JPWO2018043085A1 - Curable composition, cured film, color filter, solid-state imaging device, infrared sensor, method of producing cured film, and method of producing color filter - Google Patents

Abstract

An object of the present invention is to provide a curable composition capable of suppressing generation of a residue in an unexposed area and obtaining a cured film having an excellent pattern shape. Moreover, this invention makes it a subject to also provide the manufacturing method of a cured film, a color filter, a solid-state image sensor, an infrared sensor, a cured film, and a color filter. The curable composition of the present invention contains metal nitride-containing particles, an oxime-based polymerization initiator, a polymerizable compound, and an acid anhydride.

Description

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

Conventionally, curable compositions containing light-shielding particles such as carbon black are known.
The curable composition containing the light shielding particles as described above is used in various applications, for example, in the production of a cured film contained in a liquid crystal display device, a solid-state imaging device, and the like.
More specifically, a cured film called a black matrix on a glass substrate for the purpose of shielding light between colored pixels and improving contrast in color filters used in liquid crystal display devices and solid-state imaging devices. Is used.
In addition, in the solid-state imaging device, a cured film is used for the purpose of preventing noise generation, improving the image quality, and the like. Currently, small-sized and thin solid-state imaging devices are mounted on mobile terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants). Such a solid-state imaging device generally comprises a solid-state imaging device such as a charge coupled device (CCD) image sensor and a complementary metal-oxide semiconductor (CMOS) image sensor, and a lens for forming an object image on the solid-state imaging device. And.

  As such a curable composition, Patent Document 1 discloses a photosensitive black resin composition containing a light shielding material, an alkali soluble resin, a photopolymerization initiator, a reactive monomer, and an organic solvent, and at least as a light shielding material. A photosensitive black resin composition which contains titanium nitride particles and can form a coating film having predetermined optical properties is described.

Unexamined-Japanese-Patent No. 2010-97210

  The present inventors formed a photosensitive black resin composition layer using the photosensitive black resin composition described in Patent Document 1, exposed it, and then developed a patterned film. investigated. Although the above-mentioned film has high optical density (OD, optical density), it has been found that residue tends to be generated in the unexposed area, and that the pattern shape has not reached the required level recently.

Therefore, according to the present invention, the generation of a residue in the unexposed area is suppressed, and a cured film having an excellent pattern shape can be obtained (hereinafter, also referred to as "having the effect of the present invention"). Make provision an issue.
Moreover, this invention also makes it a subject to provide a cured film, a color filter, a solid-state image sensor, an infrared sensor, the manufacturing method of a cured film, and the manufacturing method of a color filter.

  MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be achieved with the following structure, as a result of earnestly examining in order to achieve the said subject.

[1] A curable composition containing metal nitride-containing particles, an oxime-based polymerization initiator, a polymerizable compound, and an acid anhydride.
[2] The curability according to [1], wherein the content mass ratio of the content of the acid anhydride to the content of the oxime-based polymerization initiator in the curable composition is 0.005 to 0.5. Composition.
[3] The curable composition according to [1] or [2], wherein the acid anhydride contains two or more acid anhydride groups in one molecule.
[4] The curable composition according to any one of [1] to [3], further comprising a polymerization inhibitor.
[5] The curable composition according to any one of [1] to [4], wherein the metal nitride-containing particles contain titanium nitride.
[6] The curing according to [5], wherein the diffraction angle 2θ of the peak derived from the (200) plane of the metal nitride-containing particle is 42.5 to 42.8 ° when the CuKα ray is used as the X-ray source Sex composition.
[7] The curable composition according to any one of [1] to [6], further containing an alkali-soluble resin.
[8] The curable composition according to [7], wherein the alkali-soluble resin contains at least one selected from the group consisting of a polyimide precursor and a polyimide resin.
[9] In any of [1] to [8], the content of the metal nitride-containing particles in the curable composition is 40% by mass or more based on the total solid content of the curable composition Curable composition as described.
[10] The content mass ratio of the content of the oxime-based polymerization initiator to the content of the metal nitride-containing particles in the curable composition is 0.03 to 0.2, [1] to [9] ] The curable composition in any one of.
[11] The curable composition according to any one of [1] to [10], wherein the oxime polymerization initiator contains a nitro group.
[12] The curable composition according to any one of [1] to [11], further containing a solvent.
[13] A cured film obtained by curing the curable composition according to any one of [1] to [12].
[14] A color filter containing the cured film as described in [13].
[15] A solid-state imaging device containing the cured film according to [13].
[16] An infrared sensor containing the cured film according to [13].
[17] A curable composition layer-forming step of forming a curable composition layer using the curable composition according to any one of [1] to [12], and a pattern on a curable composition layer An exposure step of irradiating with actinic rays or radiation through a photomask provided with an opening, and a developing step of developing a curable composition layer after exposure to form a cured film, The method for producing a cured film, comprising
[18] A method for producing a color filter, comprising the method for producing a cured film according to [17].

ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of the residue in an unexposed part can be suppressed, and the curable composition from which the cured film which has the outstanding pattern shape is obtained can be provided.
Further, according to the present invention, it is possible to provide a cured film, a color filter, a solid-state imaging device, an infrared sensor, a method of producing a cured film, and a method of producing a color filter.

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.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
Moreover, in the notation of the group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes not only those containing no substituent but also those containing a substituent. For example, the "alkyl group" includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
In addition, the term "actinic ray" or "radiation" in the present specification means, for example, the emission line spectrum of a mercury lamp, and far ultraviolet radiation represented by an excimer laser, extreme ultraviolet (EUV) radiation, X-rays, and electron beams. Means etc. In the present specification, light means actinic rays and radiation. Unless otherwise specified, the "exposure" in the present specification includes not only exposure by a mercury lamp, excimer laser, far ultraviolet light, X-ray, and EUV, but also writing by particle beams such as electron beams and ion beams. Do.
Also, as used herein, "(meth) acrylate" represents acrylate and methacrylate. Moreover, in this specification, "(meth) acryl" represents an acryl and a methacryl. Also, as used herein, “(meth) acryloyl” represents acryloyl and methacryloyl. Also, as used herein, "(meth) acrylamide" refers to acrylamide and methacrylamide. Moreover, in this specification, "monomer" and "monomer" are synonymous. A monomer is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, a polymerizable compound refers to a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group involved in the polymerization reaction.

[Curable composition]
The curable composition which concerns on embodiment of this invention contains metal nitride containing particle | grains, an oxime type polymerization initiator, a polymeric compound, and an acid anhydride. The mechanism by which the above-mentioned curable composition exerts the effects of the present invention is not necessarily clear, but the mechanism presumed is described below.
The present invention is not limited to those in which the effects can be obtained by the following mechanism, and is also included in the scope of the present invention when the effects of the present invention can be obtained by mechanisms other than the following mechanisms .

Recently, higher light shielding properties are required for cured films used for color filters and / or solid-state imaging devices and the like. As a photosensitive composition which can obtain a cured film having high light shielding properties as described above, one containing a large amount of light shielding particles and / or one containing metal nitride-containing particles is known.
Since the photosensitive composition containing a large amount of light shielding particles contains a large amount of light shielding particles, the resulting cured film exhibits high light shielding properties. However, on the other hand, the present inventors have found that the photosensitive composition as described above does not sufficiently transmit light in the composition during exposure, so that curing of the photosensitive composition may be insufficient. Have found out.
On the other hand, the photosensitive composition containing an oxime type polymerization initiator has excellent curability. It is presumed that this is because the oxime type polymerization initiator has excellent sensitivity and excellent polymerization efficiency.

  However, when the metal nitride-containing particles and the oxime-based polymerization initiator are used in combination as in the photosensitive composition described in Patent Document 1, the present inventors do not obtain a desired effect. Found out that there is The present inventors speculate that it is the following reason as a result of earnestly examining about the said phenomenon.

The present inventors have found that metal nitride-containing particles tend to be basic on the surface.
The above properties are not necessarily due to the particular method of manufacturing the metal nitride-containing particles. However, for the sake of simplicity, a specific manufacturing method will be taken up and described. For example, as a method for producing titanium nitride-containing particles, a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Application Laid-Open No. 2-22110) is known. In the above manufacturing method, it is presumed that the surface of the titanium nitride-containing particles to be manufactured tends to be basic because ammonia gas is used to introduce nitrogen into the titanium compound.

  On the other hand, the present inventors have also found that oxime type polymerization initiators have the property of being susceptible to hydrolysis. Therefore, when using metal nitride-containing particles in combination with an oxime-based polymerization initiator, hydrolysis of the oxime-based polymerization initiator may be promoted by the metal nitride-containing particles whose surface is basic. It is guessed.

The above tendency is remarkable when the curable composition contains a large amount of metal nitride-containing particles. When a general photosensitive composition contains a large amount of metal nitride-containing particles, the photosensitive composition is used to form a photosensitive composition layer on a substrate and the pattern composition is exposed. Was worse.
This is because the amount of light that reaches the surface on the opposite side (surface on the substrate side, lower layer area) is smaller than the area (upper layer area) near the exposed surface of the photosensitive composition layer, and curing becomes difficult. It is guessed that it is a body. It is presumed that this is due to the fact that light is more easily absorbed by the large amount of metal nitride-containing particles. When the photosensitive composition layer after exposure as described above is developed, the pattern of the lower layer region may be thinner than the upper layer region.

