WO2017175550A1

WO2017175550A1 - Composition, method for producing composition, cured film, color filter, light-blocking film, solid-state imaging element, and image display device

Info

Publication number: WO2017175550A1
Application number: PCT/JP2017/010256
Authority: WO
Inventors: 久保田　誠
Original assignee: 富士フイルム株式会社
Priority date: 2016-04-08
Filing date: 2017-03-14
Publication date: 2017-10-12
Also published as: JPWO2017175550A1; JP6571275B2; TWI726075B; KR20180115331A; TW201806850A; KR20210011080A; KR102210003B1

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

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

Conventionally, a composition containing titanium nitride is known as a black powder. Compositions containing titanium nitride have been used in various applications, for example, in the production of light-shielding films provided in liquid crystal display devices and solid-state imaging devices.
Specifically, a color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
Also in the solid-state imaging device, a light shielding film is provided for the purpose of preventing noise and improving image quality. Currently, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units. Such an imaging unit generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, a lens for forming a subject image on the solid-state imaging device, It has.

In recent years, attention has been focused on the transmittance of light of a specific wavelength, and instead of titanium nitride, a black powder using a metal oxynitride having a lower transmittance of light of a specific wavelength (high light shielding property) has been developed. It is being considered. For example, Patent Document 1 states that “a black powder composed of one or two oxynitrides of vanadium or niobium, an oxygen content of 16 wt% or less, a nitrogen content of 10 wt% or more, and a dispersion having a powder concentration of 50 ppm. "Blue shielding black powder characterized in that the transmittance X at 450 nm in the transmission spectrum is 10.0% or less."

JP 2012-96945 A

The blue shielding black powder described in Patent Document 1 has excellent properties as a black pigment having high light shielding properties. However, according to the study of the present inventor, when the composition containing the black pigment as described above is used to form a cured film processed into a pattern on a substrate on which an electrode pattern is formed. The present inventors have found that there is room for further improvement in terms of improving resolution and suppressing deterioration (corrosion) of electrode patterns. Note that the resolution is that the desired pattern is approximated by the desired pattern, specifically, the obtained pattern is not thicker than the desired shape. And not intended to be thin.

Therefore, an object of the present invention is to provide a composition capable of producing a cured film having excellent light-shielding properties, excellent resolution, and excellent electrode corrosion resistance. 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.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor is a composition containing metal nitride-containing particles containing a predetermined atom, wherein the metal nitride-containing particles are made of a group 3-11 transition metal. Of these, it has been found that a composition containing a transition metal nitride other than titanium and having an electronegativity of 1.22 to 2.36 can solve the above problems. Completed the invention.
That is, it has been found that the above-described problem can be achieved by the following configuration.

[1] A composition containing metal nitride-containing particles containing atom A, wherein the metal nitride-containing particles are transition metals excluding titanium among the group 3-11 transition metals, and It contains a transition metal nitride having an electronegativity of 1.22 to 2.36, and atom A is an element different from the transition metal constituting the transition metal nitride, and includes boron, aluminum, silicon, A composition which is at least one selected from the group consisting of manganese, iron, nickel and silver, and the content of atom A in the metal nitride-containing particles is 0.00005 to 10% by mass.
[2] The composition according to [1], wherein the conductivity of the metal nitride-containing particles is 100 × 10 ⁴ to 600 × 10 ⁴ S / m.
[3] The composition according to [1] or [2], wherein the metal nitride-containing particles have an average primary particle size of 10 to 50 nm.
[4] The composition according to any one of [1] to [3], further comprising a binder 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 transition metal according to any one of [1] to [5], wherein the transition metal is at least one selected from the group consisting of V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re. Composition.
[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 water content is 0.1 to 1% by mass relative to the total mass of the composition.
[12] The composition according to any one of [1] to [11], wherein the content of the metal nitride-containing particles is 20 to 70% by mass with respect to the total solid content of the composition.
[13] A dispersant is further contained, and the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. [1] To [12].
[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 according to any one of [1] to [15], comprising a step of obtaining metal nitride-containing particles by a thermal plasma 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 cured film according to [17].
[20] A solid-state imaging device containing the cured film according to [17].
[21] An image display device comprising the cured film according to [17].

According to the present invention, there is provided a composition capable of producing a cured film having excellent light shielding properties, excellent resolution, and excellent electrode anticorrosive properties (hereinafter also referred to as “having the effect of the present invention”). can do. Moreover, according to this invention, the manufacturing method of a composition, a cured film, a color filter, a light shielding film, a solid-state image sensor, and an image display apparatus can be provided.

Below, a composition is explained in full detail for every component which comprises a composition.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Moreover, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not contain a substituent and what contains a substituent. For example, the “alkyl group” includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
In addition, in the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, deep ultraviolet light represented by excimer laser, extreme ultraviolet lithography (EUV), X-ray, and Means an electron beam. In this specification, “light” means actinic rays and radiation. Unless otherwise specified, “exposure” in the present specification includes not only exposure with an emission line spectrum of a mercury lamp and far ultraviolet rays such as an excimer laser, X-rays and EUV light, but also an electron beam and an ion beam, etc. Also includes drawing with particle beams.
Moreover, in this specification, "(meth) acrylate" represents an acrylate and a methacrylate. In the present specification, “(meth) acryl” represents acryl and methacryl. In the present specification, “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “(meth) acrylamide” represents acrylamide and methacrylamide. In this specification, “monomer” and “monomer” are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

[Composition]
The above composition is a composition containing metal nitride-containing particles containing atoms A, and the metal nitride-containing particles are transition metals excluding titanium among the group 3-11 transition metals, And a transition metal nitride having an electronegativity of 1.22 to 2.36, and the atom A is an element different from the transition metal, and is boron, aluminum, silicon, manganese, iron, nickel And a composition in which the content of atom A in the metal nitride-containing particles is 0.00005 to 10% by mass. The reason why the above composition has the effect of the present invention is not necessarily clear, but the present inventor presumes as follows. In addition, the mechanism by which the said composition exhibits the effect of this invention by the following assumptions is not limited.

The above composition contains particles containing transition metal nitrides which are transition metals excluding titanium among the transition metals of Group 3 to 11 and have an electronegativity of 1.22 to 2.36. To do.
Since the nitride has a valence band composed of 2p orbitals of nitrogen, the valence band is on the more negative side than the oxide. Further, since the nitride is made of a transition metal having a predetermined electronegativity as described above, the band gap between the valence band and the conduction band becomes smaller. As a result, it is presumed that the transition metal nitride absorbs light in a wider wavelength range (higher light shielding properties). In addition, the electronegativity in this specification intends the electronegativity according to the definition of Pauling.
Further, the composition contains atom A. In addition to high light shielding properties, it is possible to control light transmission at a wavelength (for example, i-line: 365 nm) used for pattern formation. Specifically, light necessary for pattern formation can be transmitted. That is, the composition has excellent resolution. Further, the composition has an excellent anticorrosive property of the electrode because the content of the atom A is in a predetermined range.

[Metal nitride-containing particles]
The metal nitride-containing particles are metal nitride-containing particles containing atoms A. The aspect in which the metal nitride-containing particles contain the atom A is not particularly limited, and ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides It may be contained in any form such as a product, sulfide and oxysulfide. In addition, the atoms A contained in the metal nitride-containing particles may exist as an impurity at a position between crystal lattices, or may exist as an impurity in an amorphous state at a crystal grain boundary.

<Atom A>
Atom A is contained in the metal nitride-containing particles. The atom A is an element different from the transition metal described below, and is at least one selected from the group consisting of boron, aluminum, silicon, manganese, iron, nickel, and silver. Among these, at least one selected from the group consisting of aluminum, silicon, iron, nickel and silver is preferable in that the composition has more excellent effects of the present invention, and selected from the group consisting of iron, silicon and nickel. More preferred is at least one selected from the group consisting of The atom A may be used individually by 1 type, or may use 2 or more types together.

The content of atom A in the metal nitride-containing particles is 0.00005 to 10% by mass. When the content of atom A is less than the lower limit, the resolution of the cured film obtained from the composition is inferior. When the content of the atom A exceeds the upper limit value, the light shielding property of the cured film obtained from the composition and the anticorrosion property of the electrode are inferior. Among them, the content of the atom A is preferably 0.00005% by mass or more and less than 1%, more preferably 0.00005% by mass or more and 0% or more, in that the cured film obtained from the composition has more excellent corrosion resistance of the electrode. Less than 1% is more preferable.
Moreover, when it is 0.00005 mass% or more and less than 10 mass%, the cured film obtained by the said composition has more excellent light-shielding property.
Here, the content of atom A in the metal nitride-containing particles is measured by ICP (Inductively Coupled Plasma) emission spectroscopic analysis.

<Nitride of transition metal>
The metal nitride-containing particle contains a transition metal nitride that is a transition metal excluding titanium among the group 3-11 transition metals and has an electronegativity of 1.22 to 2.36. . As the transition metal (electronegativity in parentheses), Sc (1.36), Dy (1.22), Ho (1.23), Er (1.24), Tm (group 3 transition elements) 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); Group 4 Zr (1.33), Hf (1.3); Group 5 V (1.63), Nb (1.6), Ta (1.5) Group 6 Cr (1.66), Mo (2.16), W (2.36); Group 7 Mn (1.55), Tc (1.9), Re (1.9); 8 Group 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 these, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag are preferable in that the composition has more excellent effects of the present invention. , Hf, Ta, W, Re, Os, Ir, or Pt, Sc, V, Cr, Co, Cu, Y, Zr, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re, Os, Ir, or Pt is more preferable, V, Cr, Y, Zr, Nb, Hf, Ta, W, or Re is more preferable, V, Cr, Y, Nb, Ta, W, or Re is particularly preferable, V or Nb is particularly more preferable, and Nb is most preferable.

The content of the “transition metal constituting the transition metal nitride” in the metal nitride-containing particles is preferably 10 to 85% by mass, and preferably 15 to 75% by mass with respect to the total mass of the metal nitride-containing particles. More preferred is 20 to 70% by mass. The content of “transition metal constituting transition metal nitride” in the metal nitride-containing particles can be analyzed by ICP (Inductively Coupled Plasma) emission spectroscopy.
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 with respect to the total mass of the metal nitride-containing particles. More preferred is mass%. The nitrogen atom content can be analyzed by an inert gas melting-thermal conductivity method.
The metal nitride-containing particles contain metal nitride as a main component and may partially contain oxygen atoms due to oxidation of the particle surface. For example, the oxidation of the particle surface becomes more prominent when oxygen is mixed in the synthesis of the 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 further preferably 5 to 30% by mass with respect to the total mass of the metal nitride-containing particles. preferable. The oxygen atom content can be analyzed by an inert gas melting-infrared absorption method.

From the viewpoint of stability over time and the light-shielding properties, the specific surface area is preferably ^{5 m} 2 / g or more 100 m ² / g or less of a metal nitride-containing particles, ^{10 m} 2 / g or more ^{60 m} 2 / g or less is more preferable. The specific surface area can be determined by the BET (Brunauer, Emmett, Teller) method.

The metal nitride-containing particles may be composite fine particles composed of metal nitride-containing particles and metal fine particles.
The composite fine particles are particles in which metal nitride-containing particles and metal fine particles are complexed or in a highly dispersed state. Here, “composite” means that particles are composed of both metal nitride and metal components, and “highly dispersed state” means metal nitride-containing particles and metal particles. Means that the small amount of particles are uniformly and uniformly dispersed without aggregation.
The metal fine particles are not particularly limited. For example, copper, gold, platinum, palladium, tin, cobalt, rhodium, iridium, ruthenium, osmium, molybdenum, tungsten, niobium, tantalum, calcium, bismuth, antimony and lead, and these At least one selected from alloys can be mentioned. Among these, at least one selected from copper, gold, platinum, palladium, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, and at least selected from copper, gold, platinum, tin, and alloys thereof It is more preferable that it is 1 type.
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 with respect to the total mass of the metal nitride-containing particles.

