WO2018061644A1

WO2018061644A1 - Metal nitride-containing particles, dispersion composition, curable composition, cured film, production method for these, color filter, solid-state imaging element, solid-state imaging device, and infrared sensor

Info

Publication number: WO2018061644A1
Application number: PCT/JP2017/031852
Authority: WO
Inventors: 浜田　大輔; 久保田　誠; 貴規田口; 裕貴坂本
Original assignee: 富士フイルム株式会社
Priority date: 2016-09-30
Filing date: 2017-09-05
Publication date: 2018-04-05
Also published as: TW201815682A; JPWO2018061644A1; KR20190041493A; TWI751196B; KR102294518B1; JP2022079500A; JP7373000B2

Abstract

Provided are metal nitride-containing particles capable of being used in a curable composition that has excellent anti-settling properties and excellent stability over time and is capable of obtaining a cured film having excellent light shielding properties. Also provided are: a dispersion composition; a curable composition; a cured film; a color filter; a solid-state imaging element; a solid-state imaging device; an infrared sensor; a production method for the metal nitride-containing particles; a production method for the dispersion composition; a production method for the curable composition; and a production method for the cured film. The metal nitride-containing particles: contain a nitride of a group 3–11 transition metal; have an average primary particle diameter of no more than 200 nm; and contain a nitrogen atom and an atom T. The atom T: is not an oxygen atom, a chlorine atom, or a nitrogen atom; is selected from group 13–17 elements; and fulfils T_E/T_X < 2.0 when the atom T content on a mass basis as detected by X ray photoelectron spectroscopic analysis is T_E and the atom T content on a mass basis as detected by fluorescent X ray analysis is T_X.

Description

Metal nitride-containing particles, dispersion composition, curable composition, cured film, and production method thereof, color filter, solid-state imaging device, solid-state imaging device, infrared sensor

The present invention relates to a metal nitride-containing particle, a dispersion composition, a curable composition, a cured film, a color filter, a solid-state imaging device, a solid-state imaging device, an infrared sensor, a method for producing metal nitride-containing particles, and a dispersion composition. The present invention relates to a method, a method for producing a curable composition, and a method for producing a cured film.

Conventionally, metal nitride-containing particles are known as particles contained in a composition for producing a cured film having a light-shielding property (hereinafter also referred to as “light-shielding film”). Metal nitride-containing particles are used for various applications, and in particular, compositions containing metal nitride-containing particles include, for example, image display devices (for example, liquid crystal display devices, organic EL (electroluminescence) devices, etc.), And a light-shielding film included in a solid-state imaging device or the like.
Specifically, a color filter included in an image display device or the like includes a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
The solid-state imaging device includes a light shielding film for the purpose of preventing noise generation 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 solid-state imaging devices. Such a solid-state imaging device 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, and a lens for forming a subject image on the solid-state imaging device. It has.

As particles contained in the composition for producing a cured film as described above, for example, Patent Document 1 discloses that the mass composition ratio of titanium nitride particles and titanium carbide particles is 80/20 to 20/80. The shading material which is the range is described.

JP 2010-95716 A

The present inventors have studied the composition containing the light shielding material described in Patent Document 1, and as a result, the light-shielding property of the resulting cured film, the anti-settling property of the composition, and the stability over time are recently required. I found out that the standard was not reached.
In the present specification, the light-shielding property, anti-settling property, and stability over time mean light-shielding property, anti-settling property, and stability over time measured by the methods described in Examples.

Therefore, the present invention can be used for a curable composition having excellent anti-settling properties and excellent temporal stability, and capable of obtaining a cured film having excellent light-shielding properties. (Hereinafter also referred to as “having the effect of the present invention.”) It is an object to provide metal nitride-containing particles.
The present invention relates to a dispersion composition, a curable composition, a cured film, a color filter, a solid-state imaging device, a solid-state imaging device, an infrared sensor, a method for producing metal nitride-containing particles, a method for producing a dispersion composition, and a curable composition. Another object of the present invention is to provide a method for producing a cured film and a method for producing a cured film.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-described problems can be achieved by the following configuration.

[1] A metal nitride-containing particle containing a transition metal nitride of Group 3 to 11 and having an average primary particle diameter of 200 nm or less, containing nitrogen atoms and atoms T, , Oxygen atom, chlorine atom, and nitrogen atom, selected from group 13-17 elements, and detected by X-ray photoelectron spectroscopy, containing atomic basis of mass T on the surface of metal nitride-containing particles When the amount is T _E (mass%) and the mass-based content of atoms T in the metal nitride-containing particles detected by fluorescent X-ray analysis is T _X (mass%), T _E / T _X < Metal nitride-containing particles satisfying the relationship represented by 2.0.
[2] The metal nitride-containing particle according to [1], further containing an oxygen atom.
[3] The atomic ratio X of the nitrogen atom content to the transition metal atom content of the nitride, and the oxygen atom ratio Y of the oxygen atom content to the transition metal atom content of the nitride In addition, the metal nitride-containing particles according to [2], wherein the atomic ratio Z of the content of atoms T to the content of transition metal atoms contained in the nitride is more than 0 and less than 2.
[4] The metal nitride-containing particle according to [3], wherein the sum of X, Y, and Z is more than 0.4 and less than 1.6.
[5] When the complex dielectric constant ε of the metal nitride-containing particles at a wavelength of 400 to 1200 nm is represented by ε = ε ′ + ε ″ j, the minimum value of ε ′ is less than 0, [1] to [4] The metal nitride-containing particles according to any one of the above, wherein ε ′ represents a real part of the complex dielectric constant ε, ε ″ represents an imaginary part of the complex dielectric constant ε, and j represents an imaginary unit.
[6] In any one of [1] to [5], the atom T is selected from elements other than aluminum, gallium, indium, tin, thallium, lead, and bismuth among the elements in the second to sixth periods. The metal nitride-containing particles as described.
[7] The metal nitride-containing particle according to [6], wherein the atom T is selected from Group 13-16 elements.
[8] The metal nitride-containing material according to any one of [1] to [7], wherein the atom T is any atom selected from the group consisting of a boron atom, a carbon atom, a sulfur atom, and a phosphorus atom particle.
[9] The metal nitride-containing particle according to any one of [1] to [8], wherein the atom T is any atom selected from the group consisting of a boron atom, a sulfur atom, and a phosphorus atom.
[10] A dispersion composition comprising the metal nitride-containing particles according to any one of [1] to [9] and a resin.
[11] A curable composition containing the dispersion composition according to [10], a polymerizable compound, and a polymerization initiator.
[12] A curable composition containing the metal nitride-containing particles according to any one of [1] to [9], a resin, a polymerizable compound, and a polymerization initiator.
[13] The curable composition according to [11] or [12], further containing a solvent.
[14] A cured film obtained by curing the curable composition according to any one of [11] to [13].
[15] A color filter containing the cured film according to [14].
[16] A solid-state imaging device containing the cured film according to [14].
[17] A solid-state imaging device containing the cured film according to [14].
[18] An infrared sensor containing the cured film according to [14].
[19] A method for producing metal nitride-containing particles according to any one of [1] to [9], comprising preparing a raw material A containing nitrogen atoms and a raw material B containing transition metal atoms and atoms T Preparing a raw material A containing nitrogen atoms, a raw material C containing transition metal atoms, and a raw material D containing atoms T, and mixing two or more raw materials in a gas phase state A method for producing metal nitride-containing particles, comprising: obtaining a mixture; and condensing the gas phase mixture to obtain metal nitride-containing particles.
[20] A method for producing a dispersion composition according to [10], wherein a raw material A containing nitrogen atoms and a raw material B containing transition metal atoms and atoms T are prepared, or a raw material containing nitrogen atoms Preparing a raw material C containing A, a transition metal atom, and a raw material D containing an atom T, a step of mixing two or more raw materials in a gas phase to obtain a mixture, and a gas phase A method for producing a dispersion composition, comprising: condensing a mixture in a state to obtain metal nitride-containing particles; and mixing metal nitride-containing particles and a resin to obtain a dispersion composition.
[21] A method for producing a curable composition comprising a dispersion composition, a polymerizable compound, and a polymerization initiator, the method comprising the method for producing a dispersion composition according to [20]. Manufacturing method.
[22] A curable composition layer forming step of forming a curable composition layer using the curable composition according to any one of [11] to [13], and a pattern on the curable composition layer An exposure step of irradiating with actinic rays or radiation through a photomask having an opening of the exposure step, and a development step of developing the curable composition layer after exposure to form a cured film The manufacturing method of a cured film.

According to the present invention, the composition can be used for a curable composition having excellent anti-settling property and excellent temporal stability and capable of obtaining a cured film having excellent light-shielding properties. Metal nitride-containing particles can be provided.
According to the present invention, a dispersion composition, a curable composition, a cured film, a color filter, a solid-state imaging device, a solid-state imaging device, an infrared sensor, a method for producing metal nitride-containing particles, a method for producing a dispersion composition, and curable properties The manufacturing method of a composition and the manufacturing method of a cured film can also be provided.

It is a schematic sectional drawing which shows the structural example of a solid-state imaging device. It is a schematic sectional drawing which expands and shows the imaging part of FIG. It is a schematic sectional drawing which shows the structural example of an infrared sensor.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
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.
In the description of the 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).
“Actinic light” or “radiation” in the present specification means, for example, deep ultraviolet light, extreme ultraviolet lithography (EUV), X-rays, and electron beams. As used herein, “light” means actinic rays and radiation. Unless otherwise specified, “exposure” in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate. In the present specification, “(meth) acryl” represents acryl and methacryl. In this specification, “(meth) acryloyl” represents acryloyl and methacryloyl. In this specification, “(meth) acrylamide” represents acrylamide and methacrylamide. In the present 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.

[Metal nitride-containing particles]
The metal nitride-containing particles according to the embodiment of the present invention contain a nitride of a specific transition metal (containing a nitrogen atom) and a specific atom T.
The metal nitride-containing particles are also referred to as “ESCA” (hereinafter, also referred to as “ESCA”. ESCA is an abbreviation for Electron Spectroscopy for Chemical Analysis) on the surface of metal nitride-containing particles. The mass-based content of the atom T is T _E (mass%), and metal nitridation is detected by fluorescent X-ray analysis (hereinafter also referred to as “XRF”. XRF is an abbreviation for X-ray Fluorescence). When the mass-based content of atoms T in the substance-containing particles is T _X (mass%), the relationship represented by the following formula (1) is satisfied.
Formula (1) T _E / T _X <2.0

In this specification, ESCA refers to the inclusion of each atom present on the surface of a measurement object (metal nitride-containing particles) by irradiating the measurement object with X-rays and measuring the intrinsic energy of the generated photoelectrons. It is a method of analyzing the amount (content based on the number of atoms of each atom: atomic%), and an analysis method performed under the following conditions is intended.
・ Device: Quantera-SXM (trade name) device manufactured by PHI ・ X-ray source: Monochromatic Al Kα ray (1486.6 eV, 25 W, 15 kV, beam diameter 200 μmφ)
・ Measurement area: 200μmφ
Measurement conditions: Pass Energy = 140 eV, step = 0.1 eV, number of integrations 4 to 8 Measurement method: Press the particles using a press to obtain a thin pellet-shaped measurement sample. This measurement sample is set in the above apparatus, and the photoelectron take-off angle is set to 10 degrees.

According to ESCA, the content (atomic%) of atoms T described later on the surface of the metal nitride-containing particles can be measured. From this measured value, the mass-based content T of atoms T on the surface of the metal nitride-containing particles. _E (mass%) can be obtained.
In the present specification, the surface of the metal nitride-containing particle means a region within a depth of 5 nm from the outermost surface of the metal nitride-containing particle toward the center of the metal nitride-containing particle.

In this specification, XRF refers to the content (mass) of each atom in the measurement object (metal nitride-containing particles) from the energy and intensity of the generated fluorescent X-rays when the measurement object is irradiated with X-rays. %) Is intended to be performed under the following conditions.
・ Equipment: Rigaku ZSM Primus II type XRF
・ X-ray source: Rh 30-50 kV, 48-80 mA
・ Measurement area: 10μmφ
Measurement time: 10-240 deg / min (deg is an abbreviation for degree)
-Sample The particles are pressed using a press to obtain a thin pellet-shaped measurement sample. This measurement sample is set in the apparatus and measured.

According to XRF, the mass-based content T _X (mass%) of atoms T described later in the metal nitride-containing particles can be obtained.

The metal nitride-containing particles are characterized in that T _E and T _X satisfy the relationship represented by the following formula (1).
Formula (1) T _E / T _X <2.0

The metal nitride-containing particle having the above characteristics is a composite of a specific transition metal and a specific atom T, and the atom T is present on the surface and inside of the metal nitride-containing particle.
Among these, T _E / T _x is preferably less than 1.1 in that the metal nitride-containing particles have more excellent effects of the present invention. That is, it is preferable that the atoms T exist more uniformly on the surface and inside. The lower limit of T _E / T _x is not particularly limited, but is often 0.5 or more.
In the metal nitride-containing particles, the atom T may form any other component, for example, a eutectic that forms a crystal separate from the nitride of the transition metal, a solid solution that completely dissolves, and a compound. Good.

[Atom T]
The metal nitride-containing particles contain atoms T.
The atom T is not an oxygen atom, a chlorine atom, or a nitrogen atom, and is selected from elements in groups 13 to 17 of the periodic table, and is not particularly limited.
The atom T is preferably selected from the elements of the 2nd to 6th periods of the periodic table in that the metal nitride-containing particles have the excellent effect of the present invention, and among them, aluminum, gallium, indium, tin And more preferably selected from elements other than thallium, lead, and bismuth. In other words, as atom T, boron atom, carbon atom, oxygen, fluorine atom, silicon atom, phosphorus atom, sulfur atom, germanium atom, arsenic atom, selenium atom, bromine atom, antimony atom, tellurium atom, iodine atom, polonium More preferred are any atom selected from the group consisting of an atom and an astatine atom.
The atom T is any one selected from the group consisting of a boron atom, a carbon atom, a sulfur atom, a silicon atom, a phosphorus atom, and a fluorine atom in that the metal nitride-containing particles have a further excellent effect of the present invention. Are more preferred.
Among them, the atom T is particularly preferably selected from elements of groups 13 to 16 in the periodic table in that the metal nitride-containing particles have particularly excellent effects of the present invention, and boron atoms, carbon atoms, sulfur Any atom selected from the group consisting of an atom and a phosphorus atom is most preferable, and any atom selected from the group consisting of a boron atom, a sulfur atom, and a phosphorus atom is particularly preferable.

The content of atom T in the metal nitride-containing particles is not particularly limited, but is preferably 0.05 to 40% by mass, more preferably 0.5 to 20% by mass with respect to the total mass of the metal nitride-containing particles. preferable.
The atom T may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of atoms T together, it is preferable that total content is in the said range.

