride-containing particles is intended to be controlled, silicon oxide is preferred as a low refractive index coating, and zirconium hydroxide is preferred as a high refractive index coating. The method for coating the metal nitride-containing particles with an inorganic compound is not particularly limited, and the method for producing a metal nitride-containing particle preferably 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 an oxide and / or a hydroxide. The coating method is not particularly limited, and examples thereof include the following wet coating methods.

As a first wet coating method, first, the metal nitride-containing particles and water are mixed to prepare a slurry. Next, the 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, and decanted. After removing more alkali ions by a method and / or ion exchange resin, etc., the slurry is dried to obtain oxide-containing metal nitride-containing particles.

As a second wet coating method, first, the above-mentioned metal nitride-containing particles and an organic solvent such as an alcohol are mixed to prepare a slurry. Next, an organic metal compound such as an 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. When the slurry is fired at a high temperature, a sol-gel reaction is performed, and metal nitride-containing particles coated with an oxide can be obtained.

As a third wet coating method, a slurry containing an ionic liquid is formed using urea and aluminum chloride in the presence of metal nitride-containing particles. The metal nitride-containing particles are taken out from the slurry and dried, and then the metal nitride-containing particles are fired, whereby metal nitride-containing particles coated with aluminum hydroxide-containing hydroxide can be obtained. .

<Physical Properties of Metal Nitride-Containing Particles> (Conductivity) The conductivity of the metal nitride-containing particles is not particularly limited, but 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 more preferable, and 170 to 190 × 10 ⁴ S / m is more 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 after the metal nitride-containing particles is used. The obtained cured film has more excellent light-shielding properties and excellent electrode corrosion resistance. In addition, in this specification, the electrical conductivity shows 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 are placed in a measurement container of the measurement device, and then pressure is started. 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 this measurement result, the saturation volume resistivity under the condition that the volume resistivity is not affected by the pressure is obtained, and the conductivity (σ) is calculated using the obtained saturation volume resistivity according to the relationship of σ = 1 / ρ. The above-mentioned test was performed under a room temperature environment.

(Average primary particle diameter) The average primary particle diameter of the metal nitride-containing particles is not particularly limited, but is preferably 10 to 50 nm, more preferably 10 to 30 nm, and even more preferably 10 to 27 nm. When the average primary particle diameter is 27 nm or less, in a composition containing metal nitride-containing particles, the metal nitride-containing particles are less likely to precipitate, and as a result, the composition has more excellent stability over time. In addition, in this specification, an average primary particle diameter means the average particle diameter of a primary particle, and an 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 Example, and PGMEA was used. After the obtained dispersion was diluted 100 times, it was dropped on a carbon foil and dried. In addition, as the dispersant, a dispersant is used in which an example of a metal nitride is contained so that the primary particles of the metal nitride-containing particles can be recognized in an image obtained by the following method. Specific examples of the dispersant include the dispersants described in the examples. In addition, primary particles refer to independent particles without agglomeration. The transmission electron microscope (TEM: Transmission Electron Microscope) was used to observe the sample at a magnification of 20,000 times to obtain an image. Among the obtained metal nitride-containing particles, primary particles were selected, and the area of the primary particles was calculated by image processing. Next, the diameter when the obtained area was converted into a circle was calculated. This operation was performed on a total of 400 fields of primary particles of metal nitride-containing particles with 4 fields of view, and the average circle-evaluated diameter was arithmetically averaged as the average primary particle diameter of the metal nitride-containing particles.

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

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

The composition may contain one kind of organic solvent or two or more kinds of organic solvents. From the viewpoint of suppressing the particle size variation of the metal nitride-containing particles when the composition is adjusted, the organic composition may contain two or more kinds of organic solvents. A solvent is preferred. When two or more organic solvents are contained, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol It is preferable that two or more types of the group consisting of a monomethyl ether and propylene glycol monomethyl ether acetate are comprised.

When the 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 range.

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

When the composition further contains a solvent, the solid content of the composition is preferably 10 to 40% by mass. When the solid content of the composition is at most the upper limit value, the number of particles contained in the composition tends to be smaller. In addition, if the solid content of the composition is at least the lower limit value, the composition has more excellent coatability. The content of the metal nitride-containing particles is preferably 20 to 70% by mass based on the total solid content of the composition. When the content of the metal nitride-containing particles is equal to or higher than the lower limit, the composition has more excellent stability over time. In addition, if the content of the metal nitride-containing particles is equal to or less than the upper limit value, the number of particles contained in the composition tends to be smaller, and a composition capable of producing a cured film having more excellent resolvability can be obtained.

[Dispersant] The composition preferably contains a dispersant. The dispersant helps improve the dispersibility of the black pigment such as the metal nitride-containing particles. In this specification, a dispersant is a component different from the binder resin mentioned later. As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Among them, a polymer compound is preferred. Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated esters, modified polyurethanes, modified polyesters, Modified poly (meth) acrylate, (meth) acrylic copolymer, formalin naphthalenesulfonic acid], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and pigment derivatives. Polymer compounds can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers according to their structure.

<Polymer Compound> A black pigment, which is a preferred form of a polymer compound adsorbed on particles containing metal nitrides, and a pigment used as needed (hereinafter, also simply referred to as "black pigment"). Dispersion The surface plays a role in preventing the re-agglomeration of the dispersion. Therefore, it is preferable to include a terminally modified polymer, a graft polymer, and a block polymer that are fixed to the pigment surface. On the other hand, by modifying the surface of the metal nitride-containing particles, it is also possible to promote the adsorption 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, a "structural unit" has the same meaning as a "repeating unit." The polymer compound containing such a structural unit containing a graft chain has an affinity with a solvent due to the graft chain, and is therefore a dispersibility of a color pigment such as a black pigment and a dispersion stability over time (stability over time). Outstanding. In addition, with the presence of a graft chain, a polymer compound containing a structural unit containing the graft chain has a affinity with a polymerizable compound or another resin that can be used. As a result, residues are less likely to be generated during alkali development. When the graft chain becomes longer, the steric repulsion effect increases and the dispersibility of a black pigment or the like improves. On the other hand, if the graft chain is too long, the adsorption force to a colored pigment such as a black pigment decreases, and the dispersibility of the black pigment or the like tends to decrease. Therefore, the number of atoms other than hydrogen atoms in the graft chain is preferably 40 to 10,000, the number of atoms other than hydrogen atoms is more preferably 50 to 2,000, and the number of atoms other than hydrogen atoms is more preferably 60 to 500. good. Herein, the graft chain represents the root of the main chain of the copolymer (the atom bonded to the main chain from the main chain branched group) to the end of the main chain branched group.

The graft chain preferably contains a polymer structure. Examples of the polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, and a polyurethane. Ester structure, polyurea structure, polyamidine structure and polyether structure. In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility of black pigments, 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 type in the group is preferable, and a graft chain containing at least one of a polyester structure or a polyether structure is more preferable.

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

Corresponds to the structural units containing graft chains contained in polymer compounds. As commercially available macromonomers suitable for the synthesis of 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, (Manufactured by TOAGOSEI CO., LTD.), AK-32 (trade name, manufactured by TOAGOSEI CO., LTD.), Blemmer PP-100 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-500 (trade name, NOF CORPORATION. (Manufactured), Blemmer PP-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-1000 (trade name, manufactured by NOF CORPORATION.), Blemmer 55-PET-800 (trade name, NOF 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, manufactured by NOF CORPORATION.), Etc. Among them, AA-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), And AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.) Are used. , AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), 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 polyester. The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and a chain-shaped 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 be one in which the above-mentioned structures are contained in one dispersant alone, or one in which a plurality of these structures are contained in one dispersant. Here, the polycaprolactone structure refers to a structure containing, as a repeating unit, a ring opening of ε-caprolactone. The polyvalerolactone structure refers to a structure containing, as a repeating unit, a ring opening of δ-valerolactone. Specific examples of the dispersant containing a polycaprolactone structure include those in which j and k in the following formula (1) and the following formula (2) are five. Further, specific examples of the dispersant containing a polyvalerolactone structure include those in which j and k are 4 in the following formula (1) and the following formula (2). Specific examples of the dispersant containing a polymethyl acrylate structure include those in which X ⁵ in the following formula (4) is a hydrogen atom, and R ⁴ is a methyl group. Further, as a specific example of polymethyl methacrylate containing structures of the dispersing agent include the following formula (4) X ⁵ is a methyl group, and R ⁴ is methyl persons.

(Constitutional unit containing graft chain) As a structural unit containing a graft chain, a polymer compound preferably contains a structural unit represented by any one of the following formulae (1) to (4), and contains a structural unit represented by the following formula (1A): ), A 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 preferable.

[Chemical Formula 1]

In Formulae (1) to (4), W ¹ , W ² , W ^3, and W ⁴ each independently represent an oxygen atom or NH. It is preferable that W ¹ , W ² , W ³ and W ⁴ are oxygen atoms. In the formulae (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. As X ¹ , X ² , X ³ , X ^4, and X ⁵ , from the viewpoint of synthetic limitation, alkyl groups each independently having a hydrogen atom or a carbon number (number of carbon atoms) of 1 to 12 are preferred. Preferably, each independently is a hydrogen atom or a methyl group, and a methyl group is more preferable.