<Method for producing metal nitride-containing particles>
For the production of metal nitride-containing particles, a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because it is less contaminated with impurities, has a uniform particle diameter, and has high productivity.
A specific method for producing metal nitride-containing particles by the thermal plasma method includes, for example, a method using a metal fine particle production apparatus. The metal fine particle manufacturing apparatus includes, for example, a plasma torch that generates thermal plasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber that includes a cooling function, and a cyclone that classifies the generated metal fine particles. And a recovery unit for recovering the metal fine particles.
In the present specification, the metal fine particles mean particles having a primary particle diameter of 20 nm to 40 μm containing a metal element.

It does not specifically limit as a manufacturing method of metal nitride containing particle | grains using a metal microparticle manufacturing apparatus, A well-known method can be used. Among them, the method for producing metal nitride-containing particles using a metal fine particle production apparatus includes the following steps in that the yield of metal nitride-containing particles having the following predetermined average primary particle diameter is increased. preferable.
Step A: A step of supplying a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
Step C: Step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
Step D: A step of supplying a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch.
Step E: A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
Step F: Step of cooling the gas phase raw metal to obtain metal nitride-containing particles.
Moreover, the manufacturing method of metal nitride containing particle | grains may contain the following process G depending on necessity after the said process C and / or the process F. FIG.
Step G: A step of classifying the obtained particles.
Further, before step A, between step A and step B, between step C and step D, or between step D and E, the following step A2 may be included.
Step A2: A step of mixing atoms A into a metal raw material powder containing a transition metal.
Further, before the step A2, the following steps A3-1 to A3-3 may be included.
Step A3-1: An inert gas not containing nitrogen gas is supplied as a plasma gas in the plasma torch, and a thermal plasma flame is generated. Step A3-2: Atom A is contained in the thermal plasma flame in the plasma torch. Step A3-3 of supplying raw material powder and evaporating the raw material powder to obtain gas phase atoms A: Step of cooling the gas phase atoms A to obtain atomized atoms A Step A3- Step 3 may be further included after 3.
In the present specification, the atomized atom A means a particle having an atom A-containing primary particle diameter of 20 nm to 40 μm.

Furthermore, it is preferable that the manufacturing method of the said metal nitride containing particle | grains contains the following process H further after the process F (When the process G is included, after the process G after the process F).
Step H: A step of exposing the metal nitride-containing particles obtained in Step F (or Step G) to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
In addition, the manufacturing method of the said metal nitride containing particle | grains may contain the process G further after the process H if desired. Below, the suitable aspect of each process is explained in full detail.

・ Process A
Step A is a step of generating a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch. The generation method of the thermal plasma flame is not particularly limited, and examples thereof include a direct current arc discharge method, a multiphase arc discharge method, a high frequency plasma method, a hybrid plasma method, and the like. Is preferred.
The method of generating a thermal plasma flame by the high frequency plasma method is not particularly limited. For example, a plasma gas is supplied into a plasma torch containing a high frequency oscillation coil and a quartz tube, and a high frequency current is applied to the high frequency oscillation coil. The method of obtaining a thermal plasma flame by doing is mentioned.
As the plasma gas in step A, an inert gas not containing nitrogen gas is used. Examples of the inert gas not containing nitrogen gas include argon gas and hydrogen gas. The inert gas which does not contain nitrogen gas may be used individually by 1 type, or may use 2 or more types together.

・ Process A2
Step A2 is a step of mixing atoms 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 material supply device for supplying the metal raw material powder into the plasma torch may contain a mixing and dispersing function. Specifically, the material supply apparatus described in paragraphs [0047] to [0058] of International Publication No. 2010/147098 can be used, the contents of which are incorporated herein. The method for producing metal nitride-containing particles may further include the following steps A3-1 to A3-3 before step A2.

・ Process B
Step B is a step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in the plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal. The method for supplying the metal raw material powder to the thermal plasma flame in the plasma torch is not particularly limited, but the obtained gas phase raw material metal may be sprayed using a carrier gas in a more uniform state. preferable. In addition, it is preferable to use inert gas which does not contain nitrogen gas as carrier gas. The aspect of the inert gas not containing nitrogen gas is as described above.
In addition, when the method for producing metal nitride-containing particles includes the step A2, the metal raw material powder is maintained in a uniform dispersed state until the metal raw material powder is supplied into the plasma torch. It is preferable.

・ Process C
Step C is a step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal. The cooling method is not particularly limited, but it is preferable to use a chamber containing a cooling function. By introducing the gas phase raw material metal obtained in the step B into the chamber containing the cooling function and quenching in the chamber, metal fine particles having the following desired particle diameter can be generated. The generated metal fine particles are recovered by, for example, the recovery unit. The atmosphere in the chamber is preferably an inert gas that does not contain nitrogen gas. The aspect of the inert gas not containing nitrogen gas is as described above.
By passing through the above steps A to C, metal fine particles containing a transition metal can be obtained. The metal fine particles containing the transition metal are likely to evaporate in the process E. Even when the metal raw material powder contains impurities, the impurities can be removed by performing the steps A to C.

・ Process D
Step D is a step of generating a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch. Examples of the inert gas containing nitrogen include nitrogen gas and nitrogen gas containing an inert gas. Examples of the inert gas include argon gas and hydrogen gas. The nitrogen gas contained in the inert gas is not particularly limited, but the nitrogen gas content is usually about 10 to 90 mol%, preferably about 30 to 60 mol%. Other aspects are the same as in step A.

・ Process E
Step E is a step of supplying metal fine particles containing a transition metal to the thermal plasma flame in the plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal. The method for supplying the metal fine particles to the thermal plasma flame in the plasma torch is as described above, but the carrier gas is preferably an inert gas containing nitrogen. The aspect of the inert gas containing nitrogen is as described above.
In Step E, the raw material metal that has become fine metal particles in Steps A to C is supplied to the thermal plasma flame, so that it is easy to obtain a vapor phase raw material metal, and the state of the vapor phase raw material metal becomes more uniform. Cheap.

・ Process F
Step F is a step of cooling the gas phase raw material metal to obtain metal nitride-containing particles containing a transition metal nitride. Although the suitable aspect of the cooling method is as above-mentioned, as the atmosphere in a chamber, the inert gas containing nitrogen gas is preferable. The suitable aspect of the inert gas containing nitrogen gas is as above-mentioned.

・ Process G
Step G is a step of 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 has a container on a cone, and generates a swirling flow in the container and has a function of classifying particles using centrifugal force. The classification is preferably performed in an inert gas atmosphere. The aspect of the inert gas is as described above.

・ Process H
Step H is a step in which the metal nitride-containing particles are exposed to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment. Through this step, the metal nitride content 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 gas is not particularly limited. For example, the metal nitride-containing particles are introduced into a thermostatic bath filled with a gas mixed with water vapor and nitrogen gas. There may be mentioned a method of standing or stirring for a predetermined time, and it is more preferred that the metal nitride-containing particles are allowed to stand for stabilization of the surface and crystal boundaries.
The mixing ratio of water vapor and nitrogen gas is preferably such that the relative humidity is 25 to 95% in the atmosphere. The time for standing or stirring is preferably 0.5 to 72 hours, and the temperature at that time is preferably 10 to 40 ° C.

・ Process A3-1 to A3-3
In steps A3-1 to A3-3, an inert gas not containing nitrogen gas is supplied as a plasma gas in the plasma torch to generate a thermal plasma flame (A3-1), and a thermal plasma flame in the plasma torch is used. Supplying a raw material powder containing atoms A, evaporating the raw material powder to obtain gas phase atoms A (A3-2), and cooling the gas phase atoms A to form fine particles comprising atoms A This is the obtaining step (A3-3). The aspect in each process is the above-mentioned process A, process B (instead of a metal raw material powder containing a transition metal, using a raw material powder containing an atom A), and process C (substituting metal fine particles containing a transition metal) Thus, atomized atom A is obtained.
In addition, through the above process, the atom A is made into fine particles, and the atom A is easily evaporated in the process E. Moreover, the impurities (metal components other than the atom A) contained in the raw material powder containing the atom A can be removed through the above steps.

(Preferred embodiment of method for producing metal nitride-containing particles containing atom A)
As a suitable aspect of the manufacturing method of the metal nitride containing particle | grains containing the said atom A, the manufacturing method of the metal nitride containing particle | grains containing the atom A which has the following processes in an order from the top is mentioned.
Step A: A step of supplying an inert gas not containing nitrogen gas as a plasma gas in the plasma torch to generate a thermal plasma flame.
Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in the plasma torch and evaporating the raw material metal powder to obtain a gas phase raw material metal.
Step C: A step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
-Process G: The process of classifying the obtained particle | grains.
Step A3-1: A step of supplying an inert gas containing no nitrogen gas into the plasma torch as a plasma gas to generate a thermal plasma flame. Step A3-2: Atom A is added to the thermal plasma flame in the plasma torch. Step / step A3-3 of supplying raw material powder and evaporating the raw material powder to obtain vapor phase atoms A: Step A3-3: Cooling vapor phase atoms A to obtain atomized atom A G: A step of classifying the obtained particles.
Step A2: A step of mixing atoms A (in this case, atomized atoms A) with a metal raw material powder (in this case, metal fine particles) containing a transition metal.
Step D: A step of supplying an inert gas containing nitrogen gas into the plasma torch as a plasma gas to generate a thermal plasma flame.
Step E: A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
Step F: Step of cooling the gas phase raw material metal to obtain metal nitride-containing particles.
-Process G: The process of classifying the obtained particle | grains.
Step H: Step of exposing the metal nitride-containing particles obtained in Step G to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
In the series of steps, the order of steps A to C and steps A3-1 to A3-3 may be changed. That is, steps A to C may be performed after steps A3-1 to A3-3.

According to the preferred embodiment of the method for producing the metal nitride-containing particles containing the atom A, the metal raw material powder and the metal nitride that can remove impurities contained in the raw material particles and have a desired average primary particle diameter Containing particles can be produced.
The mechanism by which impurities are removed is not necessarily clear, but the present inventor speculates as follows. That is, the transition metal and / or atom A is ionized by plasma treatment, and when the ions are cooled, the transition metal, atom A, and impurities are presumed to be finely divided to reflect their melting points. The At this time, the atomization with a low melting point is fast, and the atomization with a high melting point is slow. Therefore, as described above, it is presumed that the fine particles (steps B and C and steps A3-2 and A3-3) once plasma-treated are likely to become a single component (single crystal). If the single component particles obtained as described above are classified, the impurity particles can be removed depending on the density and / or particle size difference between the transition metal particles and / or the atom A particles and the impurity particles. . In addition, the said classification can be performed by setting a classification condition suitably using a cyclone etc., for example.

(Purification of raw metal powder and raw material powder)
As the metal raw material powder containing transition metal (hereinafter simply referred to as “metal raw material powder”) and the raw material powder containing atom A (hereinafter simply referred to as “raw material powder”) that can be used in the above-mentioned step B, Although it does not restrict | limit in particular, It is preferable that it is a highly purified thing. The content of the transition metal in the metal raw material powder is not particularly limited, but is preferably 99.99% or more, and more preferably 99.999% or more. The same applies to the content of atom A in the raw material powder.

The metal raw material powder and / or the raw material powder may contain a desired transition metal and / or an atom other than the atom A as an impurity. Examples of impurities contained in the metal raw material powder include boron, aluminum, silicon, manganese, iron, nickel, and silver. Moreover, a metal element etc. are mentioned as an impurity contained in raw material powder.