[Group 3-11 transition metal nitrides]
The metal nitride-containing particles contain a nitride of a group 3-11 transition metal (hereinafter simply referred to as “transition metal”).
The transition metal is preferably a transition metal having an electronegativity of 1.22 to 2.36 in that the metal nitride-containing particles have a more excellent effect of the present invention.
Examples of the transition metal (electronegativity in parentheses) include, for example, Sc (1.36), Y (1.22), Dy (1.22), Ho (1.23) of Group 3 transition elements, Er (1.24), Tm (1.25), Lu (1.27), Th (1.3), Pa (1.5), U (1.38), Np (1.36), Pu (1.28), Am (1.3), Cm (1.3), Bk (1.3), Cf (1.3), Es (1.3), Fm (1.3), Md ( 1.3), No (1.3), Lr (1.3); Group 4 Ti (1.54), 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); Group 8 Fe (1.8 ), 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, Ti, Zr, Nb, Mo, Tc, metal nitride-containing particles have a more excellent effect of the present invention. Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, or Pt are preferable, Ti, Zr, V, Nb, Hf, Cr, W, Ta, Y, or Re are more preferable, and Ti , Zr, V, Hf, Cr, W, Ta, Y, or Re are more preferable, Ti, Zr, V, Hf, Cr, or W are still more preferable, Ti, Zr, or Cr are particularly preferable, and Ti is Most preferred.

The content of transition metal atoms in the metal nitride-containing particles is not particularly limited, but is preferably 10% by mass to 99% by mass, more preferably 30% to 90% by mass with respect to the total mass of the metal nitride-containing particles. 40 to 70% by mass is more preferable. The content of transition metal atoms in the metal nitride-containing particles can be analyzed by a fluorescent X-ray analyzer.
A transition metal may be used individually by 1 type, or may use 2 or more types together. When two or more transition metals are used in combination, the total content is preferably within the above range.

[Nitrogen atom]
The metal nitride-containing particles contain nitrogen atoms.
The form of the nitrogen atom in the metal nitride-containing particle is not particularly limited, and examples thereof include a form in which a transition metal nitride is formed by combining with the transition metal described above.
The content of nitrogen atoms (N atoms) in the metal nitride-containing particles is not particularly limited, but is preferably 0.1 to 80% by mass with respect to the total mass of the metal nitride-containing particles, and 5 to 70% by mass. Is more preferable, and 20 to 50% by mass is still more preferable. The nitrogen atom content can be analyzed by a fluorescent X-ray analyzer.

[Oxygen atom]
The metal nitride-containing particles preferably contain oxygen atoms.
The form of oxygen atoms in the metal nitride-containing particles is not particularly limited, but may be intentionally added in the process for producing metal nitride-containing particles, or the process for producing metal nitride-containing particles. However, it may be unintentionally mixed.
The oxygen atom content in the metal nitride-containing particles is not particularly limited, but is preferably 0.01 to 50% by mass and more preferably 1 to 20% by mass with respect to the total mass of the metal nitride-containing particles. The content of oxygen atoms can be analyzed by a fluorescent X-ray analyzer.

In the metal nitride-containing particles, the ratio of the number of nitrogen atoms contained to the content of transition metal atoms contained in the nitride (hereinafter also simply referred to as “transition metal atoms”) X, the content of transition metal atoms The content atom number ratio Y of the oxygen atom content to the content and the content atom number ratio Z of the content of the atom T to the content of the transition metal atom are each preferably greater than 0 and less than 2.

The lower limit value of the content atom number ratio X of the nitrogen atom content to the transition metal atom content in the metal nitride-containing particles is more preferably more than 0.3, still more preferably 0.4 or more, and 0.64 The above is particularly preferable. The upper limit is more preferably less than 1.3, still more preferably 1.2 or less, and particularly preferably less than 1.2.
When X is 0.4 or more, the curable composition containing metal nitride-containing particles has more excellent anti-settling property and stability over time.
When X is less than 1.3, the cured film obtained from the curable composition containing metal nitride-containing particles has more excellent light shielding properties. When X is 1.2 or less, the cured film obtained from the curable composition containing metal nitride-containing particles has further excellent light-shielding properties. When X is less than 1.2, the curable composition containing metal nitride-containing particles has better stability over time.

The lower limit value of the content atom number ratio Y of the oxygen atom content to the transition metal atom content in the metal nitride-containing particles is more preferably more than 0.03, still more preferably 0.05 or more, and 0.08. The above is particularly preferable. The upper limit value is more preferably less than 0.25, and still more preferably 0.2 or less.
When Y is 0.05 or more, the curable composition containing metal nitride-containing particles has better anti-settling property and stability over time.
When Y is 0.2 or less, the curable composition containing metal nitride-containing particles has more excellent temporal stability, and the obtained light-shielding film has more excellent light-shielding properties.

In the metal nitride-containing particles, the lower limit value of the content atom number ratio Z of the content of atoms T to the content of transition metal atoms is more preferably more than 0.03, still more preferably 0.05 or more, and 0.08. The above is particularly preferable. The upper limit is more preferably less than 1.2 and even more preferably 0.5 or less.
When Z is 0.05 or more, the curable composition containing metal nitride-containing particles has more excellent anti-settling property and stability over time.
When Y is 0.5 or less, the curable composition containing metal nitride-containing particles has better stability over time, and the resulting light-shielding film has better light-shielding properties.

The ratio of the number of nitrogen atoms to the content of transition metal atoms X, the content of oxygen atoms to the content of transition metal atoms, in that the metal nitride-containing particles have the effect of the present invention more excellent. The sum of the containing atom number ratio Y and the containing atom number ratio Z of the content of atoms T to the content of transition metal atoms (hereinafter also referred to as “sum of X, Y, and Z” or “X + Y + Z”) is 0. More than 4 and less than 1.6 is preferable.
When X + Y + Z is less than 1.6, the cured film obtained from the curable composition containing metal nitride-containing particles has more excellent light shielding properties.
When X + Y + Z exceeds 0.4, the curable composition containing metal nitride-containing particles has better anti-settling property and stability over time.

The lower limit of the sum of X, Y, and Z is more preferably 0.5 or more, still more preferably 0.8 or more, in that the metal nitride-containing particles have more excellent effects of the present invention. The above is particularly preferable. The upper limit value is more preferably 1.5 or less.
When the sum of X, Y, and Z is 0.5 or more, the curable composition containing metal nitride-containing particles has more excellent anti-settling properties and stability over time.
When the sum of X, Y, and Z is 1.5 or less, the curable composition containing metal nitride-containing particles has better temporal stability, and the resulting light-shielding film is more excellent Has light shielding properties.

[Physical properties of metal nitride-containing particles]
Below, the physical property of metal nitride containing particle | grains is demonstrated.

<Average primary particle size>
The average primary particle diameter of the metal nitride-containing particles is 200 nm or less, and is preferably 80 nm or less and more preferably less than 80 nm in terms of having a more excellent effect of the present invention.
When the average primary particle diameter of the metal nitride-containing particles is 200 nm or less, the curable composition has excellent temporal stability. When the average primary particle diameter of the metal nitride-containing particles is less than 80 nm, the curable composition has better temporal stability.
The lower limit of the average primary particle diameter of the metal nitride-containing particles is not particularly limited, but is generally preferably 1.0 nm or more. When the average primary particle size is 1.0 nm or more, the interaction between the metal nitride-containing particles is suppressed, the metal nitride-containing particles are less likely to aggregate, and as a result, the curable composition has a more stable aging stability. Have sex.
In addition, in this specification, the average primary particle diameter is an average obtained by arithmetically averaging the diameters in terms of circles evaluated for 400 metal nitride-containing particles using a transmission electron microscope (TEM: Transmission Electron Microscope). The primary particle size is intended and the test method is as described in the examples.

<Real part of complex permittivity>
When the complex dielectric constant ε of the metal nitride-containing particles is represented by ε = ε ′ + ε ″ j, the minimum value of ε ′ at a wavelength of 400 to 1200 nm is not particularly limited, but is preferably less than 0, and the metal nitride-containing particles are The minimum value of ε ′ is preferably −0.5 or less in that a cured film obtained from the curable composition contained has better light-shielding properties.
The lower limit value of the minimum value of ε ′ is not particularly limited, but is often about −20.
Ε ′ represents the real part of the complex permittivity ε, ε ″ represents the imaginary part of the complex permittivity ε, and j represents the imaginary unit. In this specification, the minimum value of the real part ε ′ of the complex permittivity Is intended to be the smallest value of the real part ε ′ of the complex dielectric constant corresponding to each wavelength of 400 to 1200 nm.

In this specification, the real part ε ′ of the complex dielectric constant is intended to be a value measured by the following method. First, a film having a thickness of 0.3 μm is formed on a silicon wafer using a composition containing metal nitride-containing particles. Thereafter, the complex dielectric constant of the formed film is measured by the method described in Examples using spectroscopic ellipsometry.
In addition, when forming a film | membrane, when a composition is a composition containing a polymeric compound, a hardening process is performed with respect to the coating film formed on the silicon wafer, and the film | membrane used as a measuring object is formed.

[Method for producing metal nitride-containing particles]
The method for producing the metal nitride-containing particles is not particularly limited, and a known method can be used. Examples of the method for producing metal nitride-containing particles include a gas phase reaction method. Examples of the gas phase reaction method include an electric furnace method, a thermal plasma method, and the like. The thermal plasma method is preferable in that impurities are less mixed, the particle diameter is easily uniformed, and productivity is high.
In the thermal plasma method, a method for generating thermal plasma is not particularly limited, and examples thereof include direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, and hybrid plasma.
The specific method for producing metal nitride-containing particles by the thermal plasma method is not particularly limited. For example, as a method for producing metal nitride-containing particles containing titanium as a transition metal, titanium tetrachloride and ammonia are used in a plasma flame. Gas reacting method (JP-A-2-22110), Titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced as a carrier gas, and nitriding is performed in the cooling process (JP-A-61-1140) And a method of injecting ammonia gas into the peripheral edge of the plasma (Japanese Patent Laid-Open No. 63-85007).

However, the method for producing metal nitride-containing particles is not limited as long as metal nitride-containing particles having desired physical properties are obtained.
Further, when producing the metal nitride-containing particles by the thermal plasma method, the raw material may be appropriately heated or cooled in order to supply the raw material into the plasma flame at a desired flow rate.

<Preferred embodiment of the method for producing metal nitride-containing particles>
As a method for producing metal nitride-containing particles, a production method including the following steps is preferred.
(A) preparing a raw material A containing a nitrogen atom and a raw material B containing a transition metal atom and an atom T, or containing a raw material A containing a nitrogen atom, a raw material C containing a transition metal atom, and an atom T To prepare raw material D to be processed (raw material preparation step)
(B) Step of mixing two or more raw materials in a gas phase to obtain a mixture (mixing step)
(C) Step of condensing a gas phase mixture to obtain metal nitride-containing particles (condensation step)
Below, each said process is explained in full detail. In the following steps, oxygen atoms may be unintentionally mixed into the raw materials, the mixture, and the condensate.

(A) Raw material preparation step The raw material preparation step is a step of preparing two or more kinds of raw materials in the following combinations.
A raw material A containing nitrogen atoms and a raw material B containing transition metal atoms and atoms T, or a raw material A containing nitrogen atoms, a raw material C containing transition metal atoms, and a raw material D containing atoms T
The raw material A contains nitrogen atoms, and examples thereof include nitrogen gas. The raw material B contains a transition metal atom and an atom T, and examples thereof include titanium tetrachloride. The raw material C contains a transition metal atom, and examples thereof include transition metal powder. Examples of the raw material D include a solid, liquid, or gas containing the atom T.
The method for preparing the raw material is not particularly limited, and examples thereof include a method in which the raw material is procured by purchase and the raw material is obtained by synthesis.
In addition, in a raw material preparation process, it will not restrict | limit especially if two or more types of raw materials of the said combination are prepared, You may prepare together with other raw materials.

The form of each raw material is not particularly limited, and may be any of solid (including sublimable solid), liquid, and gas. The raw material may be a slurry described in paragraphs 0024 and 0025 of JP-A-2005-170760.
Moreover, although the upper limit of the kind of raw material prepared in this process is not particularly limited, generally 10 or less are preferable.

(B) Mixing step The mixing step is a step of obtaining a mixture by mixing two or more raw materials including any raw material prepared in the (a) raw material preparing step in a gas phase state. The mixing step is a step of obtaining a mixture by mixing all the raw materials prepared in the raw material preparation step, that is, raw material A and raw material B, or raw material A, raw material C and raw material D in a gas phase state. Also good. A method for mixing two or more kinds of raw materials in a gas phase state is not particularly limited, but a thermal plasma method in which the raw materials are supplied to thermal plasma to evaporate the raw materials and mixed in a gas phase state is preferable.
A method for mixing raw materials in a gas phase state by a thermal plasma method is not particularly limited, and a known method can be used. Known methods include, for example, the method described in paragraphs 0015 to 0037 of JP-A-2005-170760, paragraphs 0038 to 0086 of JP-A-2015-227282, and 0017 to JP-A-2005-343784. Examples include the method described in paragraph 0047.
Among them, a method of generating a thermal plasma by arc discharge and introducing a raw material into the thermal plasma is preferable in that a metal nitride-containing particle having the better effect of the present invention can be obtained.
A method for generating a thermal plasma by arc discharge and introducing a raw material into the thermal plasma is not particularly limited, and a known method can be used.

A specific method for producing metal nitride-containing particles by the thermal plasma method is described in JP-A-2005-343784, paragraph 0042 and apparatus shown in FIG. 1, and JP-A-2005-170760, 0019 and 0020. Examples thereof include a method using the raw material supply apparatus described in the paragraph.

(C) Condensing step The condensing step is a step of condensing the gas phase mixture to obtain metal nitride-containing particles. The method in particular of obtaining a condensate is not restrict | limited, A well-known method can be used. Examples of the method for obtaining the metal nitride-containing particles include a method in which a gas phase mixture is brought into contact with the inner wall of the apparatus and rapidly cooled.

(Heating process)
The method for producing metal nitride-containing particles preferably further includes a step (heating step) of heating and removing the metal nitride-containing particles produced by the above-described production method to volatilize and remove impurities.
In the metal nitride-containing particles produced through the heating process, the minimum value of the real part ε ′ of the complex dielectric constant at a wavelength of 400 to 1200 nm tends to be less than zero.
The heating temperature in the heating step is not particularly limited and is generally preferably 150 to 500 ° C. The heating time is not particularly limited, and generally 1 hour to 3 days is preferable. The atmosphere during heating is not particularly limited, but a nitrogen atmosphere or the like in which oxygen is less than 200 ppm is preferable. Further, the pressure may be reduced during heating.

(Standing process)
It is preferable that the method for producing metal nitride-containing particles further includes a stationary step in which the metal nitride-containing particles produced by the above-described production method are allowed to stand in a nitrogen gas atmosphere.
The method of standing is not particularly limited, and a known method can be used.

[Dispersion composition]
The dispersion composition according to the embodiment of the present invention contains metal nitride-containing particles and a resin. Below, each component which a dispersion composition contains is explained in full detail.