In the formulae (1) to (4), Y ¹ , Y ² , Y ^3, and Y ⁴ each independently represent a divalent linking group, and the structure of the linking group is not particularly limited. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following linking groups (Y-1) to (Y-21). In the structure shown below, A and B each represent a bonding site. Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of simplicity 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, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group. And amine groups. Among these, as the organic group represented by Z ¹ , Z ² , Z ^3, and Z ⁴ , especially from the viewpoint of improving dispersibility, those having a steric repulsive effect are preferred, and each independently has 5 to 6 carbon atoms. An alkyl or alkoxy group of 24 is preferred, wherein each is independently 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 Kew is better. The alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic groups.

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

In the formula (3), R ³ represents a branched or linear alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 2 or 3 carbon atoms is more preferred. When p is 2 to 500, a plurality of R ³ may be the same as each other or different from each other. In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. Examples of R ⁴ include a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and a hydrogen atom or an alkyl group is more preferable. When R ⁴ is an alkyl group, 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 preferred, and a linear alkyl group having 1 to 6 carbon atoms is more preferred. In formula (4), when q is 2 to 500, a plurality of X ⁵ and R ^{4 in the} graft copolymer may be the same as each other or different from each other.

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

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

[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 preferred from the viewpoint of the stability of the composition over time and developability.

[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 a structural unit containing a graft chain, the polymer compound preferably contains a 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 2 to 90% by mass conversion with respect to the total mass of the polymer compound. The range is preferable, and the range of 5 to 30% is more preferable. When the structural unit containing a graft chain is included in this range, the dispersibility of a black pigment is high, and the developability at the time of forming a hardened film is favorable.

(Hydrophobic structural unit) It is preferable that the polymer compound contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the graft chain). In the present invention, the hydrophobic structural unit is a structural unit that does not contain an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphate group, a phenolic hydroxyl group, and the like).

The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) 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 to 8. Thereby, the effect of this invention can be shown more reliably.

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

logP represents the common logarithm of the partition coefficient P (partition coefficient). It is a quantitative value representing the physical property value of how an organic compound is distributed in the two-phase equilibrium of oil (usually 1-octanol) and water. Expression. logP = log (Coil / Cwater) In the formula, Coil represents the Mohr concentration of the compound in the oil phase, and Cwater represents the Mohr concentration of the compound in the water phase. If the value of logP increases with a positive (plus) value between 0, it means that the oil solubility increases, and if the absolute value increases with minus (minus), it means an increase in water solubility. Parameters for estimating the hydrophobicity of organic compounds are widely used.

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

[Chemical Formula 5]

In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a carbon atom having 1 to 6 Alkyl (for example, methyl, ethyl, propyl, etc.). R ¹ , R ² and R ³ are more 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 imine group (-NH-), and an oxygen atom is preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

(Functional group capable of interacting with black pigment and the like) The polymer compound can introduce a functional group capable of interacting with colored pigments such as the black pigment. Among them, it is preferable that the polymer compound further includes a structural unit containing a functional group capable of interacting with a colored pigment such as a black pigment. Examples of the functional group that can interact with a color pigment such as the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group. When a polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, it contains a structural unit having an acid group, a structural unit having a basic group, a structural unit having a coordination group, or It is preferred 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 in the composition described above contains alkali-solubility as a dispersant that facilitates the dispersion of colored pigments such as black pigments. A composition containing such a polymer compound becomes an excellent light-shielding property of the exposed portion, and the alkali developability of the unexposed portion is improved. In addition, when the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be easily integrated with a solvent, and the coatability is also improved. It is presumed that this is because the acid groups in the structural unit containing acid groups easily interact with colored pigments such as black pigments, the polymer compounds stably disperse the colored pigments such as black pigments, and the polymer compounds that disperse the colored pigments such as black pigments The viscosity becomes low, and the polymer compound itself is easily and stably dispersed.

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

As a functional group that can interact with a color pigment such as a black pigment, that is, an acid group, for example, there are a carboxylic acid group, a sulfonic acid group, a phosphate group, or a phenolic hydroxyl group. One type is preferable, and a carboxylic acid group is more preferable from the viewpoints that a color pigment such as a black pigment has good adsorption and a high dispersibility of the color pigment. That is, it is preferable that the polymer compound 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 or two or more kinds of structural units containing an acid group. The polymer compound may or may not contain a structural unit containing an acid group, but when contained, the content of the structural unit containing an acid group is calculated in terms of mass, and it is preferably 5 to 80% relative to the total mass of the polymer compound. From the viewpoint of suppressing damage to the image intensity due to alkali development, 10 to 60% is more preferable.

Basic groups that are functional groups that can interact with colored pigments such as black pigments include primary amine groups, secondary amine groups, tertiary amine groups, heterocyclic rings containing N atoms, and amidine groups From the viewpoints of good adsorption of color pigments such as black pigments and high dispersibility of the color pigments, a tertiary amine group is preferred. The polymer compound may contain one or more of these basic groups. The polymer compound may or may not contain a structural unit containing a basic group, but when contained, the content of the structural unit containing a basic group is calculated by mass, and is 0.01% or more and 50% or less with respect to the total mass of the polymer compound. From the viewpoint of suppressing the development resistance, it is more preferable to be 0.01% or more and 30% or less.

Examples of functional groups that can interact with colored pigments such as black pigments, that is, coordination groups and reactive functional groups include, for example, acetoacetoxy, trialkoxysilyl, isocyanate groups, Acid anhydride and chlorin. From the standpoint of good adsorption of colored pigments such as black pigments and high dispersibility of colored pigments, acetamidine is preferred. The polymer compound may have one or two or more of these groups. The polymer compound may include a structural unit containing a coordinating group or a structural unit containing a reactive functional group, or may not contain it, but when contained, the content of these structural units is expressed in terms of mass relative to the total of the polymer compound. The quality is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of suppressing the obstructive development property.

When the polymer compound contains a functional group capable of interacting with a coloring pigment such as a black pigment in addition to the graft chain, the above-mentioned various functional groups capable of interacting with a coloring pigment such as a black pigment may be included, which is not particularly limited. How these functional groups are introduced, the polymer compound preferably contains one or more structural units selected from the structural units derived from the monomers represented by the following general formulae (iv) to (vi).

[Chemical Formula 6]

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

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

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

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

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

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

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

In the general formulae (iv) to (vi), Z ₁ represents a functional group capable of interacting with a colored pigment such as a black pigment other than the graft chain. A carboxylic acid group and a tertiary amine group are preferred, and a carboxylic acid group For the 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.), and an alkyl group having 1 to 6 carbon atoms (for example, methyl , ethyl and propyl, etc.), - Z ₁ or L ₁ -Z _1. Wherein, L ₁ and Z ₁ meaning the same as the above L ₁ and Z _1, preferred embodiments are also the same. R ¹⁴ , R ^15, and R ¹⁶ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

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

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

The content of the structural unit containing a functional group capable of interacting with a coloring pigment such as a black pigment from the viewpoint of interaction with a coloring pigment such as a black pigment, stability over time, and permeability to a developing solution, relative to the polymer The total mass of the compound is preferably from 0.05% by mass to 90% by mass, more preferably from 1.0% by mass to 80% by mass, and even more preferably from 10% by mass to 70% by mass.

(Other structural units) In addition, in order to improve various properties such as image strength, the polymer compound may be further added without impairing the effects of the present invention, and further contains structural units containing graft chains, hydrophobic structural units, and Coloring pigments, such as pigments, have different structural units that form functional groups that interact with each other and contain other structural units with 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 a radical polymerizable compound selected from acrylonitrile and methacrylonitrile. The polymer compound can use one or two or more of these other structural units, and its content is expressed in terms of mass, and relative to the total mass of the polymer compound, 0% to 80% is preferred, and 10% to 60% is preferred. The following are particularly preferred. When the content is within the above range, sufficient pattern-formability can be maintained.

(Physical properties of polymer compound) The acid value of the polymer compound is preferably in a range of 0 mgKOH / g or more and 160 mgKOH / g or less, more preferably in a range of 10 mgKOH / g or more and 140 mg KOH / g or less, and in a range of 20 mgKOH / g or more and 120 mgKOH. The range below / g is more preferable. When the acid value of the polymer compound is 160 mgKOH / g or less, the pattern peeling during development when forming a cured film is more effectively suppressed. In addition, when the acid value of the polymer compound is 10 mgKOH / g or more, alkali developability is further improved. In addition, if the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of colored 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, for example, from the average content of acid groups in the polymer compound. In addition, a resin having a desired acid value can be obtained by changing the content of a structural unit that is a component containing a polymer compound, that is, an acid group.