The composition exhibits the effects of the present invention by setting the content of atom A in the metal nitride-containing particles to 0.00005 to 10% by mass. For this reason, if the metal raw material powder and / or the raw material powder includes the unintended impurities, it is difficult to control the content of the atoms A within a predetermined range, and thus it is difficult to obtain the effects of the present invention. Therefore, the method for producing metal nitride-containing particles may further include the following step A0 before step B (when step A2 is included, before step A2).
Step A0: A step of removing impurities from the metal raw material powder and / or the raw material powder.

・ Process A0
In step A0, the raw metal powder and / or the method for removing impurities from the raw material powder (separation and purification method) is not particularly limited. A method similar to this can be used for other raw 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, it may be a coated metal nitride-containing particle having metal nitride-containing particles and a coating layer formed using an inorganic compound that coats the metal nitride-containing particles. The composition containing metal nitride-containing particles coated with an inorganic compound has better dispersion stability.
The inorganic compound is not particularly limited, and is an oxide 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 zirconium hydroxide. And the like. Among these, aluminum hydroxide is preferable in that it can easily form a thinner film and can easily form a film having a higher coverage.
When the refractive index of the metal nitride-containing particles is intended to be controlled, silicon oxide is preferable as the low refractive index film, and zirconium hydroxide is preferable as the high refractive index film.
The method for coating the metal nitride-containing particles with the inorganic compound is not particularly limited, but the method for producing the metal nitride-containing particles preferably includes the following inorganic compound coating step.

-Inorganic compound coating process An inorganic compound coating process is a process of coat | covering said metal nitride containing particle | grains with an oxide and / or a hydroxide. Although it does not restrict | limit especially as a method to coat | cover, For example, the following wet coating methods etc. are mentioned.

As the first wet coating method, first, the metal nitride-containing particles are mixed with water 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 an excess amount. After alkali ions are removed by decantation and / or ion exchange resin or the like, the slurry is dried to obtain metal nitride-containing particles coated with oxide.

As the second wet coating method, first, the above metal nitride-containing particles are mixed with an organic solvent such as alcohol to prepare a slurry. Next, an organometallic 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 heated at a high temperature. Bake. When the slurry is fired at a high temperature, a sol-gel reaction proceeds, and metal nitride-containing particles coated with an oxide are 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 to obtain metal nitride-containing particles coated with a hydroxide containing aluminum hydroxide.

<Physical properties of metal nitride-containing particles>
(conductivity)
The conductivity of the metal nitride-containing particles is not particularly limited, but is preferably 100 × 10 ⁴ to 600 × 10 ⁴ S / m, more preferably 165 × 10 ⁴ to 340 × 10 ⁴ S / m, and 165 × 10 ⁴ S / m to 220 × 10 ⁴ S / m is more preferable, and 170 to 190 × 10 ⁴ S / m is particularly preferable. When 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 containing the metal nitride-containing particles is obtained. The cured film to be obtained has a better light-shielding property and an excellent electrode anticorrosive property.
In this specification, the term “conductivity” means the conductivity measured by the following method using a powder resistance measurement system MCP-PD51 manufactured by Mitsubishi Chemical Analytech.
First, after a predetermined amount of metal nitride-containing particles are packed in a measurement container of the measurement apparatus, pressurization is started, and the pressure is changed to 0 kN, 1 kN, 5 kN, 10 kN, and 20 kN to change the volume resistivity (ρ ). From the measurement result, the saturated volume resistivity under the condition that the volume resistivity does not depend on the pressure is obtained, and the conductivity (σ) is calculated by the relational expression of σ = 1 / ρ using the obtained saturated volume resistivity. The above test is performed in a room temperature environment.

(Average primary particle size)
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 still more preferably 10 to 27 nm. When the average primary particle size is 27 nm or less, in the composition containing the metal nitride-containing particles, the metal nitride-containing particles are less likely to settle, and as a result, the composition has better temporal stability.
In addition, in this specification, the average primary particle diameter intends the average particle diameter of primary particles, and the average primary particle diameter intends the average primary particle diameter measured by the following method.
Sample: A dispersion (25% by mass of metal nitride-containing particles, 7.5% by mass of dispersant, PGMEA; 67.5% by mass of propylene glycol monomethyl ether acetate solvent) was prepared by the method described in the following examples, and obtained. The dispersion obtained was diluted 100 times with PGMEA and then dropped on a carbon foil and dried.
As the dispersant, a dispersant that can disperse the metal nitride-containing particles to the extent that the primary particles of the metal nitride-containing particles can be recognized in an image obtained by the following method is used. Specific examples of the dispersant include the dispersants described in Examples. The primary particles are independent particles without aggregation.
The sample is observed at a magnification of 20,000 using a transmission electron microscope (TEM) to obtain an image. Primary particles are selected from the metal nitride-containing particles in the obtained image, and the area of the primary particles is calculated by image processing. Next, the diameter when the obtained area is converted into a circle is calculated. This operation is performed for a total of 400 primary particles of metal nitride-containing particles for 4 fields of view, and the evaluated circle-equivalent diameter is arithmetically averaged to obtain the average primary particle size of the metal nitride-containing particles.

〔solvent〕
The composition preferably contains a solvent. Examples of the solvent include water and organic solvents. Especially, it is preferable that the said composition contains the organic solvent.

<Organic solvent>
The organic solvent is not particularly limited. For example, acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethyleneglycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, acetic acid Examples include ethyl, butyl acetate, methyl lactate, and ethyl lactate.

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

When the above composition contains an organic solvent, the content of the organic solvent is preferably 10 to 90% by mass, more preferably 60 to 90% by mass with respect to the total mass of the composition. When two or more types of organic solvents are contained, the total amount is preferably within 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 water content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more with respect to the total mass of the composition. Preferably, it is 1% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.7% by mass or less. When the water content is within the above range, the generation of pinholes is suppressed when a cured film is produced, and the moisture resistance of the cured film is further improved. Moreover, when 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 not more than the upper limit value, the number of particles contained in the composition tends to be smaller. Moreover, when the solid content of the composition is not less than the lower limit value, the composition has more excellent coating properties.
The content of the metal nitride-containing particles is preferably 20 to 70% by mass with respect to the total solid content of the composition. When the content of the metal nitride-containing particles is at least the lower limit value, the composition has more excellent temporal stability. In addition, if the content of the metal nitride-containing particles is not more than the upper limit value, the number of particles contained in the composition is likely to be smaller, and a composition capable of producing a cured film having more excellent resolution Is obtained.

[Dispersant]
The composition preferably contains a dispersant. A dispersing agent contributes to the improvement of dispersibility of black pigments, such as the above-mentioned metal nitride content particles. In the present specification, the dispersant and the binder resin described later are different components.
As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

<Polymer compound>
The polymer compound is adsorbed on the surface of a dispersion of a black pigment, which is a preferred embodiment of the metal nitride-containing particles, and a pigment or the like to be used in combination (hereinafter also simply referred to as “black pigment etc.”). It acts to prevent re-aggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer containing an anchor site to the pigment surface are preferable.
On the other hand, the adsorptivity of the polymer compound to the metal nitride-containing particles can be promoted by modifying the surface of the metal nitride-containing particles.

The polymer compound preferably contains a structural unit containing a graft chain. In this specification, “structural unit” is synonymous with “repeating unit”.
Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent by the graft chain, the dispersibility of a colored pigment such as a black pigment, and the dispersion stability after aging ( It has excellent stability over time. Further, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the black pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to colored pigments such as black pigments is lowered, and the dispersibility of black pigments and the like tends to be lowered. For this reason, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms. More preferred is 60-500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide. Examples thereof include a structure and a polyether structure.
The graft chain was selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility of the black pigment and the like. A graft chain containing at least one kind is preferred, and a graft chain containing at least one of a polyester structure or a polyether structure is more preferred.

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

Corresponding to the structural unit containing a graft chain contained in the polymer compound, commercially available macromonomers suitably used for the synthesis of the polymer compound include AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10. (Trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AW -6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.) AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PP-100 (trade name, NOF Corporation) Blemmer PP-500 (trade name, manufactured by NOF Corporation), Blemmer PP-800 ( Product name, manufactured by NOF Corporation), BLEMMER PP-1000 (trade name, manufactured by NOF CORPORATION), BLEMMER 55-PET-800 (trade name, manufactured by NOF CORPORATION), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation) ), BLEMMER PSE-400 (trade name, manufactured by NOF Corporation), BLEMMER PSE-1300 (trade name, manufactured by NOF Corporation), BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corporation) and the like are used. Among these, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 ( Trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Bremer PME-4000 (trade name, manufactured by NOF Corporation) and the like are used.

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

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

In the formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms.
In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms) from the viewpoint of synthesis constraints. Are preferably each independently a hydrogen atom or a methyl group, more preferably a methyl group.

In the formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following (Y-1) to (Y-21) linking groups. . In the structure shown below, A and B each represent a binding site. Of the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.

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

In the 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. J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoint of the temporal stability and developability of the composition.

In formula (3), R ³ represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same 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 terms of structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

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

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

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

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

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

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

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

(Hydrophobic structural unit)
The polymer compound preferably 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). However, in this specification, a hydrophobic structural unit is a structural unit which does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

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

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

log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.

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

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

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, where R ³¹ Includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. Further, 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 still 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 the heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may also contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

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

The aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. A phenyl group and the like are included. Examples of the bridged cyclic hydrocarbon ring include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane rings , And tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.

The carbon number 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.

It is preferable that a heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms. (For example, a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Here, L and Z are as defined above. R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

As the monomer represented by the general formula (i), R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, and L is a single bond or an alkylene group or an oxyalkylene structure. A compound in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
Further, as the monomer represented by the general formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred. Further, as the monomer represented by the general formula (iii), 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. Certain compounds are preferred.

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

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

(Functional group capable of forming interaction with black pigment)
The polymer compound can introduce a functional group capable of forming an interaction with a colored pigment such as a black pigment. Here, the polymer compound preferably further contains a structural unit containing a functional group capable of interacting with a colored pigment such as a black pigment.
Examples of the functional group capable of forming an interaction with the colored pigment such as the black pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordination group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, and a coordination group, respectively. It is preferable to contain a structural unit containing a coordinate group or a structural unit having reactivity.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the acid group, developability for pattern formation by alkali development can be imparted to the polymer compound.
That is, by introducing an alkali-soluble group into the polymer compound, in the composition, the polymer compound as a dispersant that contributes to the dispersion of a colored pigment such as a black pigment contains alkali-solubility. A composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when a high molecular compound contains the structural unit containing an acid group, a high molecular compound becomes easy to become compatible with a solvent, and there exists a tendency for applicability | paintability to improve.
This is because the acid group in the structural unit containing an acid group easily interacts with a colored pigment such as a black pigment, and the polymer compound stably disperses the colored pigment such as a black pigment, and the colored pigment such as a black pigment. It is presumed that the viscosity of the polymer compound in which the polymer is dispersed is low, and the polymer compound itself is easily dispersed stably.

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

Examples of the acid group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably a carboxylic acid Group, sulfonic acid group, and at least one of phosphoric acid groups, and more preferable is that the adsorptive power to a colored pigment such as a black pigment is good and the dispersibility of the colored pigment is high, Carboxylic acid group.
That is, the polymer compound preferably further contains 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 more structural units containing an acid group.
The polymer compound may or may not contain a structural unit containing an acid group. However, when it is contained, the content of the structural unit containing an acid group is calculated by mass conversion to the total mass of the polymer compound. On the other hand, it is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.

Examples of the basic group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocyclic ring containing an N atom. And an amide group, and the preferred is a tertiary amino group from the viewpoint of good adsorbing power to a colored pigment such as a black pigment and high dispersibility of the colored pigment. The polymer compound can 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 it is contained, the content of the structural unit containing a basic group is the total amount of the polymer compound in terms of mass. Preferably it is 0.01% or more and 50% or less with respect to mass, More preferably, it is 0.01% or more and 30% or less from a viewpoint of developability inhibition suppression.