[Metal nitride-containing particles]
The metal nitride-containing particles contained in the dispersion composition are as already described in the form of the metal nitride-containing particles. The content of the metal nitride-containing particles in the dispersion composition is not particularly limited, but is generally preferably 10 to 90% by mass and more preferably 20 to 80% by mass with respect to the total solid content of the dispersion composition. The metal nitride-containing particles may be used alone or in combination of two or more. When two or more kinds of metal nitride-containing particles are used in combination, the total content is preferably within the above range.

〔resin〕
The dispersion composition contains a resin. Examples of the resin include a dispersant and an alkali-soluble resin.
The content of the resin in the dispersion composition is not particularly limited, but is generally preferably 5 to 40% by mass with respect to the total solid content of the dispersion composition. Resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of resin together, it is preferable that total content is in the said range.

<Dispersant>
The dispersion composition preferably contains a dispersant (corresponding to a resin). In addition, in this specification, a dispersing agent intends the compound different from the alkali-soluble resin mentioned later.
The content of the dispersant in the composition is not particularly limited, but is generally preferably 5 to 40% by mass and more preferably 5 to 30% by mass with respect to the total solid content of the composition.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total content is preferably within the above range.

As the dispersant, for example, a known dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include a polymer dispersant (for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type) Copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivative.
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 metal nitride-containing particles (hereinafter sometimes referred to as “pigments”) and acts to prevent re-aggregation of the dispersion. For this reason, terminal-modified polymers, graft-type (containing polymer chains), and block-type polymers containing an anchor site to the pigment surface are preferred.

The polymer compound may contain a curable group.
Examples of the curable group include an ethylenically unsaturated group (for example, (meth) acryloyl group, vinyl group, styryl group, etc.), and a cyclic ether group (for example, epoxy group, oxetanyl group, etc.). However, it is not limited to these.
Among these, an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by radical reaction. The ethylenically unsaturated group is more preferably a (meth) acryloyl group.

The resin containing a curable group preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and / or a polyether structure, and, as described later, when the resin contains a structural unit containing a graft chain, the polymer chain May contain a polyester structure and / or a polyether structure.
As for the said resin, it is more preferable that the said polymer chain contains a polyester structure.

The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
Such a polymer compound containing a structural unit containing a graft chain has an affinity for a solvent due to the graft chain, so that the dispersibility of metal nitride-containing particles, etc., and the dispersion stability after aging (stable with time) Property). 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 metal nitride-containing particles and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the metal nitride-containing particles and the like is lowered, and the dispersibility of the metal nitride-containing particles and the like tends to be lowered. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000, and still more preferably 60 to 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.
In order to improve the interaction between the graft chain and the solvent and thereby increase the dispersibility of the metal nitride-containing particles, the graft chain is made of a group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure. It is preferably a graft chain containing at least one selected, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.

A macromonomer containing such a graft chain (a monomer having a polymer structure and bound to the main chain of the copolymer to form a graft chain) is not particularly limited, but contains a reactive double bond group The macromonomer to be used 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.), and Bremer PME-4000 (trade name, manufactured by NOF Corporation) are used.

The dispersant 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 a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. 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. 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 a graft chain The polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit containing a graft chain. It is more preferable to contain a structural unit represented by any one of (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following formula (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 may each independently be a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms) from the viewpoint of synthesis constraints. Preferably, each independently, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more preferable.

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 because of the 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, the organic groups represented by Z ¹ , Z ² , Z ³ , and Z ⁴ are preferably those containing a steric repulsion effect, particularly from the viewpoint of improving dispersibility. More preferred are 24 alkyl groups or alkoxy groups, and each independently preferred is a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms. 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 Formula (1) and Formula (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are more preferably an integer of 4 to 6, and further preferably 5, from the viewpoint of the temporal stability and developability of the composition.
Moreover, in Formula (1) and Formula (2), n and m are preferably an integer of 10 or more, and more preferably an integer of 20 or more. When the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the number of repeats of the polycaprolactone structure and the number of repeats of polyvalerolactone is preferably an integer of 10 or more, and an integer of 20 or more Is more preferable.

In the formula (3), R ³ represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same or different from each other.
In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in 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, 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 is preferable, and 1 to A linear alkyl group having 20 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.
The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of temporal stability and developability of the composition.

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 contained within this range, the dispersibility of the metal nitride-containing particles is high, and the developability when forming a cured film is good.

-Hydrophobic structural unit Moreover, it is preferable that a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a 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 this specification, the ClogP value is intended to be a value calculated by the program CLOGP v4.82.
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 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 Include aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), and combinations thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. 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. 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. The heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is aliphatic. 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 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- A cyclohexylphenyl group and the like are included. Examples of the bridged cyclic hydrocarbon ring include two rings such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclic hydrocarbon rings such as tricyclo [4.3.1.1 ^2,5 ] undecane ring, 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. Bridged cyclic hydrocarbon rings include condensed cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a len ring are condensed is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. 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. The heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is aliphatic. 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 above formula (i), R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, L is a single bond or an alkylene group or a divalent linking group containing an oxyalkylene structure, A compound in which X is an oxygen atom or imino group, and Z is an aliphatic group, heterocyclic group or aromatic group is preferred.
The monomer represented by the above formula (ii) is preferably a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. As the monomer represented by the above formula (iii), a compound in which R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.

Examples of typical compounds represented by the formulas (i) to (iii) include radical 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 metal nitride-containing particles, etc. The polymer compound can introduce a functional group capable of forming interaction with metal nitride-containing particles. Here, the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with metal nitride-containing particles and the like.
Examples of the functional group that can form an interaction with the metal nitride-containing particles include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordinating group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, and the coordination, respectively. It is preferable to contain a structural unit containing a functional 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, the polymer compound as a dispersant that contributes to the dispersion of metal nitride-containing particles and the like has alkali solubility in the composition. 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 the metal nitride-containing particles and the like, and the polymer compound stably disperses the metal nitride-containing particles and the like, and the metal nitride-containing particles and the like 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 metal nitride-containing particles include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably a carboxylic acid group. , A sulfonic acid group, and a phosphoric acid group, and more preferable is a carboxylic acid group in terms of good adsorptive power to metal nitride-containing particles and high dispersibility. .
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 metal nitride-containing particles 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 a preferable one is a tertiary amino group in that it has a good adsorptive power to metal nitride-containing particles and has a high dispersibility. 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.

Examples of the coordinating group which is a functional group capable of forming an interaction with metal nitride-containing particles and the functional group having reactivity include, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chlorides. Preferable one is an acetylacetoxy group in that the adsorbing power to the metal nitride-containing particles is good and the dispersibility of the metal nitride-containing particles is high. 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 when it is contained, the content of these structural units is In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of inhibiting developability inhibition, with respect to the total mass of the polymer compound.

When the polymer compound contains a functional group capable of interacting with metal nitride-containing particles in addition to the graft chain, the functional group capable of interacting with the various metal nitride-containing particles described above. There is no particular limitation on how these functional groups are introduced, but the polymer compound is derived from the monomers represented by the following formulas (iv) to (vi) It is preferable to contain one or more structural units selected from these structural units.

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ˜6 (for example, methyl group, ethyl group, propyl group, etc.).
In the formulas (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably each independently Are 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 formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the formula (v) represents a methine group or a nitrogen atom.

L ₁ in the formulas (iv) to (v) represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above-described formula (i).

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 include 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 formulas (iv) to (vi), Z ₁ represents a functional group that can form an interaction with the metal nitride-containing particles in addition to the graft chain, and is a carboxylic acid group or a tertiary amino group. Are preferable, and a carboxylic acid group is more preferable.

In the formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms ( for example, a methyl group, an ethyl group, a propyl group, etc.), - _{Z 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 formula (iv), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is an alkylene group or a divalent oxyalkylene structure. A compound in which X ₁ is an oxygen atom or imino group and Z ₁ is a carboxylic acid group is preferable.
As the monomer represented by the formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine group. Compounds are preferred.
As the monomer represented by the formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z ₁ is Compounds that are carboxylic acid groups are preferred.

The following are typical examples of monomers (compounds) represented by the formulas (iv) to (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 hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride Reaction products, 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 metal nitride-containing particles, etc. is from the viewpoint of interaction with metal nitride-containing particles, etc., stability over time, and permeability to 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, for the purpose of improving various performances such as image strength, the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and metal nitriding, as long as the effects of the present invention are not impaired. Other structural units having various functions different from structural units containing functional groups capable of forming interactions with substance-containing particles, etc. (for example, functional groups having affinity with the solvent used in the dispersion composition, etc. May further have a structural unit containing
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
In the polymer compound, one or more of these other structural units can be used, and the content thereof is preferably 0% to 80% in terms of mass with respect to the total mass of the polymer compound. More preferably, it is 10% to 60%. When the content is in the above range, sufficient pattern formability is maintained.

-Physical properties of polymer compound The acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 250 mgKOH / g, more preferably in the range of 10 mgKOH / g to 200 mgKOH / g, and even more preferably 20 mgKOH. / G or more and 120 mgKOH / g or less.
When the acid value of the polymer compound is 250 mgKOH / g or less, pattern peeling during development when forming a cured film is more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better. If the acid value of the polymer compound is 20 mgKOH / g or more, sedimentation of metal nitride-containing particles and the like can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition can be further improved.

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

The weight average molecular weight of the polymer compound is 4 in terms of polystyrene conversion by GPC (Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a cured film. 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.

Specific examples of the polymer compound include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid ester), and 110 (copolymer containing acid group). ), 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 Oleart), MYS-IEX (polyoxyethylene monostearate), Kawano 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. Alternatively, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPER10K, 2001-DISPERBY, manufactured by BYK Chemie. DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajisper PB821, Azisper PB822, Azisper PB881 manufactured by Ajinomoto Fine Techno Co., etc.
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, a graft copolymer described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 in US2011 / 0124824) can be used. Can be incorporated and incorporated herein by reference.
In addition to the above, a structure containing a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding to columns 0075 to 0133 of US2011 / 0279759) are bonded via a linking group Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.

As the dispersant, resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, the contents of which are incorporated herein.

<Alkali-soluble resin>
The dispersion composition preferably contains an alkali-soluble resin (corresponding to a resin). In the present specification, the alkali-soluble resin means a resin containing a group that promotes alkali solubility (alkali-soluble group), and a resin different from the dispersant already described.
The content of the alkali-soluble resin in the dispersion composition is not particularly limited, but generally 1 to 30% by mass is preferable with respect to the total solid content of the dispersion composition, and the dispersion composition has more excellent effects of the present invention. In this respect, 1 to 15% by mass is more preferable.
Alkali-soluble resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said range.

Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic. / (Meth) acrylamide copolymer resin, epoxy resin, polyimide resin, and the like.

Specific examples of the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
Unsaturated carboxylic acids are not particularly limited, but monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and vinyl acetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or acid anhydrides thereof; phthalic acid And polycarboxylic acid monoesters such as mono (2- (meth) acryloyloxyethyl).

Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate. In addition, the compounds described in paragraph 0027 of JP2010-97210A and paragraphs 0036 to 0037 of JP2015-68893A can also be used, and the above contents are incorporated herein.

Also, a copolymerizable ethylenically unsaturated compound that contains an ethylenically unsaturated group in the side chain may be used in combination. As the ethylenically unsaturated group, a (meth) acrylic acid group is preferable. An acrylic resin having an ethylenically unsaturated group in the side chain is obtained by, for example, adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group. Can be obtained.

Examples of the alkali-soluble resin include JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-92723, JP-A-59-. Radical polymers containing a carboxylic acid group in the side chain described in JP-A-53836 and JP-A-59-71048; European Patent No. 993966, European Patent No. 1204000, JP-A-2001-318463, etc. Acetal-modified polyvinyl alcohol binder resin containing alkali-soluble groups described in each publication; polyvinyl pyrrolidone; polyethylene oxide; alcohol-soluble nylon, and 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydride Polyether which is a reaction product with phosphorus; International Publication No. 200 And the like can be used; polyimide resin described in JP / 123097.

As the alkali-soluble resin, for example, compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can be used, and the above contents are incorporated in the present specification.

A polyimide precursor can also be used as the alkali-soluble resin. The polyimide precursor intends a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C.
As a polyimide precursor, resin containing the repeating unit represented by following formula (1) is mentioned, for example. Examples of the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide ring-closed, and / or the following formula ( What contains the imide structure shown by 4) is mentioned.
In this specification, a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.

In the above formulas (1) to (4), R ₁ represents a tetravalent organic group having 2 to 22 carbon atoms, R ₂ represents a divalent organic group having 1 to 22 carbon atoms, and n is 1 or 2 Represents.

Specific examples of the polyimide precursor include compounds described in paragraphs 0011 to 0031 of JP 2008-106250 A, compounds described in paragraphs 0022 to 0039 of JP 2016-122101 A, and JP 2016-68401 A. The compounds described in paragraphs 0061 to 0092 of the publication are listed, and the above contents are incorporated in the present specification.

The alkali-soluble resin preferably contains at least one selected from the group consisting of polyimide resins and polyimide precursors in that the pattern shape of the patterned cured film obtained using the dispersion composition is more excellent. .
The polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include resins described in paragraph 0050 of JP2014-137523, resins described in paragraph 0058 of JP2015-187676, and 0012 of JP2014-106326A. The resins described in paragraphs -0013 are listed, and the above contents are incorporated in the present specification.

[Optional ingredients]
The said dispersion composition may contain another component in the range with the effect of this invention. Examples of other components include polymerization inhibitors, solvents, colorants, and those described as optional components of the curable composition described below. Below, the arbitrary component contained in a dispersion composition is explained in full detail.

<Polymerization inhibitor>
The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used. Examples of the polymerization inhibitor include phenol-based polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-ditert-butyl-4-methylphenol, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4-methoxynaphthol, etc.); hydroquinone polymerization inhibitor ( For example, hydroquinone and 2,6-di-tert-butylhydroquinone, etc.); quinone polymerization inhibitors (eg, benzoquinone, etc.); free radical polymerization inhibitors (eg, 2,2,6,6-tetra) Methylpiperidine 1-oxyl free radical and 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxylfu Over radicals and the like); nitrobenzene-based polymerization inhibitor (e.g., nitrobenzene, and 4-nitrotoluene and the like); phenothiazine-based polymerization inhibitor (e.g., phenothiazine and 2-methoxy phenothiazine, etc.), and the like.
Among these, a phenol polymerization inhibitor or a free radical polymerization inhibitor is preferable in that the curable composition has the more excellent effects of the present invention.
In addition, a polymerization inhibitor may be mixed with other components at the time of preparation of a dispersion composition, and what was used for the synthesis | combination etc. of the said resin may be mixed with a dispersion composition with the said resin.

The content of the polymerization inhibitor in the dispersion composition is not particularly limited, but it is dispersed in that the dispersion composition has better aging stability and the curable composition described below has better curability. The content is preferably 0.0001 to 1% by mass relative to the total solid content of the composition.
A polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
The effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group. For example, during the preparation of the dispersion composition; after the preparation of the dispersion composition; during the preparation of the curable composition to be described later; after the preparation of the curable composition; and the like, the dispersion composition and / or the curable composition is at a high temperature. Even if there is a concern that polymerization of a resin containing a curable group proceeds due to storage for a long period of time or the like, it can be used without any problem.