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

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

Specific examples of the polymer compound include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., "Disperbyk-101 (polyamidamine phosphate), 107 (carboxylic acid ester), 110 (contained by BYK Chemie) Acid-based copolymers), 111 (phosphoric acid-based dispersant), 130 (polyamidamine), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymers), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA4047, 4050-4010 to 4165 (polyurethane type), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (modified polymer manufactured by EFKA) Acrylate), 5010 (Polyamidate), 5765 (High Molecular Weight Polycarboxylate), 6220 (Fatty Acid Polyester), 6745 (Phthalocyanine Derivatives), 6750 (Azo Pigment Derivatives) ", 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) "," DISPARLON KS-860, 87 "manufactured by Kusumoto Chemicals, Ltd. 3SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "," DEMOL RN, N (formma naphthalenesulfonate) manufactured by Kao Corporation Forest polycondensate), MS, C, SN-B (formalin polycondensate of aromatic sulfonic acid) "," HOMOGENOL L-18 (polymeric polycarboxylic acid) "," EMULGEN 920, 930, 935, 985 (polyoxygen Ethylene Nonyl Phenyl Ether) "," ACETAMIN 86 (Stearylamine Acetate) "," SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) manufactured by The Lubrinzol corporation , 3000, 12000, 17000, 20000, 27000 (polymers containing functional units at the ends), 24000, 28000, 32000, 38500 (graft copolymers) "," Nikkor T106 (Polymer) manufactured by Nikkol Chemicals CO., LTD. Oxyethylene sorbitol monooleate), MYS-IEX (polyoxyethylene monostearate) ", manufactured by Kawaken Fine Chemicals CO., LTD., HINOAKUTO T-8000E, etc., manufactured by Shin-Etsu Chemical Co., Ltd. Polyorganosiloxane polymer KP341, "W001: cationic surfactant" manufactured by Yusho Co Ltd, Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene Non-ionic surfactants such as glycol distearate and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA" manufactured by MORISHITA & CO., LTD. -47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 "manufactured by SAN NOPCO LIMITED Polymer dispersant, "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION, and Sanyo Chemical Industries, Ltd. makes "Ionet (trade name) S-20" and the like. In addition, Acrylic base FFS-6752, Acrylic base FFS-187, Akurikuya-RD-F8, and Cyclomer P can also be used. Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, manufactured by BYK Additives & Instruments. DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822, and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. and the like. These polymer compounds may be used alone or in combination of two or more kinds.

In addition, as a specific example of the polymer compound, reference may be made to the polymer compound described in paragraphs 0127 to 0129 of Japanese Patent Application Laid-Open No. 2013-249417, which are incorporated into the present specification.

In addition, as the dispersant, in addition to the above-mentioned polymer compound, a graft copolymer of paragraphs 0037 to 0115 (corresponding to the columns of paragraphs 0075 to 0133 of US 2011/0124824) can be used. These contents can be referred to and incorporated into this specification. Furthermore, in addition to the above, it is also possible to use a side chain structure in which paragraphs 0028 to 0084 of Japanese Patent Application Laid-Open No. 2011-153283 (corresponding to columns of paragraphs 0075 to 0133 of US2011 / 0279759) contain acidic groups and are bonded via a linking group The constituent polymer compounds can be referred to and incorporated in this specification.

When the composition contains a dispersant, the content of the dispersant is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass, relative to the total solid content of the composition. The dispersant may be used singly or in combination of two or more kinds. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

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

In the above composition, the lower limit value of the mass ratio of the dispersant 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 more preferable. The upper limit value is preferably 270 or less, more preferably 150 or less, and even more preferably 50 or less. When the mass ratio of the dispersant to the atom A is within the above range, the composition described above has more excellent effects of the present invention. In particular, when the above-mentioned mass ratio is in the range of 1.5 to 50, the composition has further excellent effects of the present invention. Although the reason for this is not clear, it is thought that the atom A in the composition interacts with the dispersant, thereby affecting the pattern-forming property (hardenability and resolvability).

In the composition, the lower limit value of the mass ratio of the following polymerizable compound to the atom A (that is, (content of the polymerizable compound in the composition) / (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 more preferable. The upper limit value is preferably 50 or less, more preferably 11 or less, and still 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 more excellent effects of the present invention. When the 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 for this is not clear, it is thought that the atom A in the composition interacts with the polymerizable compound, thereby affecting the pattern-forming property (hardening property and resolving property).

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

Examples of the binder resin include a radical polymer containing a carboxylic acid group in a side chain. Examples of the radical polymer containing a carboxylic acid group in a side chain include Japanese Patent Laid-Open No. 59-44615, Japanese Patent No. 54-34327, Japanese Patent No. 58-12577, and Japanese Patent No. 54-25957 No., Japanese Patent Application Laid-Open No. 54-92723, Japanese Patent Application Laid-Open No. 59-53836, and Japanese Patent Application Laid-Open No. 59-71048. Examples of the radical polymer containing a carboxylic acid group in a side chain include hydrolysis of an acid anhydride unit obtained by separately or copolymerizing a monomer containing a carboxylic acid group and an monomer containing an acid anhydride. , Semi-esterified or semi-aminated resins and epoxy acrylates modified by unsaturated monocarboxylic acids and anhydrides. Examples of the carboxylic acid group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Moreover, the acidic cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned as an example. Examples of the acid anhydride-containing monomer include maleic anhydride. It is also useful to add a cyclic acid anhydride to a polymer containing a hydroxyl group. In addition, acetal-modified polyvinyl alcohol-based adhesive resins containing acid groups are described in various publications such as European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Laid-Open No. 2001-318463. The acetal-modified polyvinyl alcohol-based adhesive resin containing an acid group is preferable because it has excellent balance of film strength and developability. Moreover, as a water-soluble linear organic polymer, polyvinylpyrrolidone, polyethylene oxide, etc. are useful. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon and polyether, which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, are also useful. In 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 ethylene monomers as necessary] copolymers) and [allyl (meth) acrylate / (methyl) ) Acrylic acid / other addition polymerizable ethylene monomers as required] Copolymers are excellent in film strength, sensitivity, and developability, and are preferred. Examples of commercially available products include Acrylic base FF-187, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.), Akurikuya-RD-F8 (NIPPON SHOKUBAI CO., LTD.), And DAICEL-ALLNEX LTD. Manufacture of Cyclomer P (ACA) 230AA, etc.

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

In addition, as the binder resin, it is also preferable to use a polymer containing a structural unit 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 dispersant described above, and the preferred range is also the same. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. At least one kind of the carboxylic acid group, the sulfonic acid group, and the phosphoric acid group is preferable, and the carboxylic acid group is more preferable.

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

[Chemical Formula 7]

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

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

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

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

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

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

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

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

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

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

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

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

Content of the binder resin in the said composition is 0.1-30 mass% with respect to the total solid content of a composition, More preferably, it is 0.3-25 mass%. The adhesive resin can be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

The mass ratio of the binding resin to the metal nitride-containing particles (that is, (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, and 0.25 The following is more preferred, and 0.20 or less is further preferred. The lower limit is not particularly limited, but 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 using the composition has more excellent resolvability.

[Polymerizable Compound] The 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 compounds, and even more preferably five or more compounds. 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) acrylfluorenyl group.

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

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

As the polymerizable compound, dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku CO., LTD.), And dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku) can also be used. CO., LTD.), Dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku CO., LTD.), Dipentaerythritol hexa (meth) acrylate (as a commercial product) Sale product, KAYARAD DPHA; manufactured by Nippon Kayaku CO., LTD., A-DPH-12E; manufactured by Shin-Nakamura Chemical CO., LTD) and these (meth) acrylfluorenyl groups via ethylene glycol residues, propylene glycol residues The basic structure (for example, SR454, SR499 marketed by Sartomer company Inc.) is preferable. These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical CO., LTD) and KAYARAD RP-1040 (manufactured by Nippon Kayaku CO., LTD.) Can also be used. The following is a description of the state of a preferable polymerizable compound.

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

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

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

[Chemical Formula 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 remainder is a group 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 a 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.

A polymerizable compound containing a caprolactone structure is marketed, for example, by Nippon Kayaku CO., LTD. As the KAYARAD DPCA series. DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, and The number of groups represented by formula (Z-2) = 2, compounds where R ^{1 is} all a hydrogen atom), DPCA-30 (same formula, m = 1, the number of groups represented by formula (Z-2) = 3. Compounds in which R ^{1 is} all a hydrogen atom), DPCA-60 (same formula, m = 1, the number of groups represented by formula (Z-2) = 6, compounds in which R ^{1 is} all a hydrogen atom), DPCA -120 (a compound in which m = 2, the number of groups represented by the formula (Z-2) = 6, and all of R ¹ is a hydrogen atom) and the like.