As a coordinating group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment, and a functional group having reactivity, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chloride etc. are mentioned. A preferable one is an acetylacetoxy group in terms of good adsorbing power to a colored pigment such as a black pigment and high dispersibility of the colored pigment. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it contains, the content of these structural units Is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less, in terms of mass, in terms of suppression of developability inhibition.

When the polymer compound contains a functional group capable of interacting with a colored pigment such as a black pigment in addition to the graft chain, the functional group capable of interacting with a colored pigment such as the various black pigments described above. However, there is no particular limitation on how these functional groups are introduced, but the polymer compound is a monomer represented by the following general formulas (iv) to (vi). It is preferable to contain one or more structural units selected from the derived structural units.

In general formula (iv) to general formula (vi), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
In general formula (iv) to general formula (vi), R ¹¹ , R ¹² and R ¹³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each independently represents a hydrogen atom or a methyl group. In general formula (iv), R ¹² and R ¹³ are each particularly preferably a hydrogen atom.

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

In the general formulas (iv) to (v), L ₁ represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR ³¹ ′ — Here, R ³¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy 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 still more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy 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 the heterocyclic ring. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L ₁ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₁ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In general formula (iv) to general formula (vi), Z ₁ represents a functional group capable of forming an interaction with a colored pigment such as a black pigment in addition to the graft chain, and includes a carboxylic acid group and a tertiary amino group. It is preferable that it is a carboxylic acid group.

In general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), - _{Z 1,} or an _L 1 -Z _1. Wherein _{L 1} and _{Z 1} are the same meaning as _{L 1} and _{Z 1} in the above, it is the preferable examples. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, 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, and L ₁ contains an alkylene group or an oxyalkylene structure. A compound in which X ₁ is an oxygen atom or an imino group and Z ₁ is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Furthermore, as the monomer represented by the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, and L ₁ is a single bond or an alkylene group, A compound in which Z ₁ is a carboxylic acid group is preferred.

The following are typical examples of monomers (compounds) represented by general formula (iv) to general formula (vi).
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction containing a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. Product, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride Reaction product, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride Reaction products with acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4 Hydroxyphenyl methacrylamide.

The content of the structural unit containing a functional group capable of forming an interaction with a colored pigment such as a black pigment is from the viewpoint of interaction with the colored pigment such as a black pigment, stability over time, and permeability to a developer. The amount is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and still more preferably 10% by mass to 70% by mass with respect to the total mass of the polymer compound.

(Other structural units)
Furthermore, the polymer compound is a coloring unit such as a structural unit containing a graft chain, a hydrophobic structural unit, and a black pigment, for the purpose of improving various performances such as image strength, as long as the effects of the present invention are not impaired. Different from structural units containing functional groups capable of forming interactions with other structural units having various functions (for example, structures containing functional groups having affinity with the dispersion medium used in the dispersion) (Unit) may further be included.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.

(Physical properties of polymer compounds)
The acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably in the range of 20 mgKOH / g to 120 mgKOH / g. The range is as follows.
When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a cured film is more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable. Further, if the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of colored pigments such as black pigments can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition is further improved. it can.

The acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.

When forming a cured film, the weight average molecular weight of the polymer compound is 4 in terms of polystyrene converted by GPC (Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition during development and developability. It is preferably 000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred that
The GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID × 15 cm) as a column and THF (tetrahydrofuran) as an eluent. .

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

Specific examples of the polymer compound include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester)” manufactured by BYK Chemie, and 110 (copolymers containing acid groups). ), 111 (phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) ”,“ BYK-P104, P105 (non-high molecular weight) Saturated polycarboxylic acid) ”,“ EFKA 4047, 4050 to 4010 to 4165 (polyurethane) ”, EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (polyester), manufactured by EFKA High molecular weight polycarboxylate), 6220 (fatty acid polyester) ), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), “Ajisper PB821, PB822, PB880, PB881” manufactured by Ajinomoto Fine Techno Co., Ltd., “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow” No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA, manufactured by Enomoto Kasei Co., Ltd. -703-50, DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920" 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), manufactured by Nippon Lubrizol, 3000, 12000, 17000, 20000, 27000 (polymers containing a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan mono) manufactured by Nikko Chemicals Olate), MYS-IEX (polyoxyethylene monostearate) ”, Kawaken Fine Chemical's Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho W001: Cationic surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate Nonionic surfactants such as sorbitan fatty acid esters, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400 manufactured by Morishita Sangyo , EFKA Polymer 401, EFKA Polymer 450 ", Sannopco" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disper Polymer dispersants such as Suede 9100, manufactured by ADEKA "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P -123 ", Sanyo Kasei" Ionet (trade name) S-20 ", and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9976, Ajisper PB821, Azisper PB822, Azisper PB881, etc. manufactured by Ajinomoto Fine Techno Co., Ltd.
These polymer compounds may be used alone or in combination of two or more.

As specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A, the contents of which are incorporated herein.

As the dispersant, in addition to the above-described polymer compound, graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to columns 0075 to 0133 in US2011 / 0124824) can be used. Is incorporated herein by reference.
In addition to the above, it contains a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding to paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group. High molecular compounds containing the constituents to be used can be used, the contents of which can be incorporated and incorporated herein.

In the case where the composition contains a dispersant, the content of the dispersant is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, based on the total solid content of the composition.
A dispersing agent may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.

In the composition, the mass ratio of the dispersant to the metal nitride-containing particles (that is, (the content of the dispersant in the composition) / (the content of the metal nitride-containing particles in the composition) or less, “D / P ”) is preferably 0.05 to 0.30, more preferably 0.10 to 0.30, and still more preferably 0.12 to 0.30. 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 temporal stability.

In the composition, the lower limit value of the mass ratio of the dispersant to the atom A (that is, (content of dispersant in the composition) / (content of Fe atom in the composition)) is 0.8. The above is preferable, 1.0 or more is more preferable, and 1.5 or more is more preferable. The upper limit is preferably 270 or less, more preferably 150 or less, and even more preferably 50 or less.
The said composition has the effect of this invention more excellent because the mass ratio of the dispersing agent with respect to the atom A exists in the said range. In particular, when the mass ratio is in the range of 1.5 to 50, the composition has a further excellent effect of the present invention. The reason for this is not clear, but it is considered that the atom A in the composition and the dispersing agent interact with each other and affect patterning properties (curability and resolution).

In the composition, the lower limit of the mass ratio of the following polymerizable compound to the atom A (that is, (content of polymerizable compound in the composition) / (content of atom A in the composition)) is 0. 0.7 or more, preferably 0.85 or more, and more preferably 1.0 or more. The upper limit is preferably 50 or less, more preferably 11 or less, and even more preferably 7.0 or less.
A composition has the effect of this invention more excellent because the mass ratio of the polymeric compound with respect to the atom A exists in the said range. When the content ratio is in the range of 1.0 to 7.0, the composition has a further excellent effect of the present invention. The reason for this is not clear, but it is considered that the atom A in the composition and the polymerizable compound interact with each other and affect the patternability (curability and resolution).

[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 well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. Especially, as binder resin, alkali-soluble resin (resin containing group which accelerates | stimulates alkali solubility) is especially preferable.
The binder resin is a linear organic polymer that promotes at least one alkali solubility in the molecule (preferably a molecule having a (meth) acrylic copolymer or styrene copolymer as the main chain). It can be suitably selected from alkali-soluble resins containing a group to be used. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins, epoxy resins and Polyimide resins are preferred, and (meth) acrylic resins, (meth) acrylamide resins, (meth) acryl / (meth) acrylamide copolymer resins, or polyimide resins are more preferred from the viewpoint of control of developability.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Especially, what is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable, and an alkali-soluble resin containing a structural unit derived from (meth) acrylic acid is more preferable. These acid groups may be used alone or in combination of two or more.

Examples of the binder resin include a radical polymer containing a carboxylic acid group in the side chain. Examples of the radical polymer containing a carboxylic acid group in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-54. -92723, JP-A-59-53836, and JP-A-59-71048. As a radical polymer containing a carboxylic acid group in the side chain, a resin obtained by singly or copolymerizing a monomer containing a carboxylic acid group, an acid anhydride obtained by singly or copolymerizing a monomer containing an acid anhydride Examples thereof include resins obtained by hydrolysis, half-esterification or half-amidation of units, and epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides.
Examples of the monomer containing a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene. Moreover, the acidic cellulose derivative which contains a carboxylic acid group in a side chain is also mentioned as an example.
Examples of the monomer containing an acid anhydride include maleic anhydride. In addition, a polymer containing a hydroxyl group added to a polymer containing a hydroxyl group is useful.
Further, acetal-modified polyvinyl alcohol-based binder resins containing acid groups are described in European Patent Nos. 993966, 1204000 and JP-A 2001-318463. An acetal-modified polyvinyl alcohol-based binder resin containing an acid group is suitable because of its excellent balance of film strength and developability.
Furthermore, polyvinyl pyrrolidone or polyethylene oxide is useful as the water-soluble linear organic polymer. 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, a polyimide resin described in International Publication No. 2008/123097 is also useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition-polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity, and developability.
Examples of commercially available products include Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai), and Daicel Ornex Cyclomer P (ACA) 230AA.

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

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) as the binder resin.
The definition of the structural unit containing the graft chain is synonymous with the structural unit containing the graft chain contained in the dispersant, and the preferred range is also the same.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. More preferred is a carboxylic acid group.

<Structural unit containing acid group>
The structural unit containing an acid group preferably contains at least one structural unit selected from structural units derived from monomers represented by the following general formulas (vii) to (ix). .

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

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

In the general formulas (vii) to (ix), L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group, and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR ⁴¹ ′ — Here, R ⁴¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy 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 the heterocyclic ring. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ⁴² , where R ⁴² represents a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L ₂ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₂ may also contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

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

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

As the monomer represented by the general formula (vii), R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom or a methyl group, and L ₂ contains an alkylene group or an oxyalkylene structure. A compound in which X ₂ is an oxygen atom or an imino group and Z ₂ is a carboxylic acid group is preferred.
Further, as the monomer represented by the general formula (vii), R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Furthermore, as the monomer represented by the general formula (ix), a compound in which R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom or a methyl group and Z ₂ is a carboxylic acid group is preferable.

The binder resin can be synthesized by the same method as the dispersant containing the structural unit containing the graft chain, and the preferred acid value and weight average molecular weight are the same.

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

The content of the binder resin in the composition is preferably 0.1 to 30% by mass and more preferably 0.3 to 25% by mass with respect to the total solid content of the composition.
Binder resin may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.

The mass ratio of the binder resin to the metal nitride-containing particles (that is, (the content of the binder resin in the composition) / (the content of the metal oxide-containing particles in the composition)) is preferably 0.3 or less, 0.25 or less is more preferable and 0.20 or less is still more preferable. The lower limit is not particularly limited, but is generally 0.01 or more, preferably 0.02 or more, and more preferably 0.07 or more.
When the upper limit is 0.25 or less, the composition has more excellent temporal stability, and when it is 0.014 or more, the cured film obtained using the composition has more excellent resolution. Have.

(Polymerizable compound)
The composition preferably contains a polymerizable compound.
The polymerizable compound is preferably a compound containing at least one group containing an ethylenically unsaturated bond, more preferably a compound containing 2 or more, further preferably containing 3 or more, and containing 5 or more. Is particularly preferred. The upper limit is 15 or less, for example. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof. Monomers are 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, more preferably a 3 to 6 functional (meth) acrylate compound.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide containing a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and A dehydration condensation reaction product of a saturated carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used. Also, a reaction product of an unsaturated carboxylic acid ester or amide containing an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or tosyloxy A reaction product of an unsaturated carboxylic acid ester or amide containing a leaving substituent such as a group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure. For example, compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, and the contents thereof are incorporated herein.