<Solvent>
The dispersion composition may contain a solvent.
A solvent in particular is not restrict | limited, A well-known solvent can be used.
The content of the solvent in the dispersion composition is not particularly limited, but in general, the solid content of the dispersion composition is preferably adjusted to be 10 to 90% by mass, and adjusted to be 20 to 90% by mass. It is more preferable.
A solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of solvent together, it is preferable to adjust so that the total solid content of a composition may become in the said range.

As a solvent, water or an organic solvent is mentioned, for example.
Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone. , Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Chill ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, Examples include but are not limited to butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.

<Colorant>
The dispersion composition may contain a colorant. In this specification, the colorant intends a compound different from the metal nitride-containing particles.

Various known pigments (colored pigments) and dyes (colored dyes) can be used as the colorant. Examples of pigments include inorganic pigments and organic pigments.
When it contains a colorant, its content can be determined according to the optical properties of the light-shielding film obtained by curing. A coloring agent may be used individually by 1 type, or may use 2 or more types together.

(Inorganic pigment)
The inorganic pigment is not particularly limited, and a known inorganic pigment can be used.
Examples of inorganic pigments include carbon black, silica, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow ( Zinc yellow 1 type, zinc yellow 2 type), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bituminous blue (unrelated to Prussian blue) , Vanadium zirconium blue, chrome tin pink, ceramic red, salmon pink and the like. Further, it is preferably a black inorganic pigment, and as the inorganic pigment, carbon black, a metal pigment, and the like in that a composition capable of forming a cured film having at least a high optical density can be obtained. (Hereinafter also referred to as “black pigment”) is preferred. Examples of the metal pigment include a metal oxide containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. And metal carbides (for example, TiC, etc.).
The inorganic pigment preferably contains at least one selected from the group consisting of metal pigments containing silver, metal pigments containing tin, and metal pigments containing silver and tin. An inorganic pigment may be used individually by 1 type, or may use 2 or more types together.

Examples of the colorant include those described in JP-A-2014-42375, paragraphs 0027 to 0200, JP-A-2008-260927, paragraph 0031, and JP-A-2015-68893, paragraphs 0015 to 0025. And the above contents are incorporated herein.

As the colorant, a pigment having infrared absorptivity can also be used.
As the pigment having infrared absorptivity, a tungsten compound, a metal boride, and the like are preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding properties at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of an oxime polymerization initiator related to curing efficiency by exposure and transparency of visible light region.

Two or more of these pigments may be used in combination, or may be used in combination with a dye described later. In order to adjust the color tone and enhance the light-shielding property in a desired wavelength region, for example, chromatic pigments such as red, green, yellow, orange, purple, and blue are added to black or infrared light-shielding pigments. Or the form which mixes the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black or infrared pigment, and it is more preferable to mix a red pigment with a black pigment or infrared pigment.
Furthermore, you may add the near-infrared absorber and infrared absorber which are mentioned later.

Organic pigment Examples of the organic pigment 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, 16 7,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc .;
C. I. Pigment green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment violet 1, 19, 23, 27, 32, 37, 42, etc .; and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Is mentioned. A pigment may be used individually by 1 type, or may use 2 or more types together.

(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. A polymerizable dye having a polymerizable group in the molecule may be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries, Ltd.

(Infrared absorber)
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm is preferable.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes. Examples include compounds, dithiol metal complex compounds, and croconium compounds.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated. As the cyanine compound, for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, written by Kodansha Scientific”, the contents of which are incorporated herein.

As the colorant having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP-A-2011-16483 It is also possible to use near-infrared absorbing particles comprising a crystallite of an oxide containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication and having a number average aggregate particle diameter of 5 to 200 nm.

The compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
Further, the infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
The pyrrolopyrrole compound can be referred to paragraphs 0049 to 0062 of JP 2010-222557 A, the contents of which are incorporated herein. Cyanine compounds and squarylium compounds are disclosed in WO 2014/088063 paragraphs 0022 to 0063, WO 2014/030628, paragraphs 0053 to 0118, JP 2014-59550 A, paragraphs 0028 to 0074, international publication 2012 / No. 169447, paragraphs 0013 to 0091, JP-A-2015-176046, paragraphs 0019 to 0033, JP-A-2014-63144, paragraphs 0053 to 00099, JP-A-2014-52431, paragraphs 0085 to 0150, JP-A Paragraphs 0076 to 0124 of Japanese Patent Application Laid-Open No. 2014-44301, paragraphs 0045 to 0078 of Japanese Patent Application Laid-Open No. 2012-8532, paragraphs 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172102, and 0029 to Japanese Patent Application Laid-Open No. 2015-172004. Paragraph 067, paragraphs 0029 to 0085 of JP-A-2015-40895, paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011 to 0017 of JP-A-2014-148567, and JP-A-2015-157893. Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007 A, paragraphs 0013 to 0047 of JP 2014-80487 A, paragraphs 0007 to 0028 of JP 2013-227403 A, etc. The contents are incorporated herein.

[Method for producing dispersion composition]
The dispersion composition can be prepared by mixing the above components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like).

The method for producing a dispersion composition preferably includes the following steps.
Prepare raw material A containing nitrogen atom and raw material B containing transition metal atom and atom T, or raw material A containing nitrogen atom, raw material C containing transition metal atom, and raw material containing atom T Process for preparing D (raw material preparation process)
・ A step of mixing two or more raw materials in a gas phase to obtain a mixture (mixing step)
・ Condensation of gas phase mixture to obtain metal nitride-containing particles (condensation process)
-Mixing metal nitride-containing particles and resin to obtain a dispersion composition (dispersion step)

In the above, the raw material preparation step, the mixing step, and the condensation step are as already described in the method for producing metal nitride-containing particles.

(Dispersion process)
The dispersion step is a step of obtaining a dispersion composition by mixing metal nitride-containing particles and a resin. The method of mixing the metal nitride-containing particles and the resin is as described above. In the dispersion step, optional components other than the above may be mixed together.

[Curable composition]
The curable composition which concerns on embodiment of this invention contains metal nitride containing particle | grains, resin, a polymeric compound, and a polymerization initiator. Below, each said component is explained in full detail.

[Metal nitride-containing particles]
The form of the metal nitride-containing particles contained in the curable composition is as already described as the form of the metal nitride-containing particles. The content of the metal nitride-containing particles in the curable composition is not particularly limited, but is generally preferably 30 to 80% by mass with respect to the total solid content of the curable composition. The metal nitride-containing particles may be used alone or in combination of two or more. When two or more kinds of metal nitride-containing particles are used in combination, the total content is preferably within the above range.

〔resin〕
The form of the resin contained in the curable composition is as already described as the form of the resin contained in the dispersion composition.
The content of the resin in the curable composition is not particularly limited, but is generally preferably 3 to 60% by mass and more preferably 5 to 40% by mass with respect to the total solid content of the curable composition. Resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of resin together, it is preferable that total content is in the said range.

It is preferable that a curable composition contains a dispersing agent and alkali-soluble resin as resin. The form of the dispersant and the alkali-soluble resin is as already described as the form of the dispersant and the alkali-soluble resin contained in the dispersion composition.
The content of the dispersant in the curable composition is not particularly limited, but is generally preferably 2 to 40% by mass, more preferably 5 to 30% by mass, based on the total solid content of the curable composition. A dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total content is preferably within the above range.
The content of the alkali-soluble resin in the curable composition is not particularly limited, but is generally preferably 1 to 30% by mass with respect to the total solid content of the curable composition. Alkali-soluble resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said range.

(Polymerizable compound)
The curable composition contains a polymerizable compound. In the present specification, the polymerizable compound means a compound containing a polymerizable group and a component different from the dispersant and the alkali-soluble resin.

The content of the polymerizable compound in the curable composition is not particularly limited, but is generally preferably 5 to 30% by mass with respect to the total solid content of the curable composition. A polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that total content is in the said range.

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.

As the polymerizable compound, for example, compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the above contents are described in this specification. Incorporated.

The polymerizable compound may be in any of chemical forms such as monomers, prepolymers, oligomers, mixtures thereof, and multimers thereof.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.

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, the contents of which 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. 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 hydroxyl group of the aliphatic polyhydroxy compound. A polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toa Gosei 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. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or 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 formula (Z-1) are preferred.

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

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

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

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), -2) = the number of groups represented by 2 and R ¹ is all hydrogen atoms), DPCA-30 (formula, m = 1, the number of groups represented by formula (Z-2) = 3) , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, compounds in which R ¹ is 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 formula (Z-4) or (Z-5) can also be used.

In formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or ((CH ₂ ) _y CH (CH ₃ ) O) —. Y represents an integer of 0 to 10, and X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In the formula (Z-4), the total number 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 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 the 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 still more preferably an integer of 4 to 8.
In the 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 formula (Z-4) or (Z-5), — ((CH ₂ ) _y CH ₂ O) — or ((CH ₂ ) _y CH (CH ₃ ) O) — has a terminal on the oxygen atom side. A form 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 formula (Z-5), all six Xs are acryloyl groups, in formula (Z-5), all six Xs are acryloyl groups, and among six Xs, An embodiment which is a mixture with a compound having at least one hydrogen atom is preferred. With such a configuration, the developability can be further improved.

The total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
Of the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.

The polymerizable compound may contain a cardo skeleton.
As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.
Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).

(Polymerization initiator)
The curable composition contains a polymerization initiator.
The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. As a polymerization initiator, a photoinitiator, a thermal polymerization initiator, etc. are mentioned, for example, A photoinitiator is preferable. The polymerization initiator is preferably a so-called radical polymerization initiator.
The content of the polymerization initiator in the curable composition is not particularly limited, but is generally preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition. A polymerization initiator may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, and dimethyl- (2,2 ′)-azobis (2- Azo compounds such as methyl propionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
Specific examples of the polymerization initiator include, for example, polymerization initiators described on pages 65 to 148 of “Ultraviolet curing system” written by Kiyoto Kato (published by General Technology Center Co., Ltd .: 1989). Can do.

<Photopolymerization initiator>
The curable composition preferably contains a photopolymerization initiator.
As a photoinitiator, if a polymerization of a polymeric compound can be started, it will not restrict | limit, A well-known photoinitiator can be used. As the photopolymerization initiator, for example, those having photosensitivity from the ultraviolet region to the visible light region are preferable. Further, it may be an activator that generates an active radical by generating 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).

The content of the photopolymerization initiator in the curable composition is not particularly limited, but is generally preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition. A photoinitiator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of photoinitiators together, it is preferable that total content is in the said range.

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, aminoacetophenone compounds, and hydroxyacetophenones.
As specific examples of the photopolymerization initiator, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, the contents of which are incorporated herein.

More specifically, as the photopolymerization initiator, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used. .
As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone compound, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone compound, 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 compound, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF) can be used.

(Oxime compounds)
More preferred examples of the photopolymerization initiator include oxime ester polymerization initiators (oxime compounds). In particular, oxime compounds have high sensitivity and high polymerization efficiency, can cure the curable composition layer regardless of the content concentration of metal nitride-containing particles in the curable composition, and design a high content of metal nitride-containing particles It is preferable because it is easy to do.
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 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) iminobutan-2-one, and 2-ethoxycarbonyl And oxyimino-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. 156-162. 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 Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA), or N-1919 (carbazole oxime ester skeleton containing photoinitiator An agent (manufactured by ADEKA) can also be used.

As other oxime compounds, compounds described in JP-T-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 a benzophenone moiety; a dye moiety Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209; a ketoxime compound described in International Publication No. 2009-131189; a triazine skeleton and an oxime skeleton in the same molecule A compound described in U.S. Pat. No. 7,556,910 and a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime compound may be an (E) oxime compound, a (Z) oxime compound, a mixture of (E) isomer and (Z) isomer. Good.

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the 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 the 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, and preferably an aryl group or a heterocyclic group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
In the 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 substituents described above.

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 the formula (1), R ¹ and R ² each independently 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 carbon And when R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently hydrogen Represents an 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 is a direct bond or a carbonyl group Indicates.

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

In 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 arylalkyl having 7 to 30 carbon atoms. Each of R ³ and R ⁴ 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 4 to 4 carbon atoms; 20 represents a heterocyclic group, 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, ethyl group, n-propyl group, i-propyl group, 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.
In the above formulas (3) and (4), R ¹ is preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, 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 the compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

Specific examples of oxime compounds preferably used in the curable composition are shown below. In addition, as the oxime compound, a compound described in Table 1 of International Publication No. 2015-036910 can also be used, and the above contents are incorporated herein.

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 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. More preferably, it is 000.
For the molar extinction coefficient of the compound, a known method can be used. It is preferable to measure.
You may use a photoinitiator in combination of 2 or more type as needed.

As the photopolymerization initiator, compounds described in JP-A-2008-260927, paragraph 0052, JP-A-201097210, paragraphs 0033 to 0037, and JP-A-2015-68893, paragraph 0044 are used. The above content is also incorporated herein.

[Optional ingredients]
The curable composition may contain components other than those described above within the scope of the effects of the present invention. Examples of components other than the above include polymerization inhibitors, solvents, colorants, surfactants, ultraviolet absorbers, silane coupling agents, and adhesion improvers. Below, the arbitrary component contained in a curable composition is explained in full detail.

<Polymerization inhibitor>
The curable composition preferably contains a polymerization inhibitor.
The content of the polymerization inhibitor in the curable composition is not particularly limited. 2 mass% is more preferable. A polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
As a polymerization inhibitor, it is as having already demonstrated as a polymerization inhibitor which a dispersion composition can contain.

<Solvent>
The curable composition preferably contains a solvent.
The content of the solvent in the curable composition is not particularly limited, but in general, the solid content of the curable composition is preferably adjusted to 20 to 90% by mass, and adjusted to be 30 to 90% by mass. More preferably. A solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of solvent together, it is preferable that solid content of a curable composition is in the said range.
As a solvent, it is as having already demonstrated as a solvent which a dispersion composition can contain.

<Colorant>
The curable composition may contain a colorant.
The content of the colorant in the curable composition is not particularly limited, but is generally preferably 0.0001 to 70% by mass with respect to the total solid content of the curable composition. A coloring agent may be used individually by 1 type, or may use 2 or more types together. When two or more colorants are used in combination, the total content is preferably within the above range.
As a coloring agent, it is as having already demonstrated as a solvent which a dispersion composition can contain.

<Surfactant>
The curable composition may contain a surfactant. Surfactant contributes to the applicability | paintability improvement of a curable composition.
When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.

Examples of the surfactant include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

For example, when the curable composition contains a fluorosurfactant, the liquid properties (particularly fluidity) of the curable composition are further improved. That is, when a film is formed using a curable composition containing a fluorosurfactant, wettability to the surface to be coated is improved by reducing the interfacial tension between the surface to be coated and the coating liquid. The coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with little thickness unevenness can be more suitably formed.