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

[Chemical Formula 11]

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

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

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

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

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

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

[Chemical Formula 12]

[Chemical Formula 13]

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

As the polymerizable compound, urethane acrylic acid 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 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 an amine structure and / or sulfur contained in the molecule by using those described in JP-A-63-277653, JP-A-63-260909, and JP-A-105238. Additive polymerizable compounds having an ether structure can obtain a composition having a very excellent photosensitivity. Examples of commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp CO., LTD.), UA-7200 (manufactured by Shin-Nakamura Chemical CO., LTD), DPHA-40H (manufactured by Nippon Kayaku CO., LTD.), UA-306H, UA-306T, UA-306I, AH-600, T-600, 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 even more preferably 10.60 or more. In this specification, the SP value is obtained by the Hoy method unless otherwise specified (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118). In addition, the SP value is shown by omitting the unit, but the unit is cal ^1/2 cm ^-3/2 .

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.

Formula (Q3) [Chemical Formula 14]

In the 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 polymerizable group-containing substituent, and the carbon atom in the substituent may be substituted with a hetero atom. a and b each independently represent an integer of 1 to 5, and c and d each independently represent an integer of 0 to 4. R ¹ to R ⁴ each independently represent a substituent, e, f, g, and h each independently represent an integer of 0 or more, and the upper limits of e, f, g, and h are respectively from Ar ¹¹ to Ar ¹⁴ The number of substituents minus the value of a, b, c or d. However, 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 fused rings, X ¹ to X ⁴ and R ¹ to R ⁴ may be independently substituted with The benzene ring surrounded by a dotted line may be replaced by a ring other than the benzene ring surrounded by a dotted line.

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

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

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

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

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

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

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

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

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

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

Trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds or acetophenone compounds are further Preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is particularly preferred.

In particular, when a light-shielding film is produced using the above-mentioned composition, it is necessary to form a fine pattern in a sharp shape, and it is therefore important to develop it in the unexposed portion without residue with the hardenability. From such a viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when a fine pattern is formed, step exposure is used for the exposure for hardening. However, the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to be low. Therefore, when considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator when forming a fine pattern. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and this content is incorporated into the specification of the present application.

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

(Oxime compound) As a photopolymerization initiator, an oxime compound (oxime type initiator) is mentioned more suitably. In particular, the oxime compound has high sensitivity and high polymerization efficiency, and can be hardened irrespective of the color material concentration, and it is easy to design the color material concentration to be high, so it is preferable. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, or a compound described in JP 2006-342166 can be used. As the oxime compound that can be preferably used in the present invention, for example, 3-benzyloxyiminobutane-2-one and 3-ethoxyiminobutane-2-one can be mentioned. Ketone, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane- 1-keto, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Carbonyloxyimino-1-phenylpropane-1-one and the like. In addition, JCSPerkin II (1979) pp.1653-1660), JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japan Compounds described in JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166. Among commercially available products, IRGACURE-OXE01 (made by BASF), IRGACURE-OXE02 (made by BASF), IRGACURE-OXE03 (made by BASF), or IRGACURE-OXE04 (made by BASF) can be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), Adeka Arkls NCI-831 and Adeka Arkls NCI-930 (manufactured by ADEKA CORPORATION) or N-1919 (containing carbazole · oxime ester skeleton light) Starter (manufactured by ADEKA CORPORATION).

In addition, as the oxime compound other than the above, the compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole; and US Patent No. Compounds described in Gazette No. 7626957; compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into a pigment part; ketones described in International Publication No. 2009-131189 An oxime compound; a compound described in U.S. Patent No. 7,565,910 containing a triazine skeleton and an oxime skeleton in the same molecule; and Japanese Unexamined Patent Publication No. 2009-221114, which has a maximum absorption at 405 nm and a good sensitivity to a g-ray light source Of compounds; etc. For example, paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to preferably, and the contents are incorporated into the specification of the present application. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. The N-O bond of the oxime may be the oxime compound of the (E) form, the oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[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 nonmetal atomic group include an alkyl group, an aryl group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The substituent may be further substituted with another substituent. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a fluorenyloxy group, a fluorenyl group, an alkyl group, and an aryl group. As the monovalent substituent represented by B in the general formula (OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents. As the divalent organic group represented by A in the general formula (OX-1), an alkylene group, a cycloalkylene group, or an alkynyl group having 1 to 12 carbon atoms is preferred. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents.

As the photopolymerization initiator, a fluorine atom-containing oxime compound can also be used. Specific examples of the fluorine atom-containing oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2010-262028; compounds 24, 36-40 of Japanese Patent Application No. 2014-500852; Japanese Patent Laid-Open No. 2013 Compound (C-3) described in Gazette-164471; etc. This content is incorporated into this specification.

As the photopolymerization initiator, compounds represented by the following general formulae (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 a carbon number An aralkyl group of 7 to 30. When R ¹ and R ² are phenyl groups, the phenyl groups can be bonded to each other to form a fluorenyl group. R ³ and R ⁴ each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. An aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

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

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

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

[Chemical Formula 18]

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

When the composition contains a polymerization initiator, the content of the polymerization initiator relative to the total solid content in the composition is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and 1 to 10% by mass. Further preferred. The said composition may contain only 1 type of polymerization initiator, and may contain 2 or more types. When two or more kinds are included, it is preferable that the total measurement falls within the above range.

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

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

By containing a fluorine-based surfactant in the composition, the liquid characteristics (especially, fluidity) when the coating liquid is prepared can be further improved, and the uniformity of coating thickness and the liquid saving property can be further improved. That is, when a film is formed by using a coating liquid containing 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 applicability to the surface to be coated is improved. Therefore, it is possible to form a film having a uniform thickness with less variation in thickness.

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

Examples of the fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac F475479, Megafac F475, Megafac F475479 , 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, a compound described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used. As the fluorine-based surfactant, a block polymer can also be used. As a specific example, for example, a compound described in Japanese Patent Application Laid-Open No. 2011-89090 can be mentioned. As the fluorine-based surfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound containing a fluorine atom and a source containing 2 or more (5 or more is preferable) can also be preferably used. ) Repeating units of (meth) acrylate compounds of alkoxy groups (ethyleneoxy group and propyleneoxy group are preferred). 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 compound is preferably 3,000 to 50,000, and is, for example, 14,000. In addition, a fluorine-containing polymer containing an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, such as Megafac RS-101, RS-102, RS-718K, and RS-72 manufactured by DIC Corporation. -K and so on.

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

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

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

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

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

<Colorant> The composition may contain a coloring agent (hereinafter, simply referred to as a "coloring agent") other than the metal nitride-containing particles. The colorant is used, for example, to adjust the chromaticity of the composition, and a part of the metal nitride-containing particles can be replaced with the colorant within a range in which the OD (Optical Density) value does not decrease. Examples of such a coloring agent include pigments (black organic pigments, color organic pigments, and inorganic pigments) and dyes.

(Pigment) The pigment is not particularly limited, and a 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, 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 and so on.

In addition, as the green pigment, a zinc halide phthalocyanine pigment having an average number of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms can be used. Specific examples include compounds described in International Publication No. 2015/118720. These organic pigments can be used alone or in combination in order to improve color purity.

As the black pigment, various known black pigments can be used. Examples thereof include carbon black and / or a black metal-containing organic pigment shown below. Examples of the black metal-containing organic pigment include 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 alone, and can also be used as a mixture of two or more. In addition, a black pigment can be further combined with an inorganic pigment of another hue to produce a desired light-shielding property. Examples of specific inorganic pigments that can be used in combination include zinc white, lead white, zinc barium white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead red, and oxide. Iron red, chrome yellow, zinc yellow (1 zinc yellow, 2 zinc yellow), ultramarine blue, Prussian blue (ferrous potassium ferrocyanide), zircon gray, ochre yellow, chrome titanium yellow, chrome green, peacock, Victoria Green, iron blue (unrelated to Prussian blue), vanadium zirconium blue, chrome tin red, manganese red, 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 shades, but also a plurality of pigments may be used in combination.

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

(Dye) As the dye, for example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, and Japanese Patent Publication No. 2592207, U.S. Patent No. 4,850,001, U.S. Patent No. 5,667,920, U.S. Patent No. 505950, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, and Japanese Patent No. 6-51115 The pigment disclosed in Kaihei 6-194828 and the like. When distinguished as a chemical structure, a pyrazole azo compound, a pyrrole methylene compound, an aniline azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxonol compound, and pyridine can be used. Zolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazomethine compounds, and the like. As the dye, a pigment multimer can be used. Examples of the pigment multimer include compounds described in Japanese Patent Application Laid-Open No. 2011-213925 and Japanese Patent Application Laid-Open No. 2013-041097.

The composition may contain an extender pigment in addition to the colorant, if necessary. Examples of the constitution pigment include barium sulfate, barium carbonate, calcium carbonate, silicon dioxide, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in combination of two or more. The usage-amount of an extender pigment is 0-100 mass parts normally with respect to 100 mass parts of colorants, 5-50 mass parts is preferable, 10-40 mass parts is more preferable. Colorants and extender pigments can be used by modifying the surface of polymers.