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

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

The preferred acid value of the polymerizable compound containing an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

The polymerizable compound is also preferably a compound containing a caprolactone structure.
The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. Of these, compounds containing a caprolactone structure represented by the following general formula (Z-1) are preferred.

In the general formula (Z-1), all six R are groups represented by the following general formula (Z-2), or 1 to 5 of the six R are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).

In 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 bond.

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

Polymerizable compounds containing a caprolactone structure are commercially available, for example, from Nippon Kayaku as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), the formula (Z -2) = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (formula, m = 1, number of groups represented by formula (Z-2) = 3) , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (formula, m = 1, number of groups represented by formula (Z-2) = 6, compounds in which R ¹ are all hydrogen atoms), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R ¹ are hydrogen atoms).

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

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

In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
In the general formula (Z-4) or the general formula (Z-5), — ((CH ₂ ) _y CH ₂ O) — or ((CH ₂ ) _y CH (CH ₃ ) O) — represents an oxygen atom A form in which the terminal on the side is bonded to X is preferred.

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

The total content of the compound represented by the general formula (Z-4) or (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 (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by a reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxy group of the ring-opening skeleton. Each step is a well-known step, and a person 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 are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.

Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate containing four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku. Examples thereof include DPCA-60, which is a hexafunctional acrylate containing six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate containing three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765; Urethane compounds containing an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition-polymerizable compounds containing an amino structure and / or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 By using a kind, it is possible to obtain a composition excellent in the photosensitive speed.
Commercially available products include urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA- Examples thereof include 306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha).

The polymerizable compound preferably has an SP (Solubility Parameter) value of 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more.
In this specification, the SP value is determined by the Hoy method unless otherwise specified (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal ^1/2 cm ^−3/2 .

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

General formula (Q3)

In the general formula (Q3), Ar ¹¹ to Ar ¹⁴ each independently represents an aryl group containing a benzene ring surrounded by a broken line. X ¹ to X ⁴ each independently represents a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. a and b each independently represents an integer of 1 to 5, and c and d each independently represents an integer of 0 to 4. R ¹ to R ⁴ each independently represents a substituent, e, f, g and h each independently represents an integer of 0 or more, and the upper limit values of e, f, g and h are Ar ¹¹ to Ar ¹⁴ respectively. This is a value obtained by subtracting a, b, c, or d from the number of substituents that can be contained. However, when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ¹ to X ⁴ and R ¹ to R ⁴ are Each may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.

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

In the general formula (Q3), X ¹ to X ⁴ each independently represent a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. The substituent containing a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but is preferably an aliphatic group containing a polymerizable group.
The aliphatic group containing a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and 2 to 10 carbon atoms. And more preferably an alkylene group having 2 to 5 carbon atoms.
Further, 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 represented by —NR— (R is a substituent), an oxygen atom, or a sulfur atom. It is preferable that a non-adjacent —CH ₂ — in the aliphatic group is substituted with an oxygen atom or a sulfur atom, and a non-adjacent —CH ₂ — in the aliphatic group is preferable. More preferably, is substituted with an oxygen atom. The aliphatic group containing a polymerizable group represented by X ¹ to X ⁴ is preferably substituted at one or two positions with a hetero atom, more preferably at one position with a hetero atom, and Ar ¹¹ to More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line represented by Ar ¹⁴ is substituted with a hetero atom.
The polymerizable group contained in the aliphatic group containing the polymerizable group represented by X ¹ to X ⁴ is a radically polymerizable or cationically polymerizable group (hereinafter also referred to as a radically polymerizable group and a cationically polymerizable group, respectively). ) Is preferred.
As the radically polymerizable group, generally known radically polymerizable groups can be used, and preferable examples thereof include a polymerizable group containing an ethylenically unsaturated bond capable of radical polymerization, Can include a vinyl group, a (meth) acryloyloxy group, and the like. Among these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationic polymerizable group, generally known cationic polymerizable groups can be used. Specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group Groups and the like. Of these, alicyclic ether groups and vinyloxy groups are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
The polymerizable group contained in the substituent contained in Ar ¹ to Ar ⁴ is preferably a radical polymerizable group.
Two or more of Ar ¹ ~ Ar ⁴ comprises a substituent containing a polymerizable ^group, preferably contains a substituent 2-4 of Ar 1 ~ Ar ⁴ contains a polymerizable group, Ar More preferably, two or three of ¹ to Ar ⁴ contain a substituent containing a polymerizable group, and two of Ar ¹ to Ar ⁴ contain a substituent containing a polymerizable group. Further preferred.
When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ¹ to X ⁴ are each independently surrounded by a broken line Even if it is substituted with a benzene ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.

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

In the general formula (Q3), R ¹ to R ⁴ each independently represents a substituent. The substituent represented by R ¹ to R ⁴ is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxy groups, hydroxyalkyl groups, alkoxy groups, aryl groups, hetero groups. An aryl group, an alicyclic group, etc. can be mentioned. The substituent represented by R ¹ to R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group. And more preferably a methyl group, a methoxy group or a phenyl group.
In the general formula (Q3), when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, R ¹ to R ⁴ are Each may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.

In the general formula (Q3), e, f, g, and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g, and h can be substituted by Ar ¹¹ to Ar ^14, respectively. A value obtained by subtracting a, b, c, or d from the number of groups.
e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and still more preferably 0.
When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h may be 0 or 1 Preferably, it is 0.

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

Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, on-coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).

In the case where the composition contains a polymerizable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

(Polymerization initiator)
The composition preferably contains a polymerization initiator.
It does not restrict | limit especially as a polymerization initiator, It can select suitably from well-known polymerization initiators, For example, what has photosensitivity (what is called a photoinitiator) is preferable.
When the composition contains a photopolymerization initiator and the polymerizable compound in addition to the metal nitride-containing particles, the composition is cured by irradiation with actinic rays or radiation. Sometimes called.
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, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and may be an initiator that initiates cationic polymerization according to the type of the polymerizable compound.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within 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, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
Examples of the halogenated hydrocarbon compound containing the triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-258241, compound described in JP-A-5-281728, compound described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Preferred are compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds. .

More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, or acetophenone compounds, trihalomethyltriazine compounds, α- Particularly preferred is at least one compound selected from the group consisting of an aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

In particular, when the above composition is used for the production of a light-shielding film, it is necessary to form a fine pattern with a sharp shape. is there. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed, stepper exposure is used for exposure for curing, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

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

(Oxime compounds)
More preferred examples of the photopolymerization initiator include oxime compounds (oxime initiators). In particular, an oxime compound is preferable because it has high sensitivity and high polymerization efficiency, can be cured regardless of the color material concentration, and can be easily designed with a high color material concentration.
As specific examples of the oxime compound, a compound described in JP-A No. 2001-233842, a compound described in JP-A No. 2000-80068, or a compound described in JP-A No. 2006-342166 can be used.
Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A No. 2000-66385, JP-A No. 2000-80068, JP-T 2004-534797, and JP-A No. 2006-342166. .
IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) are also suitably used as commercial products. Also, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA), or N-1919 (carbazole oxime ester containing light An initiator (manufactured by ADEKA) can also be used.

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

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

An oxime compound containing a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound containing a fluorine atom include compounds described in JP2010-262028; compounds 24 and 36 to 40 described in JP2014-500852; compounds described in JP2013-164471A (C-3); and the like. This content is incorporated herein.

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

In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or arylalkyl group having 7 to 30 carbon atoms, R ¹ and R ² is a phenyl group, may form a fluorene group together a phenyl group are bonded to, R ³ and R ⁴ are each independently, Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.

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

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

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
In the above formulas (3) and (4), R ¹ is preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl, cyclohexyl group or phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

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

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is more preferable.
For the molar extinction coefficient of the compound, a known method can be used. For example, in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
You may use a photoinitiator in combination of 2 or more type as needed.

When the composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30% by mass with respect to the total solid content in the composition, preferably 1 to 25% by mass. More preferably, it is 1 to 10% by mass. The composition may contain only one kind of polymerization initiator, or may contain two or more kinds. When two or more types are contained, the total amount is preferably within the above range.

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

<Surfactant>
The said composition may contain various surfactant from a viewpoint of improving applicability | paintability more. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

By including a fluorosurfactant in the above composition, the liquid properties (particularly fluidity) when prepared as a coating liquid can be further improved, and the uniformity of coating thickness and liquid saving can be further improved. it can. That is, in the case of forming a film using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability | paintability to a to-be-coated surface improves. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

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

Examples of the fluorosurfactant include MegaFuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used. A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The fluorine-containing surfactant contains a repeating unit derived from a (meth) acrylate compound containing a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) ( A fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

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

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

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer 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 anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.

Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

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

<Colorant>
The composition may contain a colorant other than the metal nitride-containing particles (hereinafter also simply referred to as “colorant”). The colorant is used, for example, for adjusting the chromaticity of the composition, and it is possible to replace a part of the metal nitride-containing particles with the colorant as long as the OD (Optical Density) value does not decrease. Examples of such a colorant include pigments (black organic pigments and chromatic organic pigments, and inorganic pigments) and dyes.

(Pigment)
The pigment is not particularly limited, and a known pigment can be used. Examples of chromatic organic pigments include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 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 Etc. 168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214;
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc .;
C. I. Pigment green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment violet 1, 19, 23, 27, 32, 37, 42, etc .;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Is mentioned.

Further, as the green pigment, a zinc halide phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, bromine atoms on average 8 to 12, and chlorine atoms on average 2 to 5 should be used. Is also possible. Specific examples include the compounds described in International Publication No. 2015/118720.
These organic pigments can be used alone or in various combinations in order to increase color purity.

Various known black pigments can be used as the black pigment. Examples thereof include carbon black and / or black metal-containing inorganic pigments shown below. Examples of the black metal-containing inorganic pigment include metal oxides containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Can be mentioned. These may be used alone or as a mixture of two or more. Moreover, you may prepare so that it may have desired light-shielding property by combining and using the inorganic pigment of another hue further in a black pigment. Examples of specific inorganic pigments that can be used in combination include, for example, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, and yellow lead. , Zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, victoria green, bitumen blue (Prussian blue) ), Vanadium zirconium blue, chrome tin pink, pottery red, salmon pink and the like. In particular, these black pigments and other inorganic pigments having other hues are used not only independently but also in combination with a plurality of types of pigments for the purpose of expressing light-shielding properties in a wide wavelength range from ultraviolet to infrared. Is possible.

The average primary particle diameter of the black pigment is preferably 5 nm or more, and 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 still more preferably 100 nm or less. The average primary particle diameter of the black pigment is intended to be the average primary particle diameter measured by the same method as the average primary particle diameter of the metal nitride-containing particles.

(dye)
Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. Disclosed in U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828. Can be used. When classified as chemical structures, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazole azomethine compounds Etc. can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

The above composition may contain extender pigments as necessary in addition to the colorant. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more. The amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the colorant. Colorants and extenders can be used with their surfaces modified with polymers.

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

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

<Pigment derivative>
The composition can contain a pigment derivative. Examples of the pigment derivative include a compound containing a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthalimidomethyl group.
Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
Moreover, as an acidic group which a pigment derivative contains, a sulfonic acid group, a carboxylic acid group, and its quaternary ammonium base are preferable, a carboxylic acid group or a sulfonic acid group is still more preferable, and a sulfonic acid group is especially preferable. The basic group contained in the pigment derivative is preferably an amino group, more preferably a tertiary amino group.
Specific examples of the pigment derivative include the following compounds. In addition, the descriptions in paragraphs 0162 to 0183 of JP2011-252065 A can be referred to, and the contents thereof are incorporated in this specification.