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 fluorosurfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and / or liquid-saving properties, and has good solubility in the curable composition. .

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florad FC430, FC431, FC171 (Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, K-H-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A No. 2011-89090.

<Ultraviolet absorber>
The curable 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 paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, the contents of which are incorporated herein.
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 further preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition. preferable.

<Silane coupling agent>
The curable composition may contain a 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) Is not contained, and is a fluorine atom, a silicon atom (excluding 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 content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass with respect to the total solid content in the curable composition. More preferably, the content is 0.0 to 6% by mass.
The curable composition may contain one silane coupling agent or two or more silane coupling agents. When a curable composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.

<Adhesion improver>
The curable composition may contain a silane coupling agent as an adhesion improver. Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, and the like.
The content of the adhesion improver is not particularly limited, but is preferably 0.02 to 20% by mass with respect to the total solid content of the curable composition.

[Another form of curable composition]
Another form of the curable composition according to the embodiment of the present invention is a curable composition containing the dispersion composition described above, a polymerizable compound, and a polymerization initiator.
The dispersion composition, the polymerizable compound, and the polymerization initiator are as already described.
The content of each component in the curable composition is as already described.

[Volume average particle diameter of metal nitride-containing particles in curable composition]
The volume average particle size of the metal nitride-containing particles in the curable composition is not particularly limited, but a cumulative 90% particle size in terms of volume (measured using a particle size distribution meter based on the dynamic light scattering method) D90) is preferably less than 0.5 μm, and more preferably less than 0.2 μm.
When the volume average particle diameter of the metal nitride-containing particles in the curable composition is less than 0.5 μm, the curable composition has a more excellent effect of the present invention.
The lower limit of D90 is not particularly limited, but is generally preferably 0.01 μm or more.

[Method for producing curable composition]
The curable composition can be prepared by mixing the above components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like). . The curable composition may be prepared by mixing the above-described dispersion composition and the above-described components. Moreover, the manufacturing method of a curable composition may include the manufacturing method of the dispersion composition already demonstrated.
In preparing the curable composition, each component may be blended at once, or each component may be blended sequentially after being dissolved or dispersed in a solvent. There are no particular restrictions on the order of introduction and working conditions when blending.

The curable composition is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. Examples thereof include a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
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 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 (for example, a first filter and a second filter) 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. You may combine the 1st filter of a different hole diameter within the range mentioned above. 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 described above 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, more preferably about 0.3 to 6.0 μm.
It is preferable that a curable composition does not contain impurities, such as a metal, the metal salt containing a halogen, an acid, and an alkali. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). ) Is most preferred.
The impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

[Curing film and method for producing cured film]
The cured film which concerns on embodiment of this invention is a cured film obtained by hardening | curing the said curable composition. The thickness of the cured film is not particularly limited, but is generally preferably 0.2 to 7 μm, more preferably 0.4 to 5 μm.
The above thickness is an average thickness, and is a value obtained by measuring the thicknesses of five or more arbitrary points of the cured film and arithmetically averaging them.

Although the manufacturing method in particular of a cured film is not restrict | limited, The method of apply | coating the curable composition mentioned above on a board | substrate, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a cured film is mentioned. .
The method of the curing treatment is not particularly limited, and examples thereof include a photocuring treatment or a thermosetting treatment, and a photocuring treatment (particularly a curing treatment by irradiation with actinic rays or radiation) is preferable from the viewpoint of easy pattern formation. .

The cured film which concerns on embodiment of this invention is a cured film obtained by hardening | curing the curable composition layer formed using the said curable composition.
Although the manufacturing method in particular of a cured film is not restrict | limited, It is preferable that the following processes are included.
-Curable composition layer formation process-Exposure process-Development process Hereinafter, each process is demonstrated.

<Curable composition layer forming step>
A curable composition layer formation process is a process of forming a curable composition layer using the said curable composition. As a process of forming a curable composition layer using a curable composition, the process of apply | coating a curable composition on a board | substrate and forming a curable composition layer is mentioned, for example.
The type of substrate is not particularly limited, but when used as a solid-state imaging device, for example, a silicon substrate is used. When used as a color filter (including a color filter for a solid-state imaging device), a glass substrate (glass wafer) or the like Is mentioned.
As a coating method of the curable composition on the substrate, various coating methods such as spin coating, slit coating, ink jet method, spray coating, spin coating, cast coating, roll coating, and screen printing are applied. Can do.
The curable composition applied on the substrate is usually dried at 70 to 150 ° C. for about 1 to 4 minutes to form a curable composition layer.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step was exposed to light by irradiating actinic rays or radiation through a photomask having a pattern-shaped opening, and was irradiated with light. Only the curable composition layer is cured.
The exposure is preferably performed by irradiation of radiation. As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is preferable as a light source. The irradiation intensity is preferably 5 ~ 1500mJ / cm ^2, more preferably 10 ~ 1000mJ / cm ^2.

<Development process>
Subsequent to the exposure step, development processing (development step) is performed to elute the light non-irradiated portion in the exposure step into the developer. Thereby, only the photocured part remains.
An alkaline developer may be used as the developer. An inorganic alkali developer or an organic alkali developer can be used, but an organic alkali developer is preferably used. The development temperature is usually preferably 20 to 40 ° C., and the development time is preferably 20 to 180 seconds.
As the inorganic alkaline developer, for example, an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, and sodium metasuccinate, the concentration is preferably 0.001 to 10% by mass, preferably Is an alkaline aqueous solution dissolved so as to be 0.005 to 0.5% by mass.
Organic alkali developers include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole , Piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene have a concentration of 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass. An aqueous alkali solution dissolved in this manner can be mentioned.
For example, 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. When a developer composed of such an alkaline aqueous solution is used, the cured film is generally washed (rinsed) with pure water after development.

In addition, the manufacturing method of a cured film may contain another process.
There is no restriction | limiting in particular as another process, According to the objective, it can select suitably.
Examples of the other steps include a substrate surface treatment step, a preheating step (pre-baking step), and a post-heating step (post-baking step).
The heating temperature in the preheating step and the postheating step is preferably 80 to 300 ° C. The upper limit is more preferably 220 ° C. or lower. The lower limit is more preferably 90 ° C. or higher.
The heating time in the preheating step and the postheating step is preferably 30 to 300 seconds.

[Physical properties of cured film]
・ OD (Optical Density)
The cured film has an excellent light-shielding property, and the optical density (OD: Optical Density) per film thickness of 1.0 μm in the wavelength region of 400 to 1200 nm is preferably more than 2.0, more than 3.0. More preferred. The upper limit is not particularly limited, but is generally preferably 10 or less. The cured film can be preferably used as a light shielding film.
In addition, in this specification, an optical density intends the optical density measured by the method described in the Example. In this specification, the optical density per film thickness of 1.0 μm in the wavelength region of 400 to 1200 nm is more than 3.0. The optical density per 1.0 μm of film thickness in the entire wavelength range of 400 to 1200 nm is 3. Intended to be greater than zero.

The cured film preferably has a surface uneven structure. By doing so, the reflectance of a light shielding layer can be reduced. Even if the surface of the light shielding layer itself has a concavo-convex structure, another layer may be provided on the light shielding layer to provide the concavo-convex structure. The shape of the surface concavo-convex structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm to 1.5 μm.
The reflectance of the light shielding layer is preferably 5% or less, more preferably 3% or less, and still more preferably 2% or less.
The method for producing the surface concavo-convex structure is not particularly limited, but includes a method of adding an organic filler or an inorganic filler to the light-shielding layer or other layers, a lithography method using exposure and development, etching, sputtering, nanoimprint method, etc. A method of roughening the surface of the light shielding layer or other layers may also be used.
Moreover, as a method for reducing the reflectance of the cured film, in addition to the above, a method of providing a low refractive index layer on the light shielding layer, a method of providing a plurality of layers having different refractive indexes (for example, a high refractive index layer), For example, there is a method for forming a low optical density layer and a high optical density layer described in JP-A-2015-1654 (in this case, as a black pigment, nitriding a transition metal of Group 3 to 11 of the present invention) Metal nitride-containing particles containing the product may be used).

Hardened films are portable devices such as personal computers, tablets, mobile phones, smart phones, and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, barcode readers, automatic teller machines ( ATM (automated teller machine), high-speed camera, and industrial equipment such as equipment with identity authentication function using facial image authentication; in-vehicle camera equipment; medical equipment such as endoscope, capsule endoscope, and catheter Camera equipment; Space sensors such as biosensors, biosensors, military reconnaissance cameras, 3D map cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets; Light filter member and light shield for optical filter and module used And further is suitable for anti-reflection member and the antireflection film.

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 filter and an optical film used for a quantum dot display. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function.
Examples of quantum dot displays are described in US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. The thing which was done is mentioned.

[Solid-state imaging device and solid-state imaging device]
A solid-state imaging device and a solid-state imaging device according to an embodiment of the present invention contain the cured film. The form in which the solid-state imaging device contains a cured film is not particularly limited. For example, the solid-state imaging device includes a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate. And having the cured film of the present invention on the light receiving element forming surface side of the support (for example, the portion other than the light receiving portion and / or the color adjustment pixel) or the opposite side of the forming surface. Things.
The solid-state imaging device contains the solid-state imaging element.

Configuration examples of the solid-state imaging device and the solid-state imaging device will be described with reference to FIGS. In FIG. 1 and FIG. 2, in order to clarify each part, the ratio of the thickness and / or width is disregarded and partly exaggerated.
As shown in FIG. 1, the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Yes. Further, a lens layer 111 is provided on the cover glass 103 with a spacer 104 interposed therebetween. The lens layer 111 includes a support body 113 and a lens material 112. The lens layer 111 may have a configuration in which the support 113 and the lens material 112 are integrally formed. When stray light is incident on the peripheral region of the lens layer 111, the effect of condensing light on the lens material 112 is weakened due to light diffusion, and light reaching the imaging unit 102 is reduced. In addition, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 111 is shielded from light by providing a light shielding film 114. The cured film according to the embodiment of the present invention can also be used as the light shielding film 114.

The solid-state imaging device 101 photoelectrically converts an optical image formed by the imaging unit 102 serving as a light receiving surface thereof and outputs it as an image signal. The solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated. The laminated substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 having the same size, and the circuit substrate 107 is laminated on the back surface of the chip substrate 106.

The material of the substrate used as the chip substrate 106 is not particularly limited, and a known material can be used.

An imaging unit 102 is provided at the center of the surface of the chip substrate 106. Further, when stray light is incident on the peripheral area of the imaging unit 102, dark current (noise) is generated from a circuit in the peripheral area. Therefore, the peripheral area is shielded from light by providing a light shielding film 115. The cured film according to the embodiment of the present invention can also be used as the light shielding film 115.

A plurality of electrode pads 108 are provided on the surface edge of the chip substrate 106. The electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (not shown) provided on the surface of the chip substrate 106 (which may be a bonding wire).

External connection terminals 109 are provided on the back surface of the circuit board 107 at positions substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to an electrode pad 108 via a through electrode 110 that vertically penetrates the multilayer substrate 105. Each external connection terminal 109 is connected to a control circuit that controls driving of the solid-state imaging device 101 and an image processing circuit that performs image processing on an imaging signal output from the solid-state imaging device 101 via a wiring (not shown). Yes.

As shown in FIG. 2, the imaging unit 102 is configured by each unit provided on a substrate 204 such as a light receiving element 201, a color filter 202, and a microlens 203. The color filter 202 includes a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The cured film according to the embodiment of the present invention can also be used as the black matrix 205bm.

As the material of the substrate 204, the same material as that of the above-described chip substrate 106 can be used. A p-well layer 206 is formed on the surface layer of the substrate 204. In the p-well layer 26, light receiving elements 201, which are n-type layers and generate and store signal charges by photoelectric conversion, are arranged in a square lattice pattern.

On one side of the light receiving element 201, a vertical transfer path 208 made of an n-type layer is formed via a readout gate portion 207 on the surface layer of the p-well layer 206. On the other side of the light receiving element 201, a vertical transfer path 208 belonging to an adjacent pixel is formed via an element isolation region 209 made of a p-type layer. The read gate unit 207 is a channel region for reading signal charges accumulated in the light receiving element 201 to the vertical transfer path 208.

A gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204. A vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed on the gate insulating film 210 so as to cover the vertical transfer path 208, the read gate portion 207, and the element isolation region 209. The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer, and a read electrode that drives the read gate unit 207 to read signal charges. The signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output unit (floating diffusion amplifier), and then output as a voltage signal.

A light shielding film 212 is formed on the vertical transfer electrode 211 so as to cover the surface thereof. The light shielding film 212 has an opening at a position directly above the light receiving element 201 and shields light from other areas. The cured film according to the embodiment of the present invention can also be used as the light shielding film 212.
On the light shielding film 212, an insulating film 213 made of BPSG (borophosphosilicate glass), an insulating film (passivation film) 214 made of P-SiN, and a transparent intermediate layer made of a planarizing film 215 made of transparent resin or the like are provided. ing. The color filter 202 is formed on the intermediate layer.

[Black matrix]
A black matrix contains the cured film which concerns on embodiment of this invention. The black matrix may be contained in a color filter, a solid-state image sensor, and a liquid crystal display device.
As the black matrix, those already described above; black edges provided at the peripheral edge of a display device such as a liquid crystal display device; grids between red, blue, and green pixels, and / or striped blacks A dot-like and / or linear black pattern for light shielding a TFT (thin film transistor). For the definition of this black matrix, see Taihei Kanno, “Liquid Crystal Display Manufacturing Dictionary”, 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64.
The black matrix improves the display contrast, and in the case of an active matrix liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage, it has a high light shielding property (with an optical density OD). 3 or more).

The manufacturing method of the black matrix is not particularly limited, but can be manufactured by the same method as the manufacturing method of the cured film. Specifically, a curable composition is applied to a substrate to form a curable composition layer, and exposure and development can be performed to produce a patterned cured film (black matrix). The thickness of the cured film used as the black matrix is preferably 0.1 to 4.0 μm.

The material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more with respect to visible light (wavelength: 400 to 800 nm). Specific examples of such materials include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; From the viewpoint of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferred.

[Color filter]
The color filter according to the embodiment of the present invention contains a cured film.
The form in which the color filter contains a cured film is not particularly limited, and examples thereof include a color filter including a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.

A color filter containing a black matrix (cured film) can be produced, for example, by the following method.
First, a coating film (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a substrate. In addition, the resin composition for each color is not particularly limited, and a known resin composition can be used. In the curable composition according to the embodiment of the present invention, the metal nitride-containing particles correspond to each pixel. It is preferable to use a colorant replaced.
Next, it exposes with respect to the resin composition layer through the photomask which has a pattern corresponding to the opening part of a black matrix. Next, after removing the unexposed portions by development processing, the colored pixels can be formed in the openings of the black matrix by baking. For example, a color filter having red, green, and blue pixels can be manufactured by performing a series of operations using a resin composition for each color containing red, green, and blue pigments, for example.