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

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

<Pigment derivative> The said composition can contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group, or an iminomethyl phthalate. Examples of the organic pigment used to constitute the pigment derivative include dioxopyrrolopyrrole-based pigments, azo-based pigments, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, and dioxazine-based pigments. , Ringone-based pigments, fluorene-based pigments, thioindigo-based pigments, isoindolinone-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, Shihlin-based pigments, and metal complex-based pigments. 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 preferred, a carboxylic acid group and a sulfonic acid group are further preferred, and a sulfonic acid group is particularly preferred. As the basic group contained in the pigment derivative, an amine group is preferable, and a tertiary amine group is more preferable. Specific examples of the pigment derivative include the following compounds. In addition, reference can be made to the descriptions in paragraphs 0162 to 0183 of Japanese Patent Application Laid-Open No. 2011-252065, which are incorporated into this specification.

[Chemical Formula 20]

When the composition contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass relative to the total mass of the colorant. The said composition may contain only 1 type of pigment derivative, and may contain 2 or more types. When two or more kinds are contained, the total amount is preferably in the above range.

<Silane coupling agent> A silane coupling agent is a compound which contains a hydrolyzable group and the functional group other than that in a molecule | numerator. A hydrolyzable group such as an alkoxy group is bonded to a silicon atom. A hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond through a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, a fluorenyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. An alkoxy group having 4 or less carbon atoms or an alkenyl group having 4 or less carbon atoms is particularly preferred. In addition, when forming a cured film on a 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 silicon atoms bonded by hydrolyzable groups). It does not contain fluorine atom, silicon atom (except silicon atom bonded by hydrolyzable group), alkylene group substituted by silicon atom, straight-chain alkyl group having 8 or more carbon atoms, and 3 or more carbon atoms Is preferably a branched alkyl group.

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

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

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

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

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

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

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

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

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

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

The said composition may contain 1 type of silane coupling agent individually, and may contain 2 or more types. When the composition contains two or more kinds of silane coupling agents, the total amount may be within the above range.

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

<Polymerization inhibitor> The said composition may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, catechol, tert-butylcatechol, p-quinone, 4, 4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butylphenol), N-nitroso Phenylhydroxylamine cerium salt and the like. The content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on 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 kinds are contained, the total amount is preferably in the above range. In addition, if necessary, in order to prevent the polymerization from being hindered by oxygen, a higher fatty acid derivative such as behenic acid and / or behenyl behenate may be added, and it may be 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 based on the total solid content of the composition.

In addition to the above components, the following components may be further added to the above composition. For example, sensitizers, co-sensitizers, cross-linking agents, hardening accelerators, fillers, thermal hardening accelerators, plasticizers, diluents, and fat sensitizers can be added. Adhesion promoters and other auxiliaries on the substrate surface (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, interfacial tension modifiers, and chain transfer agents Etc.) and other well-known additives. These components can be referred to, for example, Japanese Patent Application Publication No. 2012-003225, paragraph numbers 0183 to 0228 (corresponding to US Patent Application Publication No. 2013/0034812, <0237> to <0309>), Japanese Patent Application Laid-Open No. 2008-250074 The descriptions of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of Japanese Patent Application Laid-Open No. 2013-195480 are incorporated in this specification.

[Manufacturing method of composition] The manufacturing method of the composition includes the following mixing and dispersion processes. In addition, it is more preferable to include a standing process and / or a filtering process. In the following, the preferred aspects of each process are described in detail.

<Mixing and Dispersing Process> The mixing and dispersing process is a process for obtaining a composition by mixing the above components by a known mixing method (for example, a mixer, a homogenizer, a high-pressure emulsifying device, a wet pulverizer, and a wet disperser). In the mixing and dispersing process, the components constituting the composition may be blended in a concentrated manner, or the components may be blended sequentially after being dissolved or dispersed in an organic solvent. In addition, the input sequence 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.

(Manufacturing Process of Dispersion Liquid) The manufacturing process of the dispersion liquid is a manufacturing process of mixing the metal nitride-containing particles, the dispersant, and the solvent, and dispersing the metal nitride-containing particles by the method described above. The remaining components can be mixed with the produced dispersion liquid to produce a composition. In the manufacturing process of the dispersion liquid, as the mechanical force for dispersing the pigment, compression, pressing, impact, cutting, or cavitation can be mentioned. Specific examples of these processes include bead mill, sand mill, roll mill, high-speed impeller, sand mixing, jet stream mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, it is possible to appropriately use "Distribution Technology Encyclopedia, Issued by Information Corporation, July 15, 2005" and "Distribution Technology (Suspension (Solid / Liquid Dispersion System) Centered Dispersion Technology and Practical Comprehensive Information on Industrial Applications" Collected and distributed by the Publishing Department of the Business Development Center, October 10, 1978. In addition, in the process for preparing the dispersion, the pigment can be refined by a salt milling process. The raw materials, equipment, and processing conditions used in the salt milling process can be, for example, those described in Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application No. 2012-046629. In addition, it is preferable that the method for producing the composition includes a process of obtaining the metal nitride-containing particles by a thermoplasma method. The process for obtaining the metal nitride-containing particles is performed before mixing the above components. The specific manufacturing process of the metal nitride-containing particle based on the thermoplasma method is as described above.

<Still Process> Before supplying the above-mentioned metal nitride-containing particles to a mixing and dispersion process or a process for preparing a dispersion, it is preferable to go through the following still process. The stationary process is a process in which the particles containing metal nitrides obtained by the pyroplasma method are not exposed to the atmosphere after they are manufactured, but in a sealed container whose oxygen concentration is controlled, and allowed to stand for a predetermined time (12 to 72 hours) Preferably, 12 to 48 hours is more preferred, and 12 to 24 hours is more preferred). At this time, the content of water in the sealed container is more preferably controlled.

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 the water content in the sealed container can be adjusted by adjusting the oxygen concentration and the amount of water in the inert gas supplied into the sealed container. As the inert gas, nitrogen and argon are preferred, and nitrogen is more preferred. After the above-mentioned standing process, the surfaces and grain boundaries of the metal nitride-containing particles become stable. This makes it possible to suppress the occurrence of pinholes in the cured film obtained 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 that the composition has more excellent effects of the present invention, it is preferable to replace the process H.

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

[Hardened film (light-shielding film)] The hardened film is obtained using the above composition. The cured film contains metal nitride-containing particles. The cured film is suitably used as a light-shielding film, and specifically, is suitable for light-shielding a peripheral portion of a light-receiving portion of an image sensor. Hereinafter, a case where a cured film is used as a light-shielding film in a peripheral portion of a light-receiving portion of an image sensor will be described as an example. 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 resolvability and electrode corrosion resistance.

The film thickness of the light-shielding film is not particularly limited. In view of the fact that the light-shielding film has more excellent effects of the present invention, the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and 0.3 μm or more and 10 μm. The following is more preferred, and more preferably 0.3 μm to 5 μm. 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 with a conventional composition using a black pigment. As the size of the light-shielding film (the length of one side of the light-shielding film provided around the light-receiving portion of the sensor), from the standpoint that the light-shielding film has more excellent effects of the present invention, 0.001 mm or more and 10 mm or less is preferred, and 0.05 mm It is more preferable that it is 7 mm or more, and it is more preferable that it is 0.1 mm or more and 3.5 mm or less. The above-mentioned composition has a high optical density per unit volume, so reducing the amount of coating, etc., is advantageous for microfabrication, and is excellent in resolvability and electrode corrosion resistance. Therefore, it can be used particularly preferably within the above range.

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

The manufacturing method of the color filter containing the said black matrix contains the following composition layer formation process, exposure process, and development process. Composition layer forming process: a process in which the above composition is coated on a substrate to form a composition layer (coating film). Exposure process: a process of exposing the composition layer through a photomask (hereinafter, also simply referred to as a “mask”). Development process: a process of developing the composition layer after exposure to form a patterned cured film (light-shielding film).

Specifically, the composition is coated on a substrate directly or via another layer to form a composition layer (composition layer forming process), and exposure is performed through a predetermined mask pattern, and only a portion of the coating film irradiated with light is exposed. The color filter of the present invention can be produced by curing (exposure process) and developing with a developer (developing process). Hereinafter, each process in the manufacturing method of the color filter containing the said black matrix is demonstrated.

<Composition Layer Formation Process> The composition layer formation process is a process in which the composition is applied 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 for solid-state imaging elements such as those with a transparent conductive film attached thereto ( Examples include silicone substrates, CCD (Charge Coupled Device) substrates, and CMOS (Complementary Metal-Oxide Semiconductor) substrates. In addition, in order to improve adhesion to the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate, an undercoat layer may be provided on these substrates as needed.

As a coating method for applying the composition to 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 a solid-state imaging element, the coating film thickness of the composition is preferably 0.35 μm or more and 1.5 μm or less, and 0.40 μm or more and 1.0 μm or less from the viewpoint of resolution. For the better.

The composition applied to the substrate is usually dried under conditions of 70 ° C. to 110 ° C. and 2 minutes to 4 minutes. Thereby, a composition layer can be formed.