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 with respect to the total mass of the colorant. The composition may contain only one type of pigment derivative or two or more types of pigment derivatives. When two or more types are contained, the total amount is preferably within the above range.

<Silane coupling agent>
A silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
In addition, when forming a cured film on the substrate, the silane coupling agent improves the adhesion between the substrate and the cured film, so fluorine atoms and silicon atoms (however, excluding silicon atoms to which hydrolyzable groups are bonded) It is preferable that it does not contain, a fluorine atom, a silicon atom (except a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and carbon It is desirable not to include a branched alkyl group of several or more.

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

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

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

One preferred embodiment of the silane coupling agent is a silane coupling agent X represented by the formula (W).
Formula (W) R _Z2 -Lz-Si- (R _Z1 ) ₃
R _z1 represents a hydrolyzable group, and the definition is as described above.
R _z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, —NR ¹² —, —CONR ^{_{12 -, - CO -, -}} CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof. Among them, at least one selected from the group consisting of an alkylene group which may be substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group which may be substituted with a halogen atom having 6 to 12 carbon atoms, or At least selected from the group consisting of these groups and —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, and SO ₂ —. A group composed of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO ₂ —, —O—, —CO—, —CONR ¹² —, or A group consisting of a combination of these groups is more preferred. Here, R ¹² represents a hydrogen atom or a methyl group.

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

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

The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably contains at least one organic group. The amino group structure may be present in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may be present as a substituted amino group such as aniline.
Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent. Examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide. Group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkyleneoxy group ammonium group, alkylammonium group, carboxylic acid group, or a salt thereof, sulfo group and the like.
Moreover, it is preferable that the nitrogen atom is couple | bonded with the curable functional group through arbitrary organic coupling groups. Preferred examples of the organic linking group include a substituent that can be introduced into the nitrogen atom and the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
The silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to take an embodiment in which two or more curable functional groups are contained. From the viewpoint of property, it is preferable to contain 2 to 20 curable functional groups, more preferably 4 to 15 and most preferably 6 to 10 curable functional groups in the molecule.

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

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

The above composition may contain one silane coupling agent or two or more silane coupling agents. When a composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.

<Ultraviolet absorber>
The composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used. As specific examples thereof, compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) is also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass with respect to the total solid content of the composition.

<Polymerization inhibitor>
The composition may contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the composition. The composition may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
If necessary, higher fatty acid derivatives such as behenic acid and / or behenic acid amide may be added to prevent polymerization inhibition due to oxygen and unevenly distributed on the surface of the coating film during the drying process after coating. Good. The content of the higher fatty acid derivative is preferably 0.5 to 10% by mass with respect to the total solid content of the composition.

In addition to the above components, the following components may be further added to the composition. Examples include sensitizers, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and sensitizers, and further adhesion promoters to the substrate surface. And other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) You may add a well-known additive as needed.
These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding <0237> to <0309> of US Patent Application Publication No. 2013/0034812) and JP2008-250074. The descriptions of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP 2013-195480 A can be taken into consideration, and the contents thereof are incorporated in the present specification. It is.

[Production Method of Composition]
The manufacturing method of the said composition contains the following mixing and dispersion | distribution processes. Moreover, it is more preferable to contain a stationary process and / or a filtration process. Below, a suitable aspect is explained in full detail about each process.

<Mixing and dispersing process>
A mixing and dispersion | distribution process is a process of mixing the said component with a well-known mixing method (For example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser), and obtaining a composition.
In the mixing and dispersing step, each component constituting the composition may be mixed at once, or may be sequentially added after each component is dissolved or dispersed in an organic solvent. Moreover, the order of input and the working conditions when blending are not particularly limited. Further, the mixing and dispersing step may include a step of producing a dispersion.

(Process for producing dispersion)
The step of preparing the dispersion is a step of preparing the dispersion by mixing the metal nitride-containing particles, the dispersant, and the solvent, and dispersing the metal nitride-containing particles by the above method. The remaining components can be mixed with the prepared dispersion to produce a composition.
In the step of preparing the dispersion, the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion. In addition, “Dispersion Technology Encyclopedia, Issued by Information Technology Corporation, July 15, 2005” and “Distribution technology and industrial application centered on suspension (solid / liquid dispersion system) and comprehensive application data collection, Management Development Center publication. The process and the dispersing machine described in “Issuance of the Department, October 10, 1978” can be preferably used.
Moreover, in the process of producing the said dispersion liquid, you may perform the refinement | miniaturization process of the pigment by a salt milling process. For example, materials described in JP-A-2015-194521 and JP-A-2012-046629 can be used as materials, equipment and processing conditions used in the salt milling process.
Moreover, it is preferable that the manufacturing method of the said composition contains the process of obtaining the said metal nitride containing particle | grains by a thermal plasma method. The step of obtaining metal nitride-containing particles is performed before mixing the above-described components. The embodiment of the specific manufacturing process of the metal nitride-containing particles by the thermal plasma method is as described above.

<Standing process>
The metal nitride-containing particles are preferably subjected to the following stationary step before being subjected to the mixing and dispersing step or the step of producing a dispersion.
The standing step refers to a predetermined time (preferably 12 to 72 hours) in a sealed container in which the metal nitride-containing particles obtained by the thermal plasma method are not exposed to the atmosphere after their production and the oxygen concentration is controlled. (More preferably 12 to 48 hours, still more preferably 12 to 24 hours). At this time, it is more preferable that the moisture content in the sealed container is controlled.

At this time, the oxygen (O ₂ ) concentration and the water content in the sealed container are each preferably 100 ppm or less, more preferably 10 ppm or less, and still more preferably 1 ppm or less.
The content of oxygen (O ₂₎ concentration and moisture in the sealed container can be performed by adjusting the oxygen concentration and water content in the inert gas supplied in a sealed container. As the inert gas, nitrogen gas and argon gas are preferably used, and among these, it is more preferable to use nitrogen gas.
After the standing step, the surface and crystal grain boundaries of the metal nitride-containing particles become stable. Thereby, generation | occurrence | production of the pinhole of the cured film obtained using a composition can be suppressed.
The standing step can be replaced with step H described in the method for producing metal nitride-containing particles, and can be replaced with step H in that the composition has a more excellent effect of the present invention. preferable.

<Filtration process>
A filtration process is a process of filtering the composition manufactured by the said mixing and dispersion | distribution process with a filter. In the filtration step, foreign substances can be removed from the composition and / or defects can be reduced.
Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, or a polyolefin resin such as polyethylene or polypropylene (PP) (containing high density and ultra high molecular weight) can be used. . Among these materials, polypropylene (containing high density polypropylene) and nylon are preferable.
The filter has a pore diameter of about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and still more preferably 0.3 to 0.0 μm. 7 μm. By setting it within this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within said range. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

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

The film thickness of the light shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and preferably 0.3 μm or more and 10 μm or less, in that the light shielding film has the effect of the present invention. Is more preferably 0.3 μm or more and 5 μm or less. Since the above composition has a high optical density per unit volume (because of its high light shielding properties), the film thickness can be reduced as compared with a composition using a conventional black pigment.
The size of the light-shielding film (the length of one side of the light-shielding film provided around the sensor light-receiving portion) is preferably 0.001 mm or more and 10 mm or less in that the light-shielding film has more excellent effects of the present invention. 05 mm or more and 7 mm or less are more preferable, and 0.1 mm or more and 3.5 mm or less are still more preferable. Since the above composition has a high optical density per unit volume, it is advantageous for microfabrication, such as being able to reduce the coating amount, and is excellent in resolution and anticorrosion properties of the electrode. Can do.

[Method for producing cured film]
Next, a method for manufacturing the cured film (light-shielding film) will be described using a method for manufacturing a color filter containing a black matrix as an example.
The color filter containing the black matrix contains a cured film (black matrix) obtained using the composition on the substrate.
Hereinafter, the manufacturing method of the color filter containing the said black matrix is explained in full detail for every process.

The manufacturing method of the color filter containing the said black matrix contains the following composition layer formation processes, an exposure process, and a image development process.
Composition layer forming step: a step of applying the above composition onto a substrate to form a composition layer (coating film).
Exposure step: a step of exposing the composition layer through a photomask (hereinafter also simply referred to as “mask”).
Development step: A step of developing the exposed composition layer to form a patterned cured film (light-shielding film).

Specifically, the composition is applied on a substrate directly or through another layer to form a composition layer (composition layer forming step), exposed through a predetermined mask pattern, and light. Only the irradiated coating film portion is cured (exposure process) and developed with a developer (development process), whereby the color filter can be produced.
Hereinafter, each process in the manufacturing method of the color filter containing the said black matrix is demonstrated.

<Composition layer formation step>
The composition layer forming step is a step of forming the composition layer (coating film) by coating the composition on the substrate.
Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used in liquid crystal display devices and the like, and a transparent conductive film attached to these, photoelectric devices used in solid-state imaging devices, and the like. Examples include a conversion element substrate (for example, a silicon substrate), a CCD (Charge Coupled Device) substrate, and a CMOS (Complementary Metal-Oxide Semiconductor) substrate.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

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

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

The composition coated on the substrate is usually dried at 70 ° C. or higher and 110 ° C. or lower for 2 minutes or more and 4 minutes or less. Thereby, a composition layer can be formed.

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

<Development process>
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
As the developer, when producing a light-shielding color filter containing a black matrix for a solid-state imaging device, an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.

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

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

In addition, the manufacturing method of the color filter containing the said cured film (black matrix) may contain the hardening process which hardens a cured film by a heating and / or exposure after the said image development process.

The color filter containing the cured film (black matrix) is excellent in resolution and corrosion resistance of the electrode.
Therefore, the color filter containing the said cured film (black matrix) is suitable for solid-state image sensors, such as a CCD image sensor and / or a CMOS image sensor. Particularly, it is suitable for a CCD image sensor and / or a CMOS image sensor having a high resolution exceeding 1 million pixels. That is, the color filter containing the cured film is suitable for a solid-state imaging device. Further, the color filter may include a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
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 device]
The solid-state imaging device contains the cured film (black matrix). The solid-state imaging device preferably contains a color filter that contains a black matrix and, if necessary, a patterned film composed of pixels of other colors (three colors or four colors).
The solid-state imaging device is not particularly limited as long as it contains the black matrix and functions as a solid-state imaging device. For example, a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is formed on a substrate. And a solid-state imaging device containing the black matrix on the surface opposite to the light-receiving element forming surface of the substrate.
In addition, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the solid-state imaging device containing such a structure include the solid-state imaging devices described in JP2012-227478A and JP2014-179577A.

[Image display device]
The said cured film is suitable for image display apparatuses, such as a liquid crystal display device and an organic electroluminescent display apparatus.

For the definition of image display devices and details of each image display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)” and “Display Device (Junsho Ibuki, Industrial Books ( (Issued in 1989)). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The cured film is suitable for, for example, a liquid crystal display device of the method described in the “next generation liquid crystal display technology”.

As one mode of the liquid crystal display device containing the cured film, for example, a color filter, a liquid crystal layer, and a liquid crystal driving means (simple matrix driving method and active matrix driving) are provided between a pair of substrates at least one of which is light transmissive. And a liquid crystal display device containing at least a 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 cured film (black matrix).

In another aspect of the liquid crystal display device, at least one includes a color filter, a liquid crystal layer, and liquid crystal driving means between a pair of light-transmitting substrates, and the liquid crystal driving means is an active element ( For example, a color filter containing a TFT (Thin Film Transistor) and containing the cured film (black matrix) between the active elements is contained.

The color filter containing the cured film is suitable for a liquid crystal display device of a color TFT (Thin Film Transistor) type. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the color filter is a liquid crystal display device with a wide viewing angle, such as a lateral electric field driving method such as IPS (In Plane Switching); a pixel division method such as MVA (Multi-domain Vertical Alignment); and STN (Super-Twist). Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optics).