[Liquid Crystal Display]
The liquid crystal display device according to the embodiment of the present invention contains a cured film. Although the form in which a liquid crystal display device contains a cured film is not restrict | limited, The form containing the color filter containing the black matrix (cured film) already demonstrated is mentioned.

As the liquid crystal display device according to the present embodiment, for example, a mode provided with a pair of substrates arranged opposite to each other and a liquid crystal compound sealed between the substrates can be mentioned. The substrate is as already described as the substrate for the black matrix.

As a specific form of the liquid crystal display device, for example, from the user side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) The laminated body which contains an element / board | substrate / polarizing plate / backlight unit in this order is mentioned.

The liquid crystal display device according to the embodiment of the present invention is not limited to the above. For example, “Electronic display device (Akio Sasaki, published by Industrial Research Co., Ltd., 1990)”, “Display device (Junsho Ibuki) The liquid crystal display device described in the book "Industry Books Co., Ltd." issued in 1989). Further, for example, there is a liquid crystal display device described in “Next-generation liquid crystal display technology (Uchida, edited by Tatsuo, Kogyo Kenkyukai, published in 1994)”.

[Infrared sensor]
The infrared sensor which concerns on embodiment of this invention contains the said cured film.
The infrared sensor which concerns on the said embodiment is demonstrated using FIG. In the infrared sensor 300 shown in FIG. 3, reference numeral 310 denotes a solid-state image sensor.
The imaging region provided on the solid-state imaging device 310 is configured by combining the infrared absorption filter 311 and the color filter 312 according to the embodiment of the present invention.
The infrared absorption filter 311 transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm), and transmits light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm). Preferably, it is a film that shields light having a wavelength of 900 to 1000 nm, and a cured film containing an infrared absorber (as already described in the form of the infrared absorber) as a colorant can be used.
The color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed. For example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used, and its form is as described above.
Between the infrared transmission filter 313 and the solid-state imaging device 310, a resin film 314 (for example, a transparent resin film or the like) that can transmit light having a wavelength transmitted through the infrared transmission filter 313 is disposed.
The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light having a specific wavelength, and is a colorant that absorbs light in the visible light region (for example, a perylene compound and / or bisbenzofuranone). Compound) and an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, a polymethine compound, and the like) according to an embodiment of the present invention can be used. For example, the infrared transmission filter 313 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.
A micro lens 315 is disposed on the incident light hν side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed so as to cover the microlens 315.
In the embodiment shown in FIG. 3, the resin film 314 is disposed, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared transmission filter 313 may be formed on the solid-state image sensor 310.
In the embodiment shown in FIG. 3, the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thickness of both may be different.
In the embodiment shown in FIG. 3, the color filter 312 is provided on the incident light hν side with respect to the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 is changed to change the infrared absorption filter 311. May be provided closer to the incident light hν than the color filter 312.
In the embodiment shown in FIG. 3, the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other. However, both filters do not necessarily have to be adjacent to each other, and other layers may be provided therebetween. . The cured film according to the embodiment of the present invention can be used as a light-shielding film such as an end or side surface of the surface of the infrared absorption filter 311, or can be used for an inner wall of the infrared sensor device to cause internal reflection or light reception. It is possible to prevent the incident of unintended light and improve the sensitivity.
According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including 3D information can be taken.

Next, a solid-state imaging device to which the infrared sensor is applied will be described.
The solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like. As for each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to, and the contents thereof are incorporated in this specification.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist 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.
The apparatus described in paragraph 0042 of JP-A-2005-343784 and FIG. 1 was used for the production. Specifically, in FIG. 1 of the above publication, a metal nitride is used using an apparatus (hereinafter referred to as “nanoparticle manufacturing apparatus”) in which the discharge vessel 1 is a stainless steel vacuum chamber (Fukushin Kogyo Co., Ltd.). Containing particles were produced. First, the air in the vacuum chamber was exhausted by an exhaust pump. Next, a mixed gas of helium (He) gas (purity 99.99%) and argon gas (mixing ratio 50/50% by volume in the standard state) is brought to a pressure of 600 Torr (79.99 kPa) in the vacuum chamber. Until supplied.

As the discharge electrode of the nanoparticle production apparatus, a tungsten electrode formed into a hollow rod having a length of 500 mm, a diameter of 12 mm, and a hollow diameter of 6 mm was used. The arrangement of the discharge electrodes was the same as that shown in FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in two stages of 6 each. The distance between the upper stage and the lower stage was about 160 mm.
The discharge electrode having a hollow structure is connected to a raw material supply device so that the source gas can be supplied from the hollow portion of the discharge electrode into the vacuum chamber.

The discharge starts with the tip of each discharge electrode in contact with each discharge electrode while applying an alternating current (voltage 20 to 40 V, current 70 to 100 A) having a phase difference to each discharge electrode. After the arc discharge occurs, the tip of each discharge electrode is moved outward so as to be separated, and the arc discharge is continued by setting the distance between the tips of adjacent discharge electrodes to be 5 to 10 mm. .

After performing arc discharge for 15 minutes, the supply tank of the raw material supply apparatus was heated, and the source gas was introduced into the vacuum chamber. First, NH ₃ gas (liquefied ammonium ECOAN, Showa Denko KK) 0.5 atm, H ₂ gas (hydrogen gas, Showa Denko Gas Products) 0.1 atm, Ar gas (argon gas, Taiyo Nippon Sanso) Was introduced at 0.4 atm. Subsequently, the supply tank was heated to 210 ° C., and TiCl ₄ gas (TLT-1, Toho Titanium Co., Ltd.) was introduced from the discharge electrode at 600 atm. Simultaneously with the introduction of the TiCl ₄ gas, a fine sulfur powder (fine powder sulfur 325 mesh, manufactured by Tsurumi Chemical Co., Ltd., corresponding to atom T) was supplied with nitrogen gas using a powder supply device TP-99010FDR (manufactured by JEOL). The supply amount was adjusted so that T _E / T _X in the obtained metal nitride-containing particles was as shown in Tables 2-1 to 2-9. After introducing nitrogen gas mixed with TiCl ₄ gas and fine sulfur powder into the vacuum chamber for 1 hour, voltage application from the AC power supply was stopped and supply of the gas was stopped. Next, the particles adhering to the inner wall of the vacuum chamber were collected.

Next, the obtained particles, O ₂ content, and water content was controlled to 100ppm or less each nitrogen (N ₂₎ placed in a sealed container in which the gas is introduced and allowed to stand 24 hours.

<Heating process>
The particles obtained above were heated at 200 ° C. using a vacuum oven VAC-101P (manufactured by ESPEC) to obtain metal nitride-containing particles P-1. The internal pressure of the vacuum oven during heating was 1.0 × 10 ³ Pa.

(Measurement of content of Ti, S (atom T), O, and N in metal nitride-containing particle P-1)
The content of titanium atom (Ti), sulfur atom (S), oxygen atom (O), and nitrogen atom (N) in the obtained metal nitride-containing particle P-1 was measured using a fluorescent X-ray analyzer. It was measured. As a sample, a metal nitride-containing particle P-1 formed into a pellet shape using a press was prepared. About the said sample, it measured on condition of the following using the fluorescent X ray analyzer.
・ Rigaku ZSM Primus II type XRF
・ X-ray Rh 30-50 kV, 48-80 mA
・ Measurement area 10μmφ
・ Measurement time: 10-240 deg / min

[Preparation of metal nitride-containing particles P-2 to P-63]
Similar to the metal nitride-containing particle P-1, except that each metal described below was used as the transition metal instead of Ti, and each atom described in Table 1 was used as the atom T instead of sulfur. Thus, metal nitride-containing particles P-2 to P to 63 were produced.
When each raw material is introduced into the vacuum chamber, the powder supply device is used if the raw material is powder, and the supply container is heated by a ribbon heater if the raw material is liquid or sublimable solid. Volatilized gas was supplied.
The transition metal content contained in each metal nitride-containing particle was measured using a fluorescent X-ray analyzer. The measurement conditions are as described above.

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
・ Ag powder: Ag powder made by Mitsui Kinzoku SPQ03R

[Production of metal nitride-containing particles P-C1]
Metal nitride-containing particles P-C1 were produced in the same manner except that the fine sulfur powder was not used in the production of metal nitride-containing particles P-1.

[Preparation of metal nitride-containing particles PC2]
Metal nitride-containing particles P-C2 were obtained in the same manner as the metal nitride-containing particles P-1, except that Ag powder (“SPQ03R” manufactured by Mitsui Kinzoku Co., Ltd.) was used instead of the fine sulfur powder. It was.

[Production of metal nitride-containing particles PC3]
TiN nanopowders manufactured by Nisshin Engineering Co., Ltd. were used as the metal nitride-containing particles PC3. In the preparation of the dispersion composition described later, TiC nanopowder manufactured by Hefei Kai'er was added as a colorant.
In addition, the ratio of TiN nanopowder and TiC nanopowder in the dispersion composition was adjusted as follows.
-Nissin Engineering Co., Ltd., TiN nano powder: 9.43 mass parts-Hefei Kai'er Co., TiC nano powder: 2.35 mass parts

[Production of Metal Nitride-Containing Particles P-C4]
Metal nitride-containing particles PC4 were prepared by the following method.
100 g of titanium oxide MT-150A having an average particle size of 15 nm (trade name: manufactured by Teika Co., Ltd.) and silica particles having a BET (Brunauer, Emmett, Teller) surface area of 300 m ² / g AEROPERL (registered trademark) 300/30 (manufactured by Evonik) ) And a dispersant Disperbyk190 (trade name: manufactured by Big Chemie) were weighed, 71 g of ion-exchanged water was added, and a planetary stirrer (MURASUSTAR KK-400W manufactured by KURABO) was used, and the revolution speed was 1360 rpm. (Rotation per minute) and stirred at a rotation speed of 1047 rpm for 20 minutes to obtain a uniform mixture.
This mixture was filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere was replaced with nitrogen, and ammonia gas at 100 mL / min for 5 hours at the same temperature. The nitriding reduction treatment was performed by flowing. Thereafter, the powder recovered from the quartz container was pulverized in a mortar to obtain titanium black [dispersed material containing titanium black particles and Si atoms] containing Si atoms and having a powdery specific surface area of 73 m ² / g.

[Preparation of metal nitride-containing particles PC5]
With reference to <Production Example 1> described in paragraphs 0189 to 0190 of JP-A-2006-209102, metal nitride-containing particles P-C5 were produced. A specific manufacturing method is as follows.
First, 300 g of hydrous titanium dioxide was suspended in 1 liter of water in terms of TiO ₂ to obtain a slurry. Next, the pH of the slurry was adjusted to 10 with an aqueous sodium hydroxide solution, and then the slurry temperature was heated to 70 ° C. A sodium silicate aqueous solution was dropped into the heated slurry over 2 hours. Next, the slurry temperature was heated to 90 ° C. Diluted sulfuric acid was added dropwise to the heated slurry over 2 hours to neutralize the pH of the slurry to 5. The neutralized slurry was held for 30 minutes. Next, the slurry was dehydrated to obtain a solid content. Next, the solid content was washed, and the washed solid content was heated to 850 ° C. in air and baked for 5 hours. As described above, titanium dioxide coated with silicon oxide (0.3% by mass as SiO ₂ ) was obtained. The obtained titanium dioxide was anatase type.
Next, the titanium dioxide coated with silicon oxide was put in a quartz tube having an inner diameter of 7.5 cm. Next, the quartz tube was heated at a temperature of 980 ° C. for 6 hours while ammonia gas was passed through the quartz tube at a flow rate of 10 L / min to obtain a product. Next, the obtained product was cooled to 100 ° C. under the same atmosphere, and further allowed to cool to room temperature in the atmosphere. The composition formula was expressed as TiN _0.95 O _0.20 · 0.01SiO _2. Metal nitride-containing particles PC5 were obtained.

[Production of Metal Nitride-Containing Particles PC6]
With reference to the method described in paragraph 0040 of WO 2007/102490, metal nitride-containing particles P-C6 were produced. A specific manufacturing method is as follows.
Deionized water was added to the metal nitride-containing particles P-1C to obtain a suspension having a metal nitride-containing particle P-1C content of 100 g / L. Next, 1 liter of this suspension was heated to 70 ° C. A solution obtained by dissolving 23.5 g of 50% tin chloride aqueous solution, 1.3 g of antimony chloride in 59 g of 35% hydrochloric acid aqueous solution and 17% sodium hydroxide aqueous solution was added in parallel to the heated suspension. During the addition, the pH of the suspension was maintained at 2 to 3, and the addition time was 60 minutes. Next, the suspension was filtered and washed until the specific resistance of the filtrate reached 50 μS / cm to obtain a solid content. Next, the solid content is dried at 120 ° C. for a whole day and night, and the solid content after drying is fired at 600 ° C. for 1 hour using an electric furnace to contain a metal nitride coated with a conductive layer of antimony solid solution tin oxide Particles P-1C were obtained and designated as metal nitride-containing particles PC6.

The compositions of the metal nitride-containing particles P-1 to P-63 and P-C1 to P-C6 are summarized in Tables 2-1 to 2-9.

[Measurement of T _E / T _X of Metal Nitride-Containing Particles]
T _E / T _X of the metal nitride-containing particles was measured by the following method.
Each metal nitride containing particle | grain was shape | molded into the pellet form using the press, and it was set as the sample. For the sample, X-ray photoelectron spectrometer, and using a fluorescent X-ray analyzer, the following measurement conditions, was measured T _{E /} T _X of the metal nitride-containing particles. The results were evaluated according to the following criteria and are shown in Tables 2-1 to 2-9.
A: T _E / T _X was less than 1.1.
B: T _E / T _X was 1.1 or more and less than 2.0.
C: T _E / T _X was 2.0 or more, or the value of T _E / T _X could not be calculated.

X-ray photoelectron spectroscopy (measurement of _{T E)}
・ Device: Quantera-SXM (trade name) device manufactured by PHI ・ X-ray source: Monochromatic Al Kα ray (1486.6 ev, 25 W, 15 kV, beam diameter 200 μmφ)
・ Measurement area: 200μmφ
Measurement conditions: Pass Energy = 140 eV, step = 0.1 eV, number of integrations 4 to 8 Measurement method: A sample was set in the apparatus, and the photoelectron take-off angle was 10 degrees.

X-ray fluorescence analysis (Measurement of _{T X)}
・ Rigaku ZSM Primus II type XRF
・ X-ray Rh 30-50 kV, 48-80 mA
・ Measurement area 10μmφ
・ Measurement time: 10-240 deg / min

[Preparation of Curable Compositions of Examples 1 to 85 and Comparative Examples 1 to 6]
In preparing the curable compositions of Examples 1 to 85, the components described in Tables 2-1 to 2-9 were mixed in the following ratios by the following method, and the metal nitride-containing particles were listed in the table. A dispersion composition was prepared by dispersing in each of the described dispersants. In addition, it mixed for 15 minutes using the stirrer (EUROSTAR made by IKA), and obtained the mixture.

[Synthesis of Dispersant A]
First, Dispersant A was synthesized by the following method.