<Exposure Process> The exposure process is a process of exposing the composition layer (coating film) formed in the composition layer forming process through a mask, and curing only a part of the coating film irradiated with light. The exposure is preferably performed by irradiation with 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 preferable. 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 a light-shielding film for a solid-state imaging element, exposure by an i-ray stepper is preferable.

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

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

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

Moreover, the manufacturing method of the color filter containing the said hardened film (black matrix) may include the hardening process which hardens a hardened film by heating and / or exposure after the said development process.

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

[Solid-state imaging element] The solid-state imaging element includes the cured film (black matrix). The solid-state imaging element preferably includes a color filter including a black matrix and a pattern-shaped film including pixels of other colors (3 colors or 4 colors) as required. The solid-state imaging element is not particularly limited as long as it contains the black matrix and functions as a solid-state imaging element. For example, the solid-state imaging element may include a solid-state imaging element (CCD image sensor and CMOS image sensor) on the substrate. Light-receiving area, such as a plurality of photodiodes, polycrystalline silicon, and other light-receiving elements, the solid-state imaging element of the black matrix is included on the surface opposite to the light-receiving element formation surface of the substrate. In addition, the color filter may have a structure in which a hardened film forming each color pixel is embedded in a space partitioned into a grid shape by a partition wall, for example. It is preferable that the partition wall has a low refractive index for each color pixel. Examples of the imaging element including such a structure include solid-state imaging elements described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Laid-Open No. 2014-179577.

[Image display device] The cured film is suitable for an image display device such as a liquid crystal display device and an organic electroluminescence display device.

The definition of image display devices and the details of each image display device are described in, for example, "Electronic display device (by Sasaki Akio, Kogyo Chosakai Publishing CO., LTD. 1990)", "Display device (Ibuki Junaki Book, Industrial Book Co., Ltd., published in the first year of Heisei) ". The liquid crystal display device is described in, for example, “Second-generation liquid crystal display technology (edited by Ryuo Uchida, Kogyo Chosakai Publishing CO., LTD., 1994)”. The cured film is suitable for, for example, a liquid crystal display device according to the method described in the "second generation liquid crystal display technology".

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

In addition, as another aspect of the liquid crystal display device, at least one of the light-transmitting pair of substrates includes at least a color filter, a liquid crystal layer, and a liquid crystal driving mechanism. The liquid crystal driving mechanism includes an active element (for example, a TFT ( Thin Film Transistor)), and each active element includes a color filter containing the hardened film (black matrix) described above.

The color filter including the cured film is suitable for a color TFT (Thin Film Transistor) liquid crystal display device. A color TFT-type liquid crystal display device is described in, for example, "color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD. 1996)". In addition, the above color filters are also suitable for: lateral electric field driving methods such as IPS (In Plane Switching); pixel segmentation methods such as MVA (Multi-domain Vertical Alignment); and other perspectives are enlarged LCD 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).

The color filter is suitable for a bright and high-definition COA (Color-filter On Array) type liquid crystal display device. In the liquid crystal display device of the COA method, the required characteristics of the color filter may require the required characteristics of the interlayer insulation film in addition to the usual required characteristics, that is, the low dielectric constant and the resistance to the release liquid. The COA-type liquid crystal display device including the color filter has more excellent resolvability or more excellent durability. In addition, in order to meet the required characteristics of a low dielectric constant, a resin film may be further included on the color filter layer.

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

The liquid crystal display device may include 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 color filter. The color filter can be applied to a liquid crystal display device including these known members. These components are described in, for example, "'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Shimadaro CMC-Group. Issued in 1994)", "Current Status and Future Outlook of the Liquid Crystal Related Market in 2003 (Volume 2) (Table Ryoji Fuji Chimera Research Institute, Inc., 2003). " The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et.al) and the monthly display of December 2005, pages 18 to 24 (Island Kangyu), and the monthly display of December 2005, pages 25 to 30. (Yaki Takaki) and so on.

In addition, the above-mentioned cured film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smart phones, and digital cameras; OA (Office Automation) devices such as multifunction printers and scanners; surveillance cameras, and bar code readers And industrial teller machines (ATM: automated teller machine), high-speed cameras, and personal authentication using face image authentication; automotive camera equipment; medical cameras such as endoscopes, capsule endoscopes, and catheters Equipment; biosensors, biosensors, military surveillance cameras, stereo map cameras, meteorological and ocean observation cameras, land resource surveillance cameras, and space astronomy and deep space target exploration cameras The light-shielding members and light-shielding layers of optical filters and modules used in equipment are further suitable for anti-reflection members and anti-reflection layers.

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

The cured film is suitable as an optical filter and an optical film used in a quantum dot display. Furthermore, it is suitable as a member which provides a light shielding function and an antireflection function. Examples of quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960 Recorder. [Example]

Hereinafter, the above-mentioned composition and the like will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be interpreted restrictively by the embodiments shown below.

[Production of Metal Nitride-Containing Particles P-1] The metal nitride-containing particles P-1 were produced by the following method. First, niobium (powder) <100-325 mesh> manufactured by Mituwa Chemistry, which contains niobium as a transition metal, is prepared 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 spectroscopic analysis. 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 metal raw material powder was subjected to a plasma treatment in Ar gas (processing conditions are based on the following plasma treatment (1)) to perform metal micronization. When the average primary particle diameter of the obtained metal fine particles was measured, it was 80 nm. The average primary particle diameter was determined by the following method. Sample: A dispersion liquid (metal fine particles 25% by mass, the following dispersant A7.5% by mass, PGMEA; propylene glycol monomethyl ether acetic acid) was prepared by the same method as [Preparation of metal nitride-containing particle dispersion liquid] described later. Ester solvent (67.5% by mass), and the obtained dispersion was diluted 100 times with PGMEA, and then the solution was dropped on a carbon foil and dried. The transmission electron microscope (TEM: Transmission Electron Microscope) was used to observe the sample at a magnification of 20,000 times to obtain an image. The area of the metal particles in the obtained image was calculated by image processing. Next, the diameter when the obtained area was converted into a circle was calculated. This operation was performed on a total of 400 metal particles of 4 fields of view (about 3,000 metal particles were confirmed in each field of view), and the circle-evaluated diameter was arithmetically averaged as the average primary particle diameter of the metal particles.

In addition, the impurities contained in the metal fine particles were measured by the above method. As a result, no impurities were detected. In addition, if no impurity is detected by the above method, the content of the impurity is less than 20 ppm with respect to the total mass of the metal fine particles.

<Plasma treatment (1)> Plasma treatment (1) was performed by the following method. That is, the apparatus according to the black composite fine particle manufacturing apparatus described in FIG. 1 of the International Publication No. 2010/147098 pamphlet was used as a metal fine particle manufacturing apparatus, and plasma processing was performed under the following conditions (1).・ High-frequency voltage applied to the coil for high-frequency oscillation: frequency, about 4MHz, voltage, about 80kVA ・ plasma gas: argon (supply amount 100L / min) ・ carrier gas: argon (supply amount 10L / min) ・Atmosphere in the chamber: Argon (supply amount 1000L / min, flow velocity in the chamber 5m / sec) ・ Atmosphere in the cyclone: Argon, internal pressure: 50kPa ・ Speed of supplying material from the chamber to the cyclone: 10m / s (average value)

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

Next, the metal fine particles obtained by the above and atomized atom A were mixed to obtain a raw metal powder. This raw metal powder was subjected to a plasma treatment in nitrogen (processing conditions are 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 coil for high-frequency oscillation: frequency, about 4MHz, voltage, about 80kVA ・ plasma gas: argon and nitrogen (supply amounts are 50L / min) ・ carrier gas: nitrogen (supply amount 10L / min) ・ Atmosphere in the chamber: Nitrogen (supply amount 1000L / min, flow velocity in the chamber 5m / sec) ・ Atmosphere in the cyclone: Nitrogen, internal pressure 50kPa ・ Speed of supplying material from the chamber to the cyclone: 10m / s (average value)

Using Ar gas, the metal nitride-containing particles after the plasma treatment (2) is completed, the relative humidity of 95% in the atmosphere through the split-type humidity supply device SRH manufactured by NIHON SHINTECH CO., LTD. Under the conditions, nitrogen at 20 ° C was introduced and left to stand for 24 hours. Thereafter, the obtained metal nitride-containing particles were classified using a TTSP separator manufactured by Hosokawa Micron Group under the condition that the yield became 10%, thereby obtaining a powder of metal nitride-containing particles P-1. In addition, nitrogen was supplied to the separator.

The average primary particle diameter of the metal nitride-containing particles P-1 was measured. As a result, it was 12 nm. The conductivity of the metal nitride-containing particles P-1 was measured. As a result, it was 180 × 10 ⁴ S / m. The average primary particle diameter is the average primary particle diameter measured by the method described above. In addition, the said electric conductivity is the electric conductivity measured by the following method. The measurement of the electrical conductivity was measured by the following method using a powder resistance measurement system MCP-PD51 manufactured by Mitsubishi Chemical Analytech CO., LTD. First, 1 g of metal nitride-containing particles were charged into a φ20 mm measuring container of the above-mentioned measuring device, and then pressure was started. The pressure was 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 results, the saturation volume resistivity under the condition that the volume resistivity is not affected by the pressure is obtained. Using the obtained saturation volume resistivity, the conductivity (σ) is calculated from the relationship of σ = 1 / ρ. The above-mentioned test was performed under a room temperature environment.