On the other hand, the curable composition concerning the embodiment of the present invention is characterized by containing an acid anhydride. The acid anhydride reacts with water molecules that cause hydrolysis of the oxime polymerization initiator in the curable composition to generate an acid. In other words, it has a function of removing water molecules that cause hydrolysis in the curable composition.
Therefore, in the said curable composition, an oxime type polymerization initiator is hard to be hydrolyzed, As a result, it is estimated that the cured film obtained using the said curable composition has the outstanding pattern shape.

Furthermore, the acid generated by the removal of water molecules by the acid anhydride moves to the upper layer region of the curable composition layer at the time of exposure (particularly when heating is performed after exposure), During the subsequent alkali development, it is presumed to have an effect of promoting development.
That is, when the curable composition contains an acid anhydride, the upper layer region of the curable composition layer formed thereby becomes more easily developed as compared to the lower layer region, and thus the pattern shape obtained is It is presumed to have improved. This is an unexpected synergistic effect of the curable composition containing an acid anhydride.

  Also, according to the study of the present inventors, an unintended polymerization reaction caused by decomposition of the oxime-based polymerization initiator, particularly in the unexposed area, by the acid anhydride suppressing hydrolysis of the oxime-based polymerization initiator. We also found that to suppress This is an unexpected effect. In the curable composition according to the embodiment of the present invention, it is presumed that in the unexposed area, the number of residues generated after development is suppressed by the action of the above-mentioned anhydride.

  Below, each component which a curable composition contains is explained in full detail.

[Anhydride]
The curable composition which concerns on the said embodiment contains an acid anhydride. The acid anhydride is not particularly limited as long as it has an action of removing water from the curable composition by reacting with water and trapping it, and known acid anhydrides can be used.
The content of the acid anhydride in the curable composition is not particularly limited, but generally 0.01 to 5% by mass is preferable based on the total solid content of the curable composition.
The acid anhydride may be used alone or in combination of two or more. When using 2 or more types of anhydrides together, it is preferable that total content is in the said range.
In the present specification, the acid anhydride means a compound containing one or more acid anhydride groups in one molecule.

In addition, the content mass ratio of the content of acid anhydride to the content of metal nitride-containing particles described later in the curable composition (content of acid anhydride / content of metal nitride-containing particles, hereinafter, 1.0 × 10 ^{−5 to} 1.0 is preferable, and 0.0050 to 0.50 is more preferable, simply “acid anhydride / metal nitride-containing particle”.
When the acid anhydride / metal nitride-containing particles are in the range of 0.0050 to 0.50, the curable composition has more excellent effects of the present invention.

The acid anhydride group contained in the acid anhydride is not particularly limited, and examples thereof include known acid anhydride groups. As the acid anhydride group, for example, a carboxylic acid anhydride group, a phosphonic acid anhydride group, a sulfonic acid anhydride group, etc. derived from the same kind of acid, and an acid anhydride derived from two different acids Groups are mentioned.
The number of acid anhydride groups contained in the acid anhydride is not particularly limited, but is preferably 2 or more in one molecule in that the curable composition has more excellent effects of the present invention. The upper limit of the number of acid anhydride groups contained in the acid anhydride is not particularly limited, but generally 4 or less is preferable.

  The acid anhydride is not particularly limited, but, for example, disulfuric acid, trifluoromethanesulfonic acid anhydride, dinitrogen pentoxide, diphosphoric acid, acetic anhydride, acetic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, phthalic anhydride, maleic anhydride And 2-sulfobenzoic anhydride and p-toluenesulfonic anhydride.

As the acid anhydride, a tetracarboxylic acid dianhydride represented by the formula (A1) is preferable in that the curable composition has more excellent effects of the present invention.

In formula (A1), R ₁ represents a tetravalent organic group. The tetravalent organic group is not particularly limited, and examples thereof include aliphatic or aromatic hydrocarbon groups which may have a substituent having 1 to 40 carbon atoms. As an aliphatic hydrocarbon group, the group etc. which are represented by the following formula are mentioned, for example.

In the above formulae, R _a represents a nitrogen atom or CR _b , R _b represents a hydrogen atom or a monovalent organic group, n represents an integer of 0 or 1 or more, and a plurality of them are present. R _a and R _b may be identical to or different from each other, and a plurality of R _b may be linked to each other to form a ring.

  As an aromatic hydrocarbon group, the group etc. which are represented by the following formula are mentioned, for example.