<Synthesis Example A1: Synthesis of Macromonomer A-1>
Ε-caprolactone (1044.2 g), δ-valerolactone (184.3 g), and 2-ethyl-1-hexanol (71.6 g) were introduced into a 3000 mL three-necked flask to obtain a mixture. Next, the above mixture was stirred while blowing nitrogen. Next, Disperbyk111 (12.5 g, manufactured by Big Chemie, phosphoric acid resin) was added to the mixture, and the resulting mixture was heated to 90 ° C. After 6 hours, the mixture was heated to 110 ° C. after confirming the disappearance of the signal derived from 2-ethyl-1-hexanol in the mixture by using ¹ H-NMR (nuclear magnetic resonance). After the polymerization reaction was continued at 110 ° C. for 12 hours under nitrogen, disappearance of signals derived from ε-caprolactone and δ-valerolactone was confirmed by ¹ H-NMR, and the obtained compound was subjected to GPC method (Gel permeation). The molecular weight was measured by means of chromatography (depending on the measurement conditions described later). After confirming that the molecular weight of the compound reached the desired value, 2,6-di-t-butyl-4-methylphenol (0.35 g) was added to the mixture containing the above compound, and further obtained. To the mixture, 2-methacryloyloxyethyl isocyanate (87.0 g) was added dropwise over 30 minutes. Six hours after the completion of dropping, ¹ H-NMR confirmed that the signal derived from 2-methacryloyloxyethyl isocyanate (MOI) had disappeared, and then mixed propylene glycol monomethyl ether acetate (PGMEA) (1387.0 g). To give a macromonomer A-1 solution (2770 g) having a concentration of 50% by mass. The resulting macromonomer A-1 had a weight average molecular weight of 6,000.

<Synthesis Example P-1: Synthesis of Dispersant A>
In a three-necked flask with a capacity of 1000 mL, macromonomer A-1 (200.0 g), methacrylic acid (hereinafter also referred to as “MAA”, 60.0 g, corresponding to a polymerizable monomer for obtaining structural unit B), benzyl methacrylate (Hereinafter also referred to as “BzMA”, 40.0 g, corresponding to a compound for obtaining the structural unit C), PGMEA (propylene glycol 1-monomethyl ether 2-acetate, 366.7 g) was introduced to obtain a mixture. . The mixture was stirred while blowing nitrogen. Next, the temperature of the mixture was raised to 75 ° C. while flowing nitrogen into the flask. Next, dodecyl mercaptan (5.85 g) and then 2,2′-azobis (methyl 2-methylpropionate) (1.48 g, hereinafter also referred to as “V-601”) are added to the mixture, and polymerization is performed. The reaction was started. After the mixture was heated at 75 ° C. for 2 hours, additional V-601 (1.48 g) was added to the mixture. After 2 hours, additional V-601 (1.48 g) was added to the mixture. After further reaction for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. By the above operation, the polymerization reaction was completed, and Dispersant A was obtained.

[Composition of dispersion composition]
-Each metal nitride-containing particle (described in Tables 2-1 to 2-9): 11.79 parts by mass-30% by mass of propylene glycol monomethyl ether acetate in Dispersant A: 11.79 parts by mass-Propylene glycol monomethyl Ether acetate: 23.58 parts by mass The above components were mixed, and then the resulting mixture was dispersed under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. Obtained.

(Distribution condition)
・ 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: 22 hours

[Composition of curable composition]
Next, the dispersion composition, alkali-soluble resin, polymerization initiator, polymerizable compound, surfactant, polymerization inhibitor, and organic solvent were mixed to obtain a curable composition according to each example.
Content (mass%) of the component contained in each curable composition is shown below.

-Dispersion composition prepared above: 73.00 parts by mass

Alkali-soluble resin A-1 (“Acryl RD-F8” manufactured by Nippon Shokubai Co., Ltd., solid content 40%, solvent: propylene glycol monomethyl ether): 8.32 parts by mass

Polymerization initiator: Compound represented by formula (I-1) below: 1.96 parts by mass

Polymerizable compound M1 (“KAYARAD DPHA”, manufactured by Nippon Kayaku Co., Ltd., hexafunctional polymerizable compound (amount of ethylenically unsaturated group: 10.4 mmol / g), and pentafunctional polymerizable compound (ethylenically unsaturated group) Amount of 9.5 mmol / g)): 6.82 parts by mass

Surfactant 1: Surfactant represented by the following formula (weight average molecular weight (Mw) = 15311)
However, in the following formula, the structural units represented by the formulas (A) and (B) are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a, b, and c satisfy the relationships of a + c = 14 and b = 17, respectively.

Polymerization inhibitor (p-methoxyphenol) (PI-1): 0.00025 parts by mass

Solvent (propylene glycol monomethyl ether acetate): 7.82 parts by mass

The dispersant B used in Example 64 was synthesized by the following method.

[Synthesis of Dispersant B]
After adding tetrabutylammonium bromide (TBAB, 7.5 g) and p-methoxyphenol (MEHQ, 0.13 g) to dispersant A under air, glycidyl methacrylate (hereinafter also referred to as “GMA”) 66 0.1 g) was added dropwise. After completion of the dropwise addition, the reaction was continued for 7 hours under air, and the completion of the reaction was confirmed by acid value measurement. By adding PGMEA (643.6 g) to the obtained mixture, a 20% by mass solution of Dispersant B was obtained. The obtained Dispersant B had a weight average molecular weight of 35,000 and an acid value of 50 mgKOH / mg.

Each component in Tables 2-1 to 2-9 other than the above represents the following compounds.
・ Dispersants C to I

-Dispersant J:
A mixture was prepared together with 161.3 g of 4,4'-diaminobenzanilide and 527 g of N-methyl-2-pyrrolidone. 439.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to the above mixture and reacted at 70 ° C. for 3 hours, and then 2.2 g of phthalic anhydride was added. It was made to react at 2 degreeC for 2 hours, and obtained the 20 mass% dispersing agent J solution (dispersing agent J corresponds to polyamic acid).

-Dispersant K:
176.7 g of 3′-diaminodiphenylsulfone and 18.6 g of bis (3-aminopropyl) tetramethyldisiloxane were charged together with 2667 g of γ-butyrolactone and 527 g of N-methyl-2-pyrrolidone to obtain a mixed solution. 439.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to the above mixture and reacted at 70 ° C. for 3 hours, and then 2.2 g of phthalic anhydride was added. The mixture was reacted at 0 ° C. for 2 hours to obtain a 20 mass% dispersant K solution (dispersant K corresponds to polyamic acid).

・ Alkali-soluble resin A-2
A mixed solution was obtained by charging 95.1 g of 4,4'-diaminodiphenyl ether and 6.2 g of bis (3-aminopropyl) tetramethyldisiloxane together with 525 g of γ-butyrolactone and 220 g of N-methyl-2-pyrrolidone. To the above mixed solution, 144.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and reacted at 70 ° C. for 3 hours, and then 3.0 g of phthalic anhydride was added. The mixture was reacted at 70 ° C. for 2 hours to obtain a 25 mass% resin A-2 solution (resin A-2 corresponds to polyamic acid).

Polymerizable compound M2: Shin-Nakamura Chemical Co., Ltd., trade name “U-15HA”
Polymerizable compound M3: Nippon Kayaku Co., Ltd., trade name “KAYARAD RP-1040”

Polymerizable compound M4:
A compound represented by the following formula (synthesized with reference to JP2009-169049)

-Polymerization initiator I-1: Polymerization initiator of the following formula (I-1)-Polymerization initiator I-2: Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd., polymerization initiator of the above formula (C-7))
Polymerization initiator I-3: Irgacure OXE02 (trade name, manufactured by BASF Japan, polymerization initiator of the above formula (C-11))
-Polymerization initiator I-4: Polymerization initiator of the following formula (I-4)-Polymerization initiator I-5: Polymerization initiator of the following formula (I-5)-Polymerization initiator I-6: The following formula (I -6) polymerization initiator / polymerization initiator I-7: Adeka Arcles NCI-831 (trade name, manufactured by Adeka)
Polymerization initiator I-8: N-1919 (trade name, manufactured by Adeka)

[Evaluation]
[Real part of complex dielectric constant of metal nitride-containing particles]
The real part of the complex dielectric constant of the metal nitride-containing particles contained in each curable composition was measured by the following method.
A curable composition layer was obtained by applying a curable composition on an 8-inch silicon wafer by spin coating at a rotational speed of 0.3 μm. The silicon wafer with the curable composition layer was placed on a hot plate with the silicon wafer side down, and heated at 100 ° C. for 2 minutes to dry the curable composition layer. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), it is curable at an exposure amount of 500 mJ / cm ² through a reticle (photomask) in which a 2 cm × 2 cm region is exposed at a wavelength of 365 nm. The composition layer was exposed. Next, the silicon wafer on which the curable composition layer after exposure was formed was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film). Paddle development was performed at 23 ° C. for 60 seconds using an organic alkali developer (manufactured by Electronics Materials). Next, the silicon wafer after the paddle development is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from the nozzle above the rotation center. To obtain a silicon wafer provided with a 2 cm × 2 cm patterned cured film. The obtained silicon wafer was heat-treated at 220 ° C. for 1 hour using a clean oven (High Temp Clean Oven CLH-300S, manufactured by Koyo Thermo Systems Co., Ltd.). The curable composition used was appropriately diluted with PGMEA (propyleneglycol monomethyl ether acetate) to obtain a film having a thickness of 0.3 μm.
The obtained cured film was subjected to spectroscopic ellipsometry (M-2000XI-210: spectroscopic ellipsometry manufactured by JA Woollam), and the phase difference between p-polarized light (parallel) and s-polarized light (vertical) at a wavelength of 400 to 1200 nm. A spectrum of Δ and amplitude ratio Ψ was obtained. Fitting analysis is performed on the obtained (Δ, Ψ) spectrum using a Bruggeman effective medium approximation (EMA) model, and the dielectric constant of the true metal nitride-containing particles contained in the film is determined. Asked. (The prescription value was used for the content of the metal nitride-containing particles used in the EMA model. The metal nitride-containing particles in the cured film were separated by separating the metal nitride-containing particles in the cured film by the following method. The real part of the complex dielectric constant was evaluated from the obtained complex dielectric constant according to the following criteria. The results are shown in Tables 2-1 to 2-9.
Method for separating metal nitride-containing particles from a curable composition:
First, an organic solvent containing chloroform is added to the curable composition, and components other than the metal nitride-containing particles are dissolved to obtain a solution. The lysate is centrifuged to obtain a precipitate. Next, the precipitate is heated and concentrated to obtain metal nitride-containing particles.
A: The minimum value of the real part of the complex dielectric constant was less than 0.
B: The minimum value of the real part of the complex dielectric constant was 0 or more.

[Average primary particle diameter of metal nitride-containing particles]
The average primary particle diameter of the metal nitride-containing particles contained in each curable composition was measured by the following method.
Sample: Each curable composition was diluted 100 times with PGMEA (propyleneglycol monomethyl ether acetate) to obtain a diluted solution. Next, the diluted solution was dropped on the carbon foil and dried to obtain a sample.
The sample was observed with a transmission electron microscope (TEM) at a magnification of 20,000 to obtain an image. Next, the area of the metal nitride-containing particles in the obtained image was calculated by image processing. Next, the diameter when the obtained area was converted into a circle was calculated, and the diameter in terms of a circle evaluated for 400 particles was obtained by arithmetic averaging. The results were evaluated according to the following criteria and are shown in Tables 2-1 to 2-9. In addition, all the average primary particle diameters of the metal nitride containing particle which concerns on each Example and a comparative example were 1 nm or more.
A: The average primary particle diameter of the metal nitride-containing particles was less than 80 nm.
B: The average primary particle size of the metal nitride-containing particles was 80 nm or more and 200 nm or less. C: The average primary particle size of the metal nitride-containing particles exceeded 200 nm.

[D90 of volume average particle diameter of metal nitride-containing particles]
The volume average particle diameter D90 of the metal nitride-containing particles contained in each curable composition was measured by the following method.
Sample: Each curable composition was diluted 80 times with propylene glycol monomethyl ether acetate, and the resulting diluted solution was used as a sample.
The above sample was measured using a nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd. with the dynamic light scattering method as a measurement principle, and the volume average particle diameter D90 of the metal nitride-containing particles was calculated. The results were evaluated according to the following criteria and are shown in Tables 2-1 to 2-9.
A: The volume average particle diameter D90 of the metal nitride-containing particles was less than 0.2 μm.
B: D90 of the volume average particle diameter of the metal nitride-containing particles was 0.2 μm or more and less than 0.5 μm.
C: The volume average particle diameter D90 of the metal nitride-containing particles was 0.5 μm or more.

[Precipitation prevention]
The anti-settling property of each curable composition was evaluated by the following method.
First, the curable composition was diluted twice with propylene glycol monomethyl ether acetate to obtain a diluted solution. Next, 20 mL of the diluted solution was collected, and the collected diluted solution was placed in a 50 mL resin container and allowed to stand in an environment at 23 ° C. for 6 months. After standing, 5 g of the supernatant liquid from the liquid level of the diluted liquid in the resin container to a depth of 1 cm was collected, and the solid content was measured.
The amount of change in the solid content was calculated by comparing the solid content of the supernatant with the solid content of each curable composition immediately after preparation. The results were evaluated according to the following criteria and are shown in Tables 2-1 to 2-9. The smaller the amount of change in the solid content, the more difficult the metal nitride-containing particles settle in the curable composition.
The solid content was calculated by the following method. That is, 1 g of the curable composition was weighed and heated in an oven at 165 ° C. for 60 minutes to obtain a solid content. The mass of this solid content was measured, and the solid content [mass%] = (mass of solid content / mass of curable composition (1 g)) × 100 was calculated.
A: The amount of change in the solid content concentration was less than 1%.
B: The change amount of the solid content concentration was 1% or more and less than 2%.
C: The amount of change in solid content concentration was 2% or more and less than 3%.
D: The amount of change in the solid content concentration was 3% or more.

[Stability over time]
The temporal stability of the curable composition was evaluated by the following method.
First, 50 g of each curable composition was sealed in a 100 mL glass container. Next, the container was held at 45 ° C. and allowed to stand for 7 days, then held at −20 ° C. and left to stand for 10 days. After standing, a curable composition having a depth of 1 cm from the bottom of the container was collected. The collected curable composition was applied onto a glass substrate by a spin coating method to obtain a curable composition layer. Next, the glass substrate was placed on a hot plate with the glass substrate surface facing down, and heated at 100 ° C. for 2 minutes. Next, the curable composition layer after heating was allowed to stand at room temperature for 3 days. Next, the planar shape of the curable composition layer after standing was observed using an optical microscope MT-3600LW (manufactured by FLOVEL). The temporal stability of the curable composition was evaluated by the occurrence of foreign matter in the curable composition after being left. It can be said that the smaller the foreign matter, the better the temporal stability of the curable composition. Practically, “C” or more is preferable.