[Production of Metal Nitride-Containing Particles P-2 to P-7, P-C1, and P-C5] In addition to setting the content of the atom A as described in Table 1, the content of the atom A was determined by comparing with the metal nitride-containing particles. Particle P-1 was produced in the same manner as metal nitride-containing particles P-2 to P-7, P-C1, and P-C5. In addition, the average primary particle diameter of the metal fine particles, the average primary particle diameter of the metal nitride-containing particles, and the electrical conductivity during the production of the metal nitride-containing particles are shown in Table 1.

[Production of Metal Nitride-Containing Particles P-C2] A metal nitride-containing particle P was produced by the same method as the metal nitride-containing particle P-1 except that atom A was not added to the transition metal raw material. -C2. In addition, the average primary particle diameter of the metal fine particles, the average primary particle diameter of the metal nitride-containing particles, and the electrical conductivity during the production of the metal nitride-containing particles are shown in Table 1.

[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 to this, metal nitrogen-containing particles were used. The particles P-1 of the compound were prepared in the same manner as the particles P-8 to P-15 of the metal nitride. In addition, the average primary particle diameter of the metal fine particles, the average primary particle diameter of the metal nitride-containing particles, and the electrical conductivity during the production of the metal nitride-containing particles are shown in Table 1.

[Preparation of Metal Nitride-Containing Particles P-C3 and P-C4] Instead of the transition metal raw material, each of the raw materials shown in Table 1 was used, and atom A was not added. 1 In the same manner, metal nitride-containing particles P-C3 and P-C4 were produced. In addition, the average primary particle diameter of the metal fine particles, the average primary particle diameter of the metal nitride-containing particles, and the electrical conductivity during the production of the metal nitride-containing particles are shown in Table 1.

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

・ Nb powder: Niobium (powder) made by Mituwa Chemistry. <100-325mesh> ・ V powder: Metal vanadium powder VHO made by TAIYO KOKO Co., LTD. ・ Zr powder: Zirconium powder made 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. Degassing electrolytic metal chromium powder Re powder: Rhenium alloy powder manufactured by Rhenium Alloys, Inc. W powder: tungsten powder AW3110 manufactured by Eurotungsten ・ Al powder: aluminum powder No. 22000 manufactured by METAL POWDER CO., LTD. Powder: Silicon powder manufactured by Furuchi Chemical Corporation ・ Fe powder: Fe powder JIP 270M manufactured by JFE STEEL CORPORATION ・ Ni powder: Ni powder 300 nm product manufactured by Toho Titanium Corporation ・ Ag powder: Ag powder Mitsui Mining & Smelting Co., Ltd. made SPQ03R

In addition, "ppm" in the following Table 1 represents mass ppm. In addition, in the table, "not detected" indicates a result of measurement by the above-mentioned measurement method, no impurity was detected, and specifically, 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, so the measurement is not performed. By this, "not measured" means that it is actually less than 20 mass ppm (calculated to be less than 5 mass ppm).

[Table 1]

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

・ Dispersant A [Chemical Formula 21]

・ Dispersant B [Chemical Formula 22]

・ Dispersant C [Chemical Formula 23]

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

・ Resin A: Akurikuya 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 formula below) [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

<Surfactant> ・ F-556: Megafac F-556 (manufactured by DIC Corporation)

<Organic solvents> ・ PGMEA: propylene glycol monomethyl ether acetate ・ CPN: cyclopentanone ・ Bu acetate: butyl acetate

[Preparation of Metal Nitride-Containing Particle Dispersion Liquid] First, the metal nitride-containing particles, a dispersant, and an organic solvent were mixed for 15 minutes with a mixer (EURA manufactured by IKA Works GmbH & CO. KG) to obtain the above-mentioned components. Mixed liquid. Next, the obtained mixed liquid was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by SHINMARU ENTERPRISES CORPORATION to obtain a metal nitride-containing particle dispersion liquid. Moreover, it added so that the mass ratio (D / P) of a dispersing agent with respect to the metal nitride containing particle may become the value shown in the Example and the comparative example of Table 3.

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

[Preparation of composition] Next, the above-mentioned metal nitride-containing particle dispersion liquid, a binding resin, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a surfactant were mixed and stirred, and the following Tables 2 and 3 were obtained. Each composition of Examples and Comparative Examples is shown. In addition, the content of each component in Table 2 is all by mass.

[Table 2]

<Measurement of Moisture Content in Composition> About the moisture content of each composition in Examples and Comparative Examples, MKV-710 (trade name, KYOTO ELECTRONICS INDUSTRY CO., LTD.) ). The results are shown in Table 3.

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

[OD value] A coating film was formed by spin coating on a glass plate (EagleXG, manufactured by Corning Incorporated) with a thickness of 0.7 mm and 10 cm square, using each composition. At this time, the rotation speed was adjusted so that the film thickness became 1.5 μm based on the solid content concentration of each composition. The formed coating film was dried on a hot plate by a heat treatment at 100 ° C for 2 minutes to obtain a cured film. The OD value of the substrate containing the obtained cured film was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation.). The larger the OD value, the more excellent the light-shielding property of the cured film. In addition, evaluation was performed based on the following criteria. In practical use, "C" or more 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 over time] To a container having a diameter of 50 mm and a capacity of 100 mL, 100 mL of a metal nitride-containing particle dispersion was added, and left to stand at room temperature for 9 minutes. After being left to stand, a 1-cm metal-nitride-containing particle dispersion liquid was collected from the supernatant, and its solid content concentration was measured by evaporation to dryness. The change rate of the solid content of the metal nitride-containing particle dispersion before and after standing was calculated by the following formula, and the value was evaluated by the following criteria. In practical use, "C" or more is preferred. (Formula) Solid content change rate = (Initial solid content concentration)-(Solid content concentration of 1 cm of supernatant) A: Solid content change rate is less than 3% B: Solid content change rate is more than 3% and less than 7% C : Solid content change rate is 7% or more and less than 12% D: Solid content change rate is 12% or more

[Number of Particles] A sample solution in which the above composition was diluted 500 times with PGMEA was prepared, and a flow particle image analysis apparatus (trade name "FPIA", manufactured by Malvern Instruments Ltd.) was used to measure the content of the sample solution in 10 ml. The number of metal nitride-containing particles having a size of 10 μm or more. Evaluation was performed based on the following criteria. In practical use, "C" or more is preferred. A: The number of particles is 3 or less B: The number of particles is 4 to 10 C: The number of particles is 11 to 20 D: The number of particles is 21 or more

[Resolution] An 8-inch silicon substrate was coated with the above composition to prepare 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 according to the solid content concentration of each composition. The obtained coating film was heat-treated at 100 ° C. for 2 minutes using a hot plate as a pre-baking treatment. The pre-baked substrate with a coating film was exposed (negative) to the coating film with an i-ray stepper (FPA3000i5 + manufactured by Canon Inc.) through a mask having an island-shaped pattern having a width of 10 μm. Coater Developer ACT8 manufactured by Tokyo Electron Limited was used for the exposed coating film, and CD-2060 (manufactured by FUJIFILM Electronic Materials CO., LTD.) Was used as a developer. The coating was subjected to spin-on immersion development for 30 seconds. Pure water was rinsed. The developed coating film was post-baked (temperature: 220 ° C, time: 10 minutes). The pattern shape of the post-bake coating film was measured by a scanning electron microscope (Scanning Electron Microscope). Specifically, the width of the island was measured and evaluated by the following criteria. In practical use, "C" or more is preferred. A: Island-like width is 9.5 μm to 10.5 μm B: Island-like width is 8 μm or more and less than 9.5 μm, or more than 10.5 μm and 12 μm or less C: Island-like width is less than 8 μm or more than 12 μm D: Pattern peeling Or an island is not formed due to insufficient development.