  As specific examples of the tetracarboxylic acid dianhydride represented by the formula (A1), for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, meso-butane-1,2,3,4- Tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3- (carboxymethyl) -1,2 4, 4-cyclopentane tricarboxylic acid 1,4: 2,3-dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4 -(2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride , 2,5,6-Naphthalenetetracarboxylic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, diethylenetriaminepentaacetic acid dianhydride 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, ethylenediaminetetraacetic acid dianhydride, octahydro-4a, 8b: 4b, 8a-bis (methanooxymethano) biphenylene-9, Examples thereof include, but are not limited to, 11,12,14-tetraone, and 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride.

  As the tetracarboxylic acid dianhydride, a compound represented by the following formula (A2) is more preferable in that the curable composition has more excellent effects of the present invention.

In formula (A2), R ₂ represents a single bond or a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include a group represented by the following formula and a group obtained by combining a plurality of groups represented by the following formula.

In the above formulae, R _b is as described above. Among them, a single bond, -O-, or -C (= O)-is preferable as R _{2 in} that the curable composition has more excellent effects of the present invention.

  Specific examples of the compound represented by the formula (A2) include, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride, diphenyl-3,3 ′, 4,4′-tetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic acid dianhydride, 4,4 ′-(ethine-1,2-diyl) diphthalic anhydride, 4,4 ′-(hexafluoro) Isopropylidene) diphthalic anhydride, 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride, 3,4'-oxydiphthalic anhydride, and 4,4'-oxydiphthalic anhydride Etc., but not limited thereto.

  The molecular weight of the acid anhydride is not particularly limited, but the acid anhydride is easily diffused by the upper layer region of the curable composition layer in the heating step after exposure, and the cured film having a more excellent pattern shape by the subsequent development In the point which is easy to be obtained, 100-800 are preferable and 100-600 are more preferable. In this paragraph, the molecular weight means a molecular weight that can be calculated from the structural formula.

[Metal nitride-containing particles]
The curable composition contains metal nitride-containing particles. In the present specification, metal nitride-containing particles mean particles containing nitride of metal atoms. In addition, the metal nitride-containing particles may contain metal atoms and atoms other than nitrogen atoms (for example, oxygen atoms), the form of which will be described later.

The content of the metal nitride-containing particles in the curable composition is not particularly limited, but is preferably 30% by mass or more based on the total solid content of the curable composition, and a cured film having more excellent light shielding properties 40 mass% or more is more preferable at the point which is obtained.
The upper limit of the content of the metal nitride-containing particles is not particularly limited, but in general, 70% by mass or less is preferable.
In addition, the content mass ratio of the content of the oxime-based polymerization initiator described later to the content of the metal nitride-containing particles in the curable composition (hereinafter also referred to as “oxime-based polymerization initiator / metal nitride-containing particles”) Is not particularly limited, but is preferably 0.001 to 0.4, and more preferably 0.03 to 0.2 in that a curable composition having more excellent effects of the present invention can be obtained.
The metal nitride-containing particles may be used alone or in combination of two or more. When two or more types of metal nitride-containing particles are used in combination, the total content is preferably within the above range.

The metal nitride-containing particles contain a nitride of metal atoms as described above. In addition, in this specification, when only calling it a "metal atom", it is a metal atom contained in metal nitride containing particle | grains, Comprising: The thing of the metal atom which exists as a nitride is intended.
The metal atom is not particularly limited, and known metal atoms can be used. Examples of the metal atom include transition metals, and transition metals of groups 3 to 11 are preferable in that a curable composition capable of obtaining a cured film having more excellent light shielding properties can be easily obtained, and Ti, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, or Pt is more preferable, Ti, Sc, V, Cr, Co, Cu, Y, Zr, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re, or Pt is more preferable, and Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W or Re is particularly preferred, and Ti, V, Nb, Ta or Zr is most preferred.

Although it does not restrict | limit especially as content of the metal atom in metal nitride containing particle | grains, 50-80 mass% is preferable with respect to the total mass of metal nitride containing particle | grains. The content of metal atoms in the metal nitride-containing particles can be analyzed by ICP (Inductively Coupled Plasma) emission spectroscopy.
In addition, a metal atom may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of metal atoms together, it is preferable that total content is in the said range.

The metal nitride-containing particles contain a nitride of metal atoms. The nitride of the metal atom may be mixed with oxygen at the time of its synthesis.
0.001-40 mass% is preferable with respect to the total mass of the nitride of a metal atom, as for content of the oxygen atom in the nitride of a metal atom, 0.001-35 mass% is more preferable, and 0.001 -30 mass% is still more preferable. The content of oxygen atoms can be analyzed using an inert gas melting-infrared absorption method.
In addition, it is preferable that the nitride of a metal atom does not contain an oxygen atom substantially in the point which the light-shielding property which the cured film obtained by hardening | curing a curable composition has more excellent. The phrase "containing substantially no oxygen atom" means that no oxygen atom is detected using the above-mentioned measurement method.