The color filter is suitable for a bright, high-definition COA (Color-filter On Array) type liquid crystal display device. In the COA type liquid crystal display device, the required characteristics for the color filter may require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling solution, in addition to the normal required characteristics. The COA type liquid crystal display device containing the color filter has better resolution or better durability. In order to satisfy 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, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(Toray Research Center Research Division, issued in 2001)". In the above, EL stands for Electroluminescence, PDP stands for PlasmaPDisplay Panel, and LCD stands for liquid crystal display.

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

The cured film is composed of portable devices such as personal computers, tablets, mobile phones, smartphones and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, bar code readers, and automatic cash deposits. Machine (ATM: automated teller 本 machine), high-speed camera and industrial equipment such as personal authentication using facial image authentication; in-vehicle camera equipment; medical camera equipment such as endoscope, capsule endoscope and catheter; Optics used in space equipment such as sensors, biosensors, military reconnaissance cameras, 3D map cameras, meteorological and oceanographic observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets. Filter and module shading member and Shielding layer, further is suitable for anti-reflection member and the antireflection layer.

The cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The cured film is suitable for members that provide a light shielding function or an antireflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.
Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.

The cured film is suitable as an optical and optical film used in quantum dot displays. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function.
Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.

Hereinafter, the composition and the like will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[Preparation of metal nitride-containing particles P-1]
Metal nitride-containing particles P-1 were produced by the following method.
First, niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemicals, which contains niobium as a transition metal, was 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 spectroscopy. For the ICP emission spectroscopic analysis, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.

Next, the metal raw material powder was subjected to plasma treatment in Ar gas (treatment conditions were as described in the following plasma treatment (1)) to form metal fine particles. It was 80 nm when the average primary particle diameter of the obtained metal fine particle was measured. In addition, the average primary particle diameter was calculated | required with the following method.
Sample: [Preparation of metal nitride-containing particle dispersion] to be described later for a dispersion (25% by mass of fine metal particles, 7.5% by mass of dispersant A described below, PGMEA; 67.5% by mass of propylene glycol monomethyl ether acetate solvent) A dispersion prepared by the same method, diluted 100 times with PGMEA, dropped onto a carbon foil and dried.
The sample was observed with a transmission electron microscope (TEM) at a magnification of 20,000 to obtain an image. The area of the metal fine 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 is performed on a total of 400 metal fine particles (approximately 3000 metal fine particles are confirmed in each visual field) for four visual fields, and the average diameter of the metal fine particles is calculated by arithmetically averaging the evaluated diameters in terms of circles. It was.

Further, when impurities contained in the metal fine particles were measured by the above method, no impurities were detected. In addition, it means that content of an impurity is less than 20 ppm with respect to the total mass of metal microparticles that an impurity is not detected by said method.

<Plasma treatment (1)>
Plasma treatment (1) was performed by the following method. That is, a plasma treatment (1) was performed under the following conditions using an apparatus according to the black composite fine particle production apparatus shown in FIG. 1 of International Publication No. 2010/147098 as the metal fine particle production apparatus.
・ High-frequency voltage applied to the coil for high-frequency oscillation: Frequency, about 4 MHz, voltage, about 80 kVA ・ Plasma gas: Argon gas (Supply rate: 100 L / min)
Carrier gas: Argon gas (Supply amount: 10 L / min)
-Chamber atmosphere: Argon gas (Supply rate 1000L / min, Chamber flow rate 5m / sec)
・ Cyclone atmosphere: Argon gas, Internal pressure: 50 kPa
・ Material supply speed from chamber to cyclone: 10 m / s (average value)

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

Next, the metal fine particles obtained above and the atomized atom A were mixed to obtain a raw metal powder. About this raw material metal powder, the metal nitride containing particle | grains were obtained by carrying out plasma processing in nitrogen gas (a processing condition is based on the following plasma processing (2)).

<Plasma treatment (2)>
Plasma treatment (2) was performed by the following method. The apparatus used is the same as in the plasma treatment (1).
・ High frequency voltage applied to the coil for high frequency oscillation: Frequency, about 4 MHz, voltage, about 80 kVA ・ Plasma gas: Argon gas and nitrogen gas (Supply amount 50 L / min each)
・ Carrier gas: Nitrogen gas (Supply amount: 10L / min)
・ Atmosphere in chamber: Nitrogen gas (amount supplied: 1000 L / min, flow velocity in chamber: 5 m / sec)
・ Cyclone atmosphere: Nitrogen gas, internal pressure 50kPa
・ Material supply speed from chamber to cyclone: 10 m / s (average value)

When the metal nitride-containing particles after the plasma treatment (2) are finished, the nitrogen gas at 20 ° C. is used under the condition that the relative humidity is 95% in the atmosphere by using a shunt type humidity supply device SRH manufactured by Nippon Shintec Co., Ltd. using Ar gas. It was introduced and allowed to stand for 24 hours. Thereafter, the obtained metal nitride-containing particles were classified using a TTSP separator manufactured by Hosokawa Micron under the conditions of a yield of 10% to obtain metal nitride-containing particles P-1. Nitrogen gas was supplied to the separator.

The average primary particle diameter of the metal nitride-containing particles P-1 was measured and found to be 12 nm. Further, the conductivity of the metal nitride-containing particle P-1 was measured and found to be 180 × 10 ⁴ S / m.
In addition, an average primary particle diameter is an average primary particle diameter measured by said method.
In addition, the said electrical conductivity is the electrical conductivity measured by the following method.
The conductivity was measured by the following method using a powder resistance measurement system MCP-PD51 manufactured by Mitsubishi Chemical Analytech.
First, 1 g of metal nitride-containing particles are packed in a measuring container having a diameter of 20 mm of the above measuring apparatus, and then pressurization is started to change the pressure to 0 kN, 1 kN, 5 kN, 10 kN, 20 kN, and the volume resistivity of the particles ( ρ) was measured. From the measurement results, the saturated volume resistivity under the condition that the volume resistivity does not depend on the pressure was obtained, and the conductivity (σ) was calculated by the relational expression of σ = 1 / ρ using the obtained saturated volume resistivity. The above test was conducted in a room temperature environment.

[Production of Metal Nitride-Containing Particles P-2 to P-7, P-C1 and P-C5]
The metal nitride-containing particles P-2 to P-7, P-C1 and P- are the same as the metal nitride-containing particles P-1, except that the content of atoms A is as described in Table 1. C5 was produced.
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 related to the production of the metal nitride-containing particles are summarized in Table 1.

[Preparation of metal nitride-containing particles PC2]
Metal nitride-containing particles P-C2 were produced in the same manner as the metal nitride-containing particles P-1, except that the atom A was not added to the transition metal raw material.
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 related to the production of the metal nitride-containing particles are summarized in Table 1.

[Production of Metal Nitride-Containing Particles P-8 to P-15]
The metal nitride-containing particles P-8 are the same as the metal nitride-containing particles P-1 except that the transition metal raw materials shown in Table 1 are used and the content of atoms A is as described in Table 1. To P-15 were produced.
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 related to the production of the metal nitride-containing particles are summarized in Table 1.

[Production of Metal Nitride-Containing Particles PC3 and PC4]
Instead of the transition metal raw material, the raw materials shown in Table 1 were used, and the metal nitride-containing particles P-C3 and the metal nitride-containing particles P-1 were the same as the metal nitride-containing particles P-1, except that the atoms A were not added. PC4 was prepared.
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 related to the production of the metal nitride-containing particles are summarized in Table 1.

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

Nb powder: Niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemicals
・ V powder: Metal vanadium powder VHO made by Taiyo Mining
-Zr powder: Zirconium powder made by Wako Pure Chemical Industries-Tantalum Nodal: Tantalum Nodal made by Global Advanced Metal
・ Hf powder: Hafnium powder made by Furuuchi Chemical ・ Y powder: Yttrium powder made in Japan yttrium ・ Cr powder: Degassed electrolytic metal chrome powder made by Kosei ・ Re powder: Rhenium powder made by Rhenium Alloys ・ W powder: Tungsten powder AW3110 made by Eurotungsten
・ Al powder: Aluminum powder No. 22000
・ Si powder: Silicon powder made by Furuuchi Chemical ・ Fe powder: JIP 270M made by Fe powder JFE Steel
・ Ni powder: Ni powder 300 nano product made by Toho Titanium ・ Ag powder: Ag powder made by Mitsui Kinzoku SPQ03R

In addition, "ppm" in the following Table 1 intends mass ppm.
In the table, “not detected” indicates that no impurity was detected when measured by the above measurement method, specifically, less than 20 ppm by mass. “Not added” indicates that the atom A was not added, and “Not measured” indicates that the measurement was not performed because the atom A was not added. Therefore, “not measured” indicates substantially less than 20 ppm by mass (calculated less than 5 ppm by mass).

<Dispersant>
Dispersants A to C having the following structures were used as the dispersant. In the dispersants A and C, the numerical value described in each structural unit intends the mass% of each structural unit with respect to the total structural units. In the dispersant B, the letters described in each structural unit intend mol% of each structural unit with respect to all the structural units.

・ Dispersant A

・ Dispersant B

・ Dispersant C

<Binder resin>
As the binder resin, the following resin A and resin B were used. The structures of the resin A and the resin B are shown below. In the resin A and the resin B, the numbers described in each structural unit are intended to be mol% of each structural unit with respect to all the structural units.

Resin A: ACRYCURE RD-F8 (trade name, manufactured by Nippon Shokubai Co., Ltd.)

・ Resin B

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

<Polymerizable compound>
Polymerizable compound M1: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD”, see the following formula)

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)

<Polymerization inhibitor>
・ PMF: p-methoxyphenol

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

<Organic solvent>
-PGMEA: Propylene glycol monomethyl ether acetate-CPN: Cyclopentanone-Acetic acid Bu: Butyl acetate

[Preparation of metal nitride-containing particle dispersion]
First, metal nitride-containing particles, a dispersant and an organic solvent were mixed for 15 minutes with a stirrer (EUROSTAR manufactured by IKA) to obtain a mixed solution of the above components. Next, the obtained mixed solution was subjected to a dispersion treatment using NPM-Pilot made by Shinmaru Enterprises under the following conditions to obtain a metal nitride-containing particle dispersion. In addition, it added so that the mass ratio (D / P) of the dispersing agent with respect to metal nitride containing particle | grains might become the value shown in the Example of Table 3, and a comparative example.

<Distribution conditions>
・ Bead diameter: 0.05mm, (Nikkato zirconia beads, YTZ)
・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 13m / s
・ Amount of liquid mixture to be dispersed: 15kg
・ Circulating flow rate (pump supply amount): 90 kg / hour
・ Processing liquid temperature: 19-21 ℃
・ Cooling water: Water ・ Processing time: About 22 hours

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

<Measurement of water content in composition>
The water content of each of the compositions of Examples and Comparative Examples was measured by MKV-710 (trade name, manufactured by Kyoto Electronics Industry Co., Ltd.) using the Karl Fischer method as a measurement principle. The results are shown in Table 3.

[Evaluation test]
The following evaluation tests were performed on the compositions of the examples and comparative examples. The results are summarized in Table 3.