(Evaluation criteria)
AA: No foreign matter was observed in the curable composition layer.
A: Several foreign substances were observed in the curable composition layer.
B: Dozens of foreign matters were observed in the curable composition layer.
C: Hundreds of foreign matters were observed in the curable composition layer, but there were places where the generation of foreign matters was small in the plane of the curable composition layer.
D: Foreign matter was observed on the entire surface of the curable composition layer.

[Light shielding]
The light shielding property of the cured film was evaluated by the following method.
First, each curable composition was applied by spin coating on a glass substrate (Eagle XG, manufactured by Corning) having a thickness of 0.7 mm and a size of 10 cm square to obtain a curable composition layer. At this time, the rotational speed of the spin coater was adjusted so that the thickness of the curable composition layer after drying was 1.0 μm.
Next, the glass substrate was placed on a hot plate with the glass substrate surface down, and heat-treated at 100 ° C. for 2 minutes to dry the curable composition layer.
Next, the curable composition layer was exposed with a wavelength of 365 nm and an exposure amount of 500 mJ / cm ² using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon). Next, the glass substrate on which the curable composition layer after exposure was formed was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemtronics), and CD-2000 (Fuji Film). Paddle development was performed at 23 ° C. for 60 seconds using an organic alkali developer (manufactured by Electronics Materials). Next, the silicon wafer after the paddle development is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from the nozzle above the rotation center. And then rinsed to obtain a cured film.
About the obtained cured film, OD (optical density: optical density) was measured using the transmission densitometer (X-rite 361T (visual) densitometer). The results were evaluated according to the following criteria and are shown in Tables 2-1 to 2-9. The OD values in Tables 1 to 2-9 are the minimum values at wavelengths of 400 to 1200 nm. That is, the cured film (film thickness: 1.0 μm) of each example has an OD value equal to or greater than the OD value shown in the table over the entire wavelength range of 400 to 1200 nm.
A: The OD was over 3.0.
B: The OD was more than 2.0 and 3.0 or less.
C: The OD was 2.0 or less.

In Tables 2-1 to 2-9, “/” indicates that they are used together.

From the results shown in Tables 2-1 to 2-9, the curable compositions of Examples 1 to 85 had the effects of the present invention. On the other hand, the curable compositions of Comparative Examples 1 to 6 did not have the effects of the present invention.
The curable composition of Example 1 in which X, Y, and Z are each greater than 0 and less than 2 is superior to the curable composition of Example 61 in terms of anti-settling property and superior It was stable over time.
The curable composition of Example 1 in which the sum of X, Y, and Z is more than 0.4 and less than 1.6 is superior to the curable composition of Example 50 in terms of anti-settling property, And better stability over time. Moreover, the curable composition of Example 1 has more excellent temporal stability compared with the curable composition of Example 55, and the cured film obtained by the said curable composition is more excellent. It had a light-shielding property.
The curable composition of Example 1 in which the minimum value of the imaginary part ε ′ of the complex dielectric constant of the metal nitride-containing particles at a wavelength of 400 to 1200 nm is less than 0 is compared with the curable composition of Example 63. It had a better light-shielding property.
The curable composition of Example 1 in which the atom T is selected from elements other than aluminum, gallium, indium, tin, thallium, lead, and bismuth among the elements of the second to sixth periods is the examples 9-12. Compared with the curable composition, it had better anti-settling property and stability over time.
The curable composition of Example 1 in which the atom T is selected from Group 13 to 16 elements is superior to the curable compositions of Examples 6 to 8 in terms of anti-settling property and superior It was stable over time.
According to the curable composition of Example 1, wherein the atom T is any atom selected from the group consisting of a boron atom, a carbon atom, a sulfur atom, and a phosphorus atom, the curable composition of Example 5 Compared to the above, it had better temporal stability.
The curable composition of Example 1 in which the atom T is any atom selected from the group consisting of a boron atom, a sulfur atom, and a phosphorus atom is compared with the curable composition of Example 3, It had better aging stability.
The curable composition of Example 1 containing a dispersant A, having a polycaprolactone structure and / or a polyvalerolactone structure, wherein the sum of the number of repetitions of the polycaprolactone structure and the polyvalerolactone structure is 10 or more, dispersion The curable composition of Example 64 containing Agent B, the curable composition of Example 67 containing Dispersant E, and the curable composition of Example 68 containing Dispersant F were Example 65, As compared with the curable composition of Example 66, the anti-settling property was more excellent.
Further, in the formula (OX-1), the curable composition of Example 1 containing the polymerization initiator I-1 in which the monovalent substituent represented by B is an aryl group or a heterocyclic group, the polymerization initiator I The curable composition of Example 80 containing -3, the curable composition of Example 83 containing polymerization initiator I-6, the curable composition of Example 84 containing polymerization initiator I-7, And the curable composition of Example 85 containing the polymerization initiator I-8 has superior temporal stability compared to the curable compositions of Example 79, Example 81, and Example 82. It was.

[Example 1-WL: Production and evaluation of cured film for wafer level lens]
By the following method, a wafer level lens provided with a cured film obtained by curing the curable composition of Example 1 as a light-shielding film was produced, and its performance was evaluated.

First, a lens film was formed by the following operation.
[Formation of thermosetting cured film]
5 × 5 cm of a curable composition for lenses (a composition obtained by adding 1% by mass of an arylsulfonium salt derivative (SP-172 manufactured by ADEKA) to an alicyclic epoxy resin (EHPE-3150 manufactured by Daicel Chemical Industries) The film was coated on a glass substrate (thickness 1 mm, manufactured by Schott, BK7), and the coating film was cured by heating at 200 ° C. for 1 minute to form a film on which the residue on the lens could be evaluated.

On the glass wafer in which the said lens film was formed, the curable composition of Example 1 was apply | coated and the curable composition layer was obtained. Next, the glass wafer was placed on a hot plate and heated at 120 ° C. for 120 seconds. The film thickness of the curable composition layer after heating was 2.0 μm. (Curable composition layer forming step)
Next, the curable composition layer after heating was exposed using a high-pressure mercury lamp. It exposed through the photomask which has a 10 mm hole pattern, and the exposure amount was 500 mJ / cm < ² >. (Exposure process)
Next, the curable composition layer after exposure is subjected to paddle development for 60 seconds at a temperature of 23 ° C. using a 0.3% aqueous solution of tetramethylammonium hydroxide to obtain a patterned cured film (light-shielding film). It was. Next, the light shielding film was rinsed using a spin shower, and further, the light shielding film was washed with pure water. (Development process)

[Production and evaluation of solid-state imaging device]
On the glass wafer formed with the light-shielding film prepared above, a curable composition for lenses (alicyclic epoxy resin (EHPE-3150 manufactured by Daicel Chemical Industries) and arylsulfonium salt derivative (SP-172 manufactured by ADEKA)). 1% by weight of the composition), a curable resin layer is formed, the shape is transferred with a quartz mold having a lens shape, and cured by a high-pressure mercury lamp at an exposure amount of 400 mJ / cm ² , thereby producing a wafer. A wafer level lens array having a plurality of level lenses was produced.
The produced wafer level lens array was cut and a lens module was produced using the obtained wafer level lens, and then an imaging device and a sensor substrate were attached to produce an imaging unit (solid-state imaging device).
The obtained wafer level lens had no residue at the lens opening and had good transparency, and the light shielding layer also had high uniformity of the coated surface and high light shielding properties.

[Example 1-BL: Production and evaluation of a color filter including a black matrix]
[Formation of black matrix]
The curable composition of Example 1 was applied to a glass wafer by a spin coat method to obtain a curable composition layer. Next, the glass wafer was placed on a hot plate and heated at 120 ° C. for 2 minutes. The film thickness of the curable composition layer after heating was 2.0 μm.
Next, using an i-line stepper, the curable composition layer was exposed at a dose of 500 mJ / cm ² through a photomask having an Island pattern with a pattern of 0.1 mm.
Next, the curable composition layer after exposure was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide to obtain a cured film. Next, the cured film was rinsed using a spin shower, and the cured film was washed with pure water. Thus, a patterned light-shielding film (black matrix) was obtained. When a color filter was produced using the above black matrix, it had good performance.

When a curable composition was prepared and evaluated in the same manner as in Example 1 except that the surfactant was not used, the same result as in Example 1 was obtained.

A curable composition was prepared and evaluated in the same manner as in Example 1 except that the polymerization inhibitor was not used. The evaluation was the same as in Example 1 except that the temporal stability was B. Results were obtained.

In the curable composition of Example 1, instead of the metal nitride-containing particles P-1, the metal nitride-containing particles P-1 and a colorant (carbon black, trade name “Color Black S170”, manufactured by Degussa, average A curable composition was prepared using a mixture of a primary particle diameter of 17 nm, a BET specific surface area of 200 m ² / g, and carbon black produced by a gas black method. The mass ratio of the metal nitride-containing particles P-1 and the colorant in the curable composition (colorant / metal nitride-containing particles P-1) was adjusted to 2/8. When the said curable composition was evaluated, it turned out that it has a performance equivalent to Example 1. FIG.

In the curable composition of Example 1, instead of the metal nitride-containing particles P-1, the metal nitride-containing particles P-1 and a colorant (Pigment Yellow 150, manufactured by Hangzhou Star-up Pigment Co., Ltd., A curable composition was prepared using a mixture with trade name 6150 Pigment Yellow 5GN). The mass ratio of the metal nitride-containing particles P-1 and the colorant in the curable composition (colorant / metal nitride-containing particles P-1) was adjusted to 2/8. When the said curable composition was evaluated, it turned out that it has the performance equivalent to Example 1, and also it turned out that a darker light-shielding film is obtained. From this result, it was found that the effect of the present invention can be obtained even when used in combination with a colorant (organic pigment or chromatic dye).

DESCRIPTION OF SYMBOLS 100 ... Solid-state imaging device 101 ... Solid-state image sensor 102 ... Imaging part 103 ... Cover glass 104 ... Spacer 105 ... Laminated substrate 106 ... Chip substrate 107 ... Circuit board 108 ... Electrode pad 109 ... External connection terminal 110 ... Penetration electrode 111 ... Lens layer 112 ... Lens material 113 ... Supports 114, 115 ... Curing film 201 ... Light receiving element 202 ... Color filter 201 ... Light receiving element 202 ... Color filter 203 ... Micro lens 204 ... Substrate 205b ... Blue pixel 205r ... Red pixel 205g ... Green pixel 205bm ... Black matrix 206... P well layer 207... Readout gate portion 208... Vertical transfer path 209. Insulating film 211... Vertical transfer electrode 212... Cured

film

213, 214... Insulating film 215. Absorption filter 312 ... Color filter 313 ... Infrared transmission filter 314 ... Resin film 315 ... Micro lens 316 ... Flattening film

Claims

Metal nitride-containing particles containing a nitride of a transition metal of group 3-11,
The average primary particle size is 200 nm or less,
Containing a nitrogen atom and an atom T;
The atom T is not an oxygen atom, a chlorine atom, or a nitrogen atom, and is selected from Group 13-17 elements;
The mass-based content of the atom T on the surface of the metal nitride-containing particle detected by X-ray photoelectron spectroscopy is calculated as T E ,
The metal nitride-containing particles satisfying the relationship represented by the following formula (1), where T X is the mass-based content of the atoms T in the metal nitride-containing particles detected by fluorescent X-ray analysis particle. The unit of T E and T X is the mass%.
Formula (1) T E / T X <2.0
The metal nitride-containing particle according to claim 1, further comprising an oxygen atom.
The atomic ratio X of the content of the nitrogen atom to the content of the transition metal atom contained in the nitride,
The content atom number ratio Y of the oxygen atom content to the content of transition metal atoms contained in the nitride, and the number of atoms contained in the content of the atoms T relative to the content of transition metal atoms contained in the nitride The metal nitride-containing particles according to claim 2, wherein the ratio Z is more than 0 and less than 2.
The metal nitride-containing particles according to claim 3, wherein the sum of X, Y, and Z is more than 0.4 and less than 1.6.
The minimum value of ε 'is less than 0 when the complex dielectric constant ε of the metal nitride-containing particles at a wavelength of 400 to 1200 nm is expressed by the following formula (2). Metal nitride-containing particles.
Expression (2) ε = ε ′ + ε ″ j
In the above formula (2), ε ′ represents a real part of the complex dielectric constant ε, ε ″ represents an imaginary part of the complex dielectric constant ε, and j represents an imaginary unit.
Among the elements of the second to sixth periods, the atom T is
The metal nitride-containing particles according to any one of claims 1 to 5, which are selected from elements other than aluminum, gallium, indium, tin, thallium, lead, and bismuth.
The metal nitride-containing particle according to claim 6, wherein the atom T is selected from group 13 to group 16 elements.
The metal nitride-containing particle according to any one of claims 1 to 7, wherein the atom T is any atom selected from the group consisting of a boron atom, a carbon atom, a sulfur atom, and a phosphorus atom.
The metal nitride-containing particle according to any one of claims 1 to 8, wherein the atom T is any atom selected from the group consisting of a boron atom, a sulfur atom, and a phosphorus atom.
A dispersion composition comprising the metal nitride-containing particles according to any one of claims 1 to 9 and a resin.
A curable composition comprising the dispersion composition according to claim 10, a polymerizable compound, and a polymerization initiator.
A curable composition containing the metal nitride-containing particles according to any one of claims 1 to 9, a resin, a polymerizable compound, and a polymerization initiator.
Furthermore, the curable composition of Claim 11 or 12 containing a solvent.
A cured film obtained by curing the curable composition according to any one of claims 11 to 13.
A color filter comprising the cured film according to claim 14.
A solid-state imaging device containing the cured film according to claim 14.
A solid-state imaging device containing the cured film according to claim 14.
An infrared sensor containing the cured film according to claim 14.
A method for producing metal nitride-containing particles according to any one of claims 1 to 9,
Prepare a raw material A containing a nitrogen atom and a raw material B containing a transition metal atom and an atom T, or a raw material A containing a nitrogen atom, a raw material C containing a transition metal atom, and a raw material D containing an atom T The raw material preparation process,
Mixing two or more raw materials in a gas phase to obtain a mixture;
A step of condensing the mixture in a gas phase to obtain metal nitride-containing particles.
A method for producing the dispersion composition according to claim 10,
Prepare a raw material A containing a nitrogen atom and a raw material B containing a transition metal atom and an atom T, or a raw material A containing a nitrogen atom, a raw material C containing a transition metal atom, and a raw material D containing an atom T The raw material preparation process,
Mixing two or more raw materials in a gas phase to obtain a mixture;
Condensing the mixture in a gas phase to obtain metal nitride-containing particles;
And a step of mixing the metal nitride-containing particles and the resin to obtain a dispersion composition.
A method for producing a curable composition comprising a dispersion composition, a polymerizable compound, and a polymerization initiator, comprising the method for producing a dispersion composition according to claim 20. .
A curable composition layer forming step of forming a curable composition layer using the curable composition according to any one of claims 11 to 13;
An exposure step of exposing the curable composition layer by irradiating actinic rays or radiation through a photomask having a pattern-shaped opening; and
A development method of a cured film including the development process of developing the curable composition layer after the exposure, and forming a cured film.