  The metal nitride-containing particles preferably contain titanium nitride. The titanium nitride is not particularly limited, and known titanium nitride can be used.

The titanium nitride, for _{example, TiN, TiO 2, Ti n} O 2n-1 low-order titanium oxide represented by (1 ≦ n ≦ 20), _{and, TiN x O y (0 <} x <2.0,0. The form containing the titanium oxynitride which can be represented by 1 <y <2.0) is mentioned.
Generally, the diffraction angle 2θ of the peak derived from the (200) plane when the CuKα ray is used as the X-ray source is preferably 42.5 ° to 43.5 °, and the above titanium nitride has a more excellent light shielding property 42.5 degrees-42.8 degrees are more preferable, and 42.5-42.7 are still more preferable at the point which is easy to obtain the curable composition which can obtain a cured film.

When the X-ray diffraction spectrum of metal nitride-containing particles is measured using CuKα radiation as an X-ray source, the peak with the highest intensity is as follows: TiN has a peak derived from the (200) plane around 2θ = 42.5 °; The peak derived from the (200) plane is observed in the vicinity of 2θ = 43.4 °. On the other hand, although not the strongest peak, anatase-type TiO ₂ has a peak derived from the (200) plane near 2θ = 48.1 °, and a rutile TiO ₂ has a peak derived from the (200) plane 2θ = 39 . Observed near 2 °. Therefore, the peak position shifts to the high angle side with respect to 42.5 ° as the titanium nitride contains more oxygen atoms.

The diffraction angle 2θ of the peak derived from the (200) plane of the metal nitride-containing particles is preferably 42.5 ° or more and 43.5 ° or less, more preferably 42.5 ° or more and 42.8 or less, and 42.5 ° More preferably, it is 42.7 ° or less.
When the metal nitride-containing particles contain titanium oxide TiO ₂ , the peak derived from anatase-type TiO ₂ (101) as the strongest peak is around 2θ = 25.3 °, rutile-type TiO ₂ (110) The peak derived from is seen near 2θ = 27.4 °. However, TiO ₂ is white and is a factor to reduce the light shielding property of the light shielding film obtained by curing the curable composition, and therefore, it is preferable that the content is reduced to such an extent that it is not observed as a peak.

  The crystallite size of the metal nitride-containing particle can be determined from the half width of the peak obtained by the measurement of the above-mentioned X-ray diffraction spectrum. The crystallite size can be calculated using Scheller's equation.

  The crystallite size of the metal nitride-containing particles is preferably 50 nm or less, preferably 20 nm or more, and more preferably 20 to 50 nm. When the crystallite size is 20 to 50 nm, the light shielding film formed using the curable composition tends to have a higher transmittance of ultraviolet light (especially i-line (365 nm)), and a curable composition having higher photosensitivity The thing is obtained.

The specific surface area of the metal nitride-containing particles is not particularly limited, but can be determined using the BET (Brunauer, Emmett, Teller) method. 5-100 m < ² > / g is preferable and, as for the specific surface area of a titanium nitride, 10-60 m < ² > / g is more preferable.

The metal nitride may be complexed with other metal particles.
In the present specification, the term “complexing” refers to particles in which metal nitride and metal fine particles are complexed or in a highly dispersed state. Here, "composed" means that the particles are composed of both metal nitride and other metal components, and "highly dispersed state" means metal nitride and the other metals. It means that the metals are present individually, and the particles of the other metals are not aggregated and uniformly and uniformly dispersed.
The material of the metal fine particles is not particularly limited. For example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium And at least one selected from bismuth, antimony, lead, and alloys thereof. Among them, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and at least one selected from these alloys are preferable, and copper, silver, gold, platinum and tin, and alloys thereof At least one selected is more preferable. Silver is preferable from the viewpoint of being excellent in moisture resistance.
The content of the metal fine particles in the metal nitride-containing particles is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 30% by mass, with respect to the total mass of the metal nitride-containing particles.