[OD value]
A coating film was formed by spin coating on each glass composition (Eagle XG, manufactured by Corning) having a thickness of 0.7 mm and a 10 cm square. At this time, the number of revolutions was adjusted so that the film thickness became 1.5 μm according to the solid content concentration of each composition. The formed coating film was dried by heat treatment at 100 ° C. for 2 minutes on a hot plate to obtain a cured film. About the board | substrate containing the obtained cured film, OD value was measured with the spectrophotometer U-4100 (made by Hitachi High-Technologies). The higher the OD value, the better the light-shielding property of the cured film. Evaluation was performed according to the following criteria. Practically “C” or more is preferable.
A: OD value is over 4 B: OD value is over 3 and 4 or less C: OD value is over 2 and 3 or less D: OD value is 2 or less

[Stability over time]
100 mL of the metal nitride-containing particle dispersion was added to a container having a diameter of 50 mm and a capacity of 100 mL, and allowed to stand at room temperature for 9 minutes. After standing, the metal nitride-containing particle dispersion for 1 cm of the supernatant was withdrawn, and the 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 according to the following criteria. Practically “C” or more is preferable.
(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 3% or more 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 by PGMEA was prepared, and the number of metal nitride-containing particles having a size of 10 μm or more contained in 10 ml of the sample solution was determined by a flow particle image analyzer (trade name “FPIA”). , Manufactured by Malvern). Evaluation was performed according to the following criteria. Practically “C” or more is preferable.
A: Number of particles is 3 or less B: Number of particles is 4 to 10 C: Number of particles is 11 to 20 D: Number of particles is 21 or more

[Resolution]
The composition was applied onto an 8-inch silicon substrate to prepare a coating film. The coating film was prepared using a coater developer ACT8 manufactured by Tokyo Electron, and the number of revolutions was adjusted so that the film thickness became 1.5 μm corresponding to the solid content concentration of each composition. The obtained coating film was subjected to heat treatment at 100 ° C. for 2 minutes as a pre-bake treatment on a hot plate. The coating film was exposed (negative) through a photomask on which an island pattern with a width of 10 μm was formed using an i-line stepper (Canon FPA3000i5 +) on the substrate with the coating film after the pre-baking. The exposed coating film is subjected to paddle development for 30 seconds using CD-2060 (manufactured by FUJIFILM Electronics Materials) as a developer using a coater developer ACT8 manufactured by Tokyo Electron, and rinsed with pure water after development. Went. The developed coating film was post-baked (temperature: 220 ° C., time: 10 minutes). The pattern shape of the coating film after post-baking was measured with a length measuring SEM (Scanning Electron Microscope). Specifically, the width of the island was measured and evaluated according to the following criteria. Practically “C” or more is preferable.
A: The width of the island is 9.5 μm to 10.5 μm
B: The width of the island is 8 μm or more and less than 9.5 μm, or more than 10.5 μm and 12 μm or less C: The width of the island is less than 8 μm or more than 12 μm D: The island was not formed due to pattern peeling or insufficient development.

[Anti-corrosion of electrode]
Using the composition, a coating film was formed on an image sensor device substrate by a spin coater. The coating film was pre-baked on a hot plate at 100 ° C. for 2 minutes. On the substrate after the pre-baking treatment, an i-line exposure apparatus (FPA3000i5 +, manufactured by Canon) was used to form a light shielding layer covering the outer periphery of the light receiving portion on the substrate except for the dicing line and the electrode portion. Furthermore, heat treatment was performed at 220 ° C. for 5 minutes using a hot plate (post-baking step). After the light shielding film forming treatment, the substrate was exposed for 7 days under conditions of 130 ° C. and 90% relative humidity, and then wiring was formed by wire bonding. The occurrence of wire breakage was evaluated by a wire bonding inspection device manufactured by Canon Machinery. 50 chips were evaluated, and the number of wirings per chip was 40. Evaluation was performed according to the following criteria. Practically “C” or more is preferable.
A: No more than 1 wire break B: 2 or more but less than 5 wire C: 5 or more but less than 10 wire breaks D: 10 or more wire breaks

From the results shown in Table 3, the transition metal in which the metal nitride-containing particles are transition metals excluding titanium among the transition metals of Groups 3 to 11 and the electronegativity is 1.22 to 2.36. Cured films (light-shielding films) produced using the compositions of Examples 1 to 32 containing the nitrides described above have excellent light-shielding properties, excellent resolution, and excellent corrosion resistance of the electrodes. all right. On the other hand, the cured film (light-shielding film) produced using the compositions of Comparative Examples 1 to 5 did not achieve the desired effect.
Also, a cure made using the compositions of Examples 3, 8, 10, 12, 13, 14, and 15 where the transition metal is niobium, vanadium, tantalum, yttrium, chromium, rhenium, or tantagsten, respectively. The film (light-shielding film) has an OD value (light-shielding property) superior to a cured film (light-shielding film) produced using the composition of Example 9 or 11 in which the transition metal is zirconium or hafnium. It was. Especially, the cured film (light shielding film) produced using the composition of Example 3 or 8 whose transition metal is niobium or vanadium, respectively, had a further excellent OD value.
Further, the composition of Example 21 having a solid content of 10 to 40% by mass had a smaller number of particles than the composition of Example 22 having a solid content of more than 40% by mass.
In addition, the composition of Example 23 having a water content of 0.1 to 1% by mass had fewer particles than the composition of Example 24 having a content of more than 1% by mass.
In addition, the composition of Example 2 in which the content of metal nitride-containing particles is 20 to 70% by mass relative to the total solid content of the composition is compared with the composition of Example 29 that is less than 20% by mass. Thus, it had better temporal stability. In addition, the composition of Example 2 is more than 70% by mass, and the number of particles is smaller than that of the composition of Example 28, and the resulting cured film (light-shielding film) is more excellent. It had image properties.
In addition, the composition of Example 2 in which the mass ratio of the dispersant to the metal nitride-containing particles is 0.05 to 0.30 is compared with the composition of Example 32 in which the mass ratio is less than 0.05. Therefore, it had better temporal stability. Moreover, the cured film (light-shielding film) produced using the composition of Example 2 has a better resolution than the cured film (light-shielding film) produced using the composition of Example 18. Had sex.

[Production and Evaluation of Metal Nitride-Containing Particles P-1 (A)]
Metal nitride-containing particles P-1 (A) in which the surface of metal nitride-containing particles P-1 produced by the above method was coated with aluminum hydroxide were produced by the following method.
First, 100 g of metal nitride-containing particles P-1 were weighed and added to 750 mL of pure water, and well dispersed to obtain a slurry. Next, the above slurry was added to a solution obtained by dissolving 220 g of an aluminum chloride aqueous solution having a concentration of 10% by mass as aluminum oxide and 160 g of urea in 500 mL of water, and mixed well to obtain a mixture. The mixture was heated at 90 ° C. for 8 hours and cooled to room temperature. The cooled mixture is filtered, then washed with water, dried at 110 ° C. for 24 hours, and further calcined at 600 ° C. for 5 hours, so that the surface of the metal nitride-containing particles P-1 is coated with aluminum hydroxide. Nitride-containing particles P-1 (A) were obtained. The metal nitride-containing particles P-1 (A) had an average primary particle size of 13 nm and a conductivity of 100 S / m.
Next, using the metal nitride-containing particles P-1 (A), a dispersion and a composition were prepared in the same manner as in Example 1 above, and the OD value, resolution, corrosiveness of the electrode, When the stability and particles were evaluated, the results were the same as in 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)]
Using the metal nitride-containing particles P-2 to P-15 in the same manner as the metal nitride-containing particles P-1 (A), the metal nitride-containing particles P-2 (A) to P-15 ( A) was prepared. Table 4 shows the average primary particle diameter and conductivity of each.
Next, using the metal nitride-containing particles P-2 (A) to P-15 (A), a dispersion and a composition were prepared in the same manner as in Examples 2 to 32, and the OD value, When the image properties, the corrosiveness of the electrodes, the stability with time, and the particles were evaluated, the results were the same as in Examples 2 to 32 using the metal nitride-containing particles P-2 to P-15, respectively.

In Example 1, the evaluation was performed in the same manner except that the polymerization initiator was changed from OXE-02 to Irgacure OXE03 (trade name, manufactured by BASF Japan Ltd.), and the same result as in Example 1 could be obtained. I understood. Furthermore, compared to Example 1, the robustness with respect to the exposure amount was wide, and the resolution could be maintained even when the exposure amount was reduced.

Evaluation was conducted in the same manner as in Example 1 except that the polymerization initiator was changed from OXE-02 to Adeka Arcles NCI-831 (manufactured by ADEKA), and the same results as in Example 1 were obtained. I understood. Furthermore, compared to Example 1, the robustness with respect to the exposure amount was wide, and the resolution could be maintained even when the exposure amount was reduced.

Example 1 In the same manner as in Example 1 except that the polymerizable compound was changed from the polymerizable compound M1 to the polymerizable compound M2, the same results as in Example 1 were obtained.

In Example 1, the polymerizable compound was changed from the polymerizable compound M1 to a mixture of the polymerizable compounds M1 and M2 (1: 1 by mass ratio) without changing the content of the polymerizable compound with respect to the entire composition. Was evaluated in the same manner, and it was found that the same results as in Example 1 were obtained.

Example 1 In the same manner as in Example 1 except that PGMEA was used instead of the solvent CPN, it was found that the same result as in Example 1 was obtained.

In Example 1, evaluation was performed in the same manner except that PGMEA was used instead of the solvent CPN and Bu acetate, and it was found that the same result as in Example 1 was obtained.

Evaluation was conducted in the same manner as in Example 1 except that the surfactant F-556 was not used. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

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

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

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

<Preparation of chromatic pigment dispersion (PY dispersion)>
In preparation of the above-mentioned metal nitride-containing particle dispersion, Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN) was used instead of metal nitride-containing particles. A chromatic pigment dispersion (PY dispersion) was obtained by the same method.

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

Claims

A composition containing metal nitride-containing particles containing atoms A,
The metal nitride-containing particles contain a transition metal nitride that is a transition metal excluding titanium among the transition metals of Group 3 to 11, and has an electronegativity of 1.22 to 2.36. ,
The atom A is an element different from the transition metal constituting the nitride of the transition metal, and is at least one selected from the group consisting of boron, aluminum, silicon, manganese, iron, nickel, and silver,
The composition wherein the content of the atom A in the metal nitride-containing particles is 0.00005 to 10% by mass.
2. The composition according to claim 1, wherein the conductivity of the metal nitride-containing particles is 100 × 10 4 to 600 × 10 4 S / m.
The composition according to claim 1 or 2, wherein the metal nitride-containing particles have an average primary particle size of 10 to 50 nm.
The composition according to any one of claims 1 to 3, further comprising a binder resin.
The composition according to claim 4, wherein a mass ratio of the binder resin to the metal nitride-containing particles is 0.3 or less.
The composition according to any one of claims 1 to 5, wherein the transition metal is at least one selected from the group consisting of V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re. object.
The composition according to any one of claims 1 to 6, wherein the transition metal is at least one selected from the group consisting of V and Nb.
The composition according to any one of claims 1 to 7, further comprising a polymerizable compound.
The composition according to any one of claims 1 to 8, further comprising a polymerization initiator.
The composition according to any one of claims 1 to 9, further comprising a solvent and having 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 with respect to the total mass of the composition.
The composition according to any one of claims 1 to 11, wherein the content of the metal nitride-containing particles is 20 to 70 mass% with respect to the total solid content of the composition.
Furthermore, a dispersant is contained, and the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. The composition as described in any one of these.
The composition according to claim 13, wherein a mass ratio of the dispersant to the metal nitride-containing particles is 0.05 to 0.30.
The composition according to any one of claims 1 to 14, wherein the metal nitride-containing particles are metal nitride-containing particles coated with an inorganic compound containing aluminum hydroxide.
A method for producing the composition according to any one of claims 1 to 15,
A method for producing a composition, comprising a step of obtaining the metal nitride-containing particles by a thermal plasma method.
A cured film obtained using the composition according to any one of claims 1 to 15.
A color filter comprising the cured film according to claim 17.
A light-shielding film comprising the cured film according to claim 17.
A solid-state imaging device containing the cured film according to claim 17.
An image display device comprising the cured film according to claim 17.