[Corrosion Resistance of Electrode] A coating film was formed on the image sensor device substrate by spin coating using the composition. The coating film was pre-baked on a hot plate at 100 ° C for 2 minutes. With respect to the substrate after the pre-baking treatment, 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 electrode portion on the peripheral portion of the light-receiving portion on the substrate. In addition, a heating plate was subjected to a heat treatment at 220 ° C. for 5 minutes (post-baking process). After forming the light-shielding film, the substrate was exposed to 130 ° C. and a relative humidity of 90% for 7 days, and then wiring was formed by bonding wires. The occurrence of disconnection was evaluated by a bonding wire inspection device manufactured by Canon Machinery Inc. The number of evaluated wafers was 50, and the number of wirings per wafer was 40. Evaluation was performed by the following criteria. In practical use, "C" or more is preferred. A: The number of broken wires is less than one B: The number of broken wires is 2 or more and less than 5 C: The number of broken wires is 5 or more and less than 10 D: The number of broken wires is 10 or more

[table 3]

From the results shown in Table 3, it can be seen that Example 1 using metal nitride-containing particles containing a transition metal other than titanium among transition metals of Groups 3 to 11 and a transition metal having a electronegativity of 1.22 to 2.36 A cured film (light-shielding film) made of a composition of ~ 32 has excellent light-shielding properties, excellent resolvability, and excellent electrode corrosion resistance. On the other hand, the desired effect was not obtained with the cured film (light-shielding film) produced using the composition of Comparative Examples 1 to 5. In addition, the hardened films (light-shielding films) produced using the compositions of Examples 3, 8, 10, 12, 13, 14, and 15 in which transition metals are niobium, vanadium, tantalum, yttrium, chromium, rhenium, or tungsten, respectively, have a specific ratio. The hardened film (light-shielding film) produced using the composition of Example 9 or 11 made of transition metal-based zirconium or hafnium has a better OD value (light-shielding property). Among them, the hardened film (light-shielding film) produced using the composition of Example 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 fewer 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 fewer particles than the composition of Example 24 exceeding 1% by mass. In addition, the composition of Example 2 in which the content of the 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 exceeding 70% by mass, and the obtained cured film (light-shielding film) has more excellent resolvability. In addition, the composition of Example 2 having a mass ratio of the dispersant with respect to the metal nitride-containing particles of 0.05 to 0.30 has more excellent stability over time than the composition of Example 32 having a mass ratio of less than 0.05. . In addition, the cured film (light-shielding film) produced using the composition of Example 2 has a better resolving property than the cured film (light-shielding film) produced using the composition of Example 18.

[Production and evaluation of metal nitride-containing particles P-1 (A)] The metal nitride-containing particles P-1 (A) and the metal nitride-containing particles P-1 (A) were produced by the following method. The surface of the metal nitride-containing particles P-1 produced by the above method is coated with aluminum hydroxide. First, 100 g of metal nitride-containing particles P-1 were weighed and added to 750 mL of pure water to disperse them well to obtain a slurry. Next, a solution obtained by dissolving 220 g of an aluminum chloride aqueous solution having a concentration of 10% by mass as alumina and 160 g of urea in 500 mL of water was added to the above slurry 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. Thus, the surface of the metal nitride-containing particles P-1 was coated with aluminum hydroxide. Particles of metal nitride P-1 (A). The average primary particle diameter of the metal nitride-containing particles P-1 (A) was 13 nm, and the electrical conductivity was 100 S / m. Next, using the metal nitride-containing particles P-1 (A), a dispersion liquid and a composition were prepared by the same method as in Example 1 above, and the OD value, resolution, electrode rottenness, and time The stability and particles were evaluated, and the results were the same as those of Example 1 using the metal nitride-containing particles P-1.

[Production and Evaluation of Metal Nitride-Containing Particles P-2 (A) to P-15 (A)] The metal nitride-containing particles were used in the same manner as the above-mentioned metal nitride-containing particles P-1 (A). The particles P-2 to P-15 were made of metal nitride-containing particles P-2 (A) to P-15 (A). Table 4 shows the average primary particle size and the electrical conductivity. Next, using the metal nitride-containing particles P-2 (A) to P-15 (A), a dispersion liquid and a composition were prepared by the same method as in Examples 2 to 32 above, and the OD value and resolution were determined. The electrode's rottenness, stability over time, and particles were evaluated. The results were the same as those of Examples 2 to 32 using particles P-2 to P-15 containing metal nitrides.

[Table 4]

In Example 1, the polymerization initiator was replaced from OXE-02 to Irgacure OXE03 (trade name, manufactured by BASF), and the same method was used for evaluation. As a result, it was found that the same results as in Example can be obtained. 1 same result. Moreover, compared with Example 1, it is more robust with respect to the exposure amount, and it is possible to maintain the resolution even when the exposure amount is reduced.

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

Except that the polymerizable compound was replaced by the polymerizable compound M1 with the polymerizable compound M2 in Example 1, it was evaluated by the same method. As a result, it was found that the same results as in Example 1 were obtained.

In Example 1, the polymerizable compound was extracted from the polymerizable compound M1 without changing the content of the polymerizable compound with respect to all the components, and replaced with a mixture of the polymerizable compounds M1 and M2 (mass ratio 1: 1) ), Except that evaluation was performed by the same method. As a result, it was found that the same result as that of Example 1 can be obtained.

Except that PGMEA was used instead of the solvent CPN in Example 1, it was evaluated by the same method. As a result, it was found that the same result as in Example 1 was obtained.

Except that PGMEA was used instead of the solvents CPN and Bu acetate in Example 1, it was evaluated by the same method. As a result, it was found that the same results as in Example 1 were obtained.

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

Evaluation was performed in the same manner as in Example 1 except that the polymerization inhibitor PMF was not used. 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 Liquid)> In the preparation of the pigment dispersion described above, carbon black (trade name "Color Black S170", manufactured by Degussa-Hüls AG was used instead of metal nitride-containing particles), and averaged once. A carbon black dispersion was obtained by preparing a dispersion by the same method as described above, except that the particle diameter was 17 nm, the BET specific surface area was 200 m ² / g, and carbon black was produced by a gas black method.

In the preparation of the composition of Example 1, a metal nitride-containing particle dispersion was used instead of the metal nitride-containing particle dispersion liquid added so that the composition contained 21% by mass of metal nitride-containing particles P-1. A mixture of the metal nitride-containing particle dispersion liquid of the particles P-1 and the 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. ] Except that a composition was produced by the same method and evaluated using it. As a result of the evaluation, the same OD value as in Example 1 was obtained, and it was found that the same light-shielding property as in Example 1 was obtained.

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

In the preparation of the composition of Example 1, a metal nitride-containing particle dispersion liquid was used instead of the metal nitride-containing particle dispersion liquid added so that the composition contained 21% by mass of the metal nitride-containing particles P-1. A mixture of the pigment dispersion liquid of particles P-1 and the PY dispersion liquid [metal nitride-containing particles P-1 in the composition: pigment yellow 150 in the composition = 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 that a composition was prepared by the same method and evaluated using the composition. As a result of the evaluation, the same OD value as in Example 1 was obtained, and it was found that the same light-shielding property as that in Example 1 was obtained, and a film having a thicker black was obtained.

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Claims (21)

A composition containing metal nitride-containing particles containing atom A, the metal nitride-containing particles containing a transition metal other than titanium among transition metals of Groups 3 to 11 and having a transition having an electronegativity of 1.22 to 2.36 A metal nitride, 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. For example, the content of the atom A in the metal nitride-containing particles is 0.00005 to 10% by mass. The composition according to item 1 of the scope of patent application, wherein the electrical conductivity of the aforementioned metal nitride-containing particles is 100 × 10 ⁴ to 600 × 10 ⁴ S / m. The composition according to item 1 or item 2 of the scope of patent application, wherein the average primary particle diameter of the metal nitride-containing particles is 10 to 50 nm. The composition according to item 1 or item 2 of the scope of patent application, further comprising a binding resin. The composition according to item 4 of the scope of patent application, wherein the mass ratio of the binder resin to the metal nitride-containing particles is 0.3 or less. The composition as described in claim 1 or 2, wherein the transition metal is at least 1 selected from the group consisting of V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re. Species. The composition according to claim 1 or claim 2, wherein the transition metal is at least one selected from the group consisting of V and Nb. The composition according to item 1 or 2 of the scope of patent application, further comprising a polymerizable compound. The composition according to item 1 or item 2 of the scope of patent application, further comprising a polymerization initiator. The composition according to item 1 or item 2 of the scope of patent application, which further contains a solvent and has a solid content of 10 to 40% by mass. The composition according to claim 10, wherein the solvent contains water, and the content of the water is 0.1 to 1% by mass based on the total mass of the composition. The composition according to claim 1 or 2, wherein the content of the metal nitride-containing particles is 20 to 70% by mass based on the total solid content of the composition. The composition according to item 1 or item 2 of the scope of patent application, further comprising a dispersant, the dispersant contains a material selected from polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester At least one structure in a group. The composition according to 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 claim 1 or 2, wherein the metal nitride-containing particles are metal nitride-containing particles coated with an inorganic compound containing aluminum hydroxide. A method for manufacturing a composition, which is a method for manufacturing a composition according to any one of claims 1 to 15 of a patent application scope, and comprises a process for obtaining the aforementioned metal nitride-containing particles by a thermoplasma method . A cured film obtained by using the composition described in any one of claims 1 to 15 of the scope of patent application. A color filter containing the hardened film described in claim 17 of the scope of patent application. A light-shielding film comprising the hardened film described in item 17 of the scope of patent application. A solid-state photographic element comprising the hardened film described in claim 17 of the scope of patent application. An image display device includes the hardened film described in claim 17 of the scope of patent application.