(Method of producing metal nitride-containing particles)
It does not restrict | limit especially as a manufacturing method of metal nitride containing particle | grains, A well-known method can be used. Examples of the method for producing the metal nitride-containing particles include a gas phase reaction method. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable from the viewpoint that the mixing of impurities is small, the particle diameter is easy to be uniform, and the productivity is high.
In the thermal plasma method, the method of generating thermal plasma is not particularly limited, and direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, etc. may be mentioned, and contamination with impurities from the electrode is small. High frequency plasma is more preferred.
Although there is no particular limitation on a specific method of producing nitrides of metal atoms by the thermal plasma method, for example, a method of reacting titanium tetrachloride and ammonia gas in a plasma flame as a method of producing titanium nitride 2-22110), a method of evaporating titanium powder by high-frequency thermal plasma, introducing nitrogen as a carrier gas, nitriding it in the cooling process and synthesizing it (JP-A-61-11140), and at the periphery of plasma The method of blowing in ammonia gas (Unexamined-Japanese-Patent No. 63-85007) etc. is mentioned.
However, the method for producing a nitride of a metal atom is not limited to the above, and the production method is not limited as long as a nitride of a metal atom having desired physical properties can be obtained.

  The raw material containing metal atoms (hereinafter referred to as "metal raw material") used for producing metal nitride-containing particles is preferably high purity. The purity of the metal raw material is not particularly limited, but the purity of the metal atom is preferably 99.99% by mass or more, and more preferably 99.999% by mass or more.

The metal raw material may contain atoms other than metal atoms as impurities (hereinafter referred to as "impurity atoms"). The impurity atoms are not particularly limited, and include Fe atoms, Si atoms, and the like.
When the metal raw material contains Si atoms, the content of Si atoms is more than 0.002% by mass and preferably less than 0.3% by mass, with respect to the total mass of the metal raw material, and 0.01 to 0 15 mass% is more preferable, and 0.02 to 0.1 mass% is further preferable. When the content of Si atoms exceeds 0.002 mass%, the patterning property of the cured film is further improved. Further, when the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained metal nitride-containing particles is stabilized, and when the metal nitride-containing particles are dispersed, the metal nitride-containing particles are It is considered that there is an effect of suppressing particle generation by improving the adsorptivity of the dispersant and reducing the non-dispersion of the metal nitride-containing particles.
Moreover, less than 1 mass% is preferable with respect to the total mass of a metal raw material, and, as for the water | moisture content in the metal raw material used for manufacture of metal nitride containing particle | grains, less than 0.1 mass% is more preferable, It does not contain substantially Is more preferred.

Here, the method for causing the metal nitride-containing particles to contain an Fe atom is not particularly limited, and examples thereof include a method of introducing an Fe atom in the step of obtaining a metal raw material. More specifically, when producing a metal material by the Kroll method or the like, a reaction vessel is used which is made of a material containing an Fe atom such as stainless steel (SUS) or a press for crushing the metal material. Fe atoms can be attached to the surface of titanium particles by using a material containing Fe atoms as the material of the machine and the grinder.
Moreover, when using a thermal plasma method in manufacture of metal nitride containing particles, in addition to the metal atom which is a raw material, components, such as Fe particle and Fe oxide, are added and these are nitrided by a thermal plasma method. Thus, the metal nitride-containing particles can contain Fe atoms.
The Fe atoms contained in the metal nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, nitrides, oxynitrides, and sulfides. And acid sulfide etc. may be contained in any form. In addition, Fe atoms contained in the metal nitride-containing particles may be present as an impurity at a position between crystal lattices, or may be present as an impurity in an amorphous state at grain boundaries.

  The content of Fe atoms in the metal nitride-containing particles is preferably more than 0.001% by mass and less than 0.4% by mass with respect to the total mass of the metal nitride-containing particles. Among these, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is more preferable. Here, the content of Fe atoms in the metal nitride-containing particles is measured by ICP (Inductively Coupled Plasma; high frequency inductively coupled plasma) emission spectroscopy.

The metal nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of a cured film improves more. The reason why the patterning property is improved by containing the Si atom is considered to be the same as the Fe atom described above.
The content of Si atoms in the metal nitride-containing particles is more than 0.002% by mass, preferably less than 0.3% by mass, and preferably 0.01 to 0.15% with respect to the total mass of the metal nitride-containing particles. % Is more preferable, and 0.02 to 0.1% by mass is further preferable. The content of Si atoms in the metal nitride-containing particles is measured by the same method as the Fe atoms described above.
Further, the method for causing the metal nitride-containing particles to contain Si atoms is not particularly limited, and is the same as the method for introducing Fe atoms.

[Oxime-based polymerization initiator]
The said curable composition contains an oxime type polymerization initiator. The oxime-based polymerization initiator is not particularly limited, and known oxime-based polymerization initiators can be used.
The content of the oxime-based polymerization initiator in the curable composition is not particularly limited, but generally 0.5 to 30% by mass is preferable with respect to the total solid content of the curable composition, and the curable composition is From the point of having the more excellent effect of the present invention, 1 to 20% by mass is more preferable.
Moreover, as content of the said oxime type polymerization initiator, it is preferable to adjust so that the anhydride / initiator already demonstrated may become in a predetermined | prescribed range.
In addition, an oxime type polymerization initiator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of oxime type polymerization initiators together, it is preferable that total content is in the said range.

As specific examples of the oxime-based polymerization initiator, for example, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, or a compound described in JP-A-2006-342166 may be used. it can.
As an oxime compound, for example, 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-ethoxy Examples include carbonyloxyimino-1-phenylpropan-1-one and the like.
Also, J.J. C. S. Perkin II (1979) pp. 1653-1660), J.F. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. And the compounds described in JP-A-2000-80068, JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166. .
Among commercially available products, IRGACURE OXE 01 (manufactured by BASF), IRGACURE OXE 02 (manufactured by BASF), IRGACURE OXE 03 (manufactured by BASF), or IRGACURE OXE 04 (manufactured by BASF) are also suitably used. In addition, TR-PBG-304 (made by Changzhou High Power Electronic New Material Co., Ltd.), Adeka Akurus NCI-831 and Adeka Akurus NCI-930 (made by ADEKA), N-1919 (carbazole oxime ester skeleton containing photoinitiator) (Made by ADEKA), and NCI-730 (made by ADEKA) etc. can also be used.

Further, compounds described in JP-A-2009-519904 in which an oxime is linked to a carbazole N-position as an oxime-based polymerization initiator other than the above-mentioned; described in US Pat. No. 7,626,957 Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at a dye site; ketoximetic compounds described in WO-2009-131189; triazine skeleton and oxime A compound described in US Pat. No. 7,556,910 containing a skeleton in the same molecule; a compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-line light source; May be
Preferably, for example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, as the oxime-based polymerization initiator, a compound represented by the following formula (OX-1) is preferable. In addition, whether the N-O bond of the oxime polymerization initiator is an (E) isomer oxime compound or a (Z) isomer oxime compound, the (E) isomer and the (Z) isomer It may be a mixture.

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 Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetal atomic group.
Examples of the monovalent nonmetal 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. Also, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by the other 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, an aryl group and the like.
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. These groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.
As a bivalent organic group represented by A in Formula (OX-1), a C1-C12 alkylene group, a cycloalkylene group, or an alkynylene group is preferable. These groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.

  As a photoinitiator, the oxime type compound containing a fluorine atom can also be used. Specific examples of the oxime-based compound containing a fluorine atom include compounds described in JP-A-2010-262028; compounds 24 and 36-40 described in JP-A-2014-500852; and JP-A-2013-164471. Compound (C-3); and the like. This content is incorporated herein.

  Compounds represented by the following formulas (1) to (4) can also be used as the photopolymerization initiator.

In Formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or R ⁷ represents an arylalkyl group having 7 to 30 carbon atoms, and when R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to form a fluorene group, and R ³ and R ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a single bond (directly Bond or a carbonyl group is shown.

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 atom or a hydroxyl group, and 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 single bond or a carbonyl group, and a represents an integer of 0 to 4.

In Formula (3), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl having 7 to 30 carbon atoms R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 4 carbon atoms To 20 heterocyclic group, and X represents a single 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, -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 represents a single 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 each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a single bond.
In the above formulas (3) and (4), R ¹ is preferably independently methyl, ethyl, n-propyl, i-propyl, cyclohexyl or phenyl. 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 single bond.
As a specific example of a compound represented by Formula (1) and Formula (2), the compound described in stage number 0076-0079 of Unexamined-Japanese-Patent No. 2014-137466 is mentioned, for example. This content is incorporated herein by reference.

As an oxime type polymerization initiator, it is preferable to contain a nitro group at the point from which the curable composition which has the more outstanding effect of this invention is obtained.
Although it does not restrict | limit especially as a number of the nitro group which an oxime type compound contains, 1-4 pieces are preferable, 1 piece, or 2 pieces are preferable.
As a specific example of the oxime type polymerization initiator containing a nitro group, NCI-831 (a brand name, ADEKA company make) etc. which have the following structures are mentioned, for example.

  The specific example of an oxime type polymerization initiator is shown below.

The oxime-based polymerization initiator preferably has a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 to 480 nm, and further has a high absorbance at 365 nm and 405 nm preferable.
From the viewpoint of sensitivity, the molar absorption coefficient of the oxime-based polymerization initiator compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, 5, More preferably, it is 0000 to 200,000.
The molar absorption coefficient of the compound can be determined according to a known method, for example, using an ethyl acetate solvent in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), at a concentration of 0.01 g / L. It is preferable to measure.

  As the photopolymerization initiator, a bifunctional or trifunctional or higher functional compound may be used. As specific examples of such compounds, JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, JP-A-2016-532675, paragraphs 0417 to 0412, International Publication No. Dimers of the oxime compounds described in paragraphs 0039 to 0055 of 2017/033680, compounds (E) and (G) described in JP-A-2013-522445, and WO 2016/034963 Cmpd 1-7 mentioned are mentioned.

[Polymerizable compound]
The curable composition contains a polymerizable compound. In the present specification, a polymerizable compound intends a compound containing a polymerizable group and intends a compound different from an anhydride.
The content of the polymerizable compound in the curable composition is not particularly limited, but is preferably 5 to 30% by mass, and more preferably 10 to 25% by mass, with respect to the total solid content of the curable composition.
The polymerizable compounds may be used alone or in combination of two or more. When two or more types of polymerizable compounds are used in combination, the total content is preferably in the above range.

  The polymerizable compound is preferably a compound containing one or more groups containing an ethylenically unsaturated bond, more preferably a compound containing two or more groups, still more preferably a compound containing three or more groups, and a compound containing five or more groups. Is particularly preferred. The upper limit is preferably, for example, 15 or less. As a group containing an ethylenically unsaturated bond, a vinyl group, a (meth) allyl group, and a (meth) acryloyl group etc. are mentioned, for example.

  As the polymerizable compound, for example, the 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 incorporated in the present specification. Be

The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and 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 more under normal pressure. For example, the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and the contents thereof are incorporated in the present specification.

The polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), Pentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E; Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol residue or propylene glycol residue (for example, SR454, SR499 commercially available from Sartomer) are preferable. These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) can also be used.
The form of a preferable polymeric compound is 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 nonaromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to produce an acid. The polymerizable compound having a group is more preferable, and more preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronics TO-2349, M-305, M-510, and M-520 manufactured by Toa Gosei Co., Ltd.

  As a preferable acid value of the polymeric compound containing an acidic radical, it is 0.1-40 mgKOH / g, More preferably, it is 5-30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the developing dissolution property is good, and when it is 40 mg KOH / g or less, it is advantageous in terms of 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, and examples thereof include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, and tripenta Examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerol, diglycerol and trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Among them, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferable.

  In the formula (Z-1), all six R's are a group represented by the following formula (Z-2), or 1 to 5 of the six R's are 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.

The polymerizable compound containing a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and in DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, the formula (Z -2) the number of groups represented by 2 = 2, a compound wherein all R ¹ are hydrogen atoms, DPCA-30 (the same formula, m = 1, the number of groups represented by the formula (Z-2) = 3) , A compound wherein all R ^{1 s} are hydrogen atoms, DPCA-60 (the same formula, m = 1, the number of groups represented by formula (Z-2) = 6, a compound wherein all R ^{1 s} are hydrogen atoms), DPCA-120 (in the formula, m = 2, number of groups represented by formula (Z-2) = 6, compounds in which all R ¹ are hydrogen atoms), and the like.

  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)- And y each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, m each independently represents an integer of 0 to 10, and the sum of m is an integer of 0 to 40.
In formula (Z-5), the total of (meth) acryloyl groups is 5 or 6, n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60.

In formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and, as for the sum of each m, the integer of 4-8 is still more preferable.
In formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 3-60 is preferable, the integer of 3-24 is more preferable, and, as for the sum of each n, the integer of 6-12 is still more preferable.
Further, the formula (Z-4) or formula (Z-5) in the _{- ((CH 2) y CH} 2 O) - , or _{((CH 2) y CH (} CH 3) O) - , the oxygen atom side A form in which the end is bonded to X is preferred.

  The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in a form in which all six X's are an acryloyl group in formula (Z-5), a compound in which all six X's are an acryloyl group in formula (Z-5), and Preferred is a form that is a mixture with a compound in which at least one hydrogen atom is present. With such a configuration, developability can be further improved.

Moreover, as a total content in the polymeric compound of a compound represented by Formula (Z-4) or Formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.
Among the compounds represented by Formula (Z-4) or Formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

In addition, the polymerizable compound may contain a cardo skeleton.
The polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton.
Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, On Coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).

[Optional component]
The said curable composition may contain the arbitrary components other than the above. Examples of optional components include dehydrating agents, polymerization inhibitors, alkali-soluble resins, dispersants, solvents, silane coupling agents, UV absorbers, surfactants, adhesion improvers, and colorants. In addition, a coloring agent means coloring agents other than metal nitride containing particle | grains. Below, each component is explained in full detail.

<Dehydration agent>
The curable composition may contain a dehydrating agent. As used herein, dehydrating agents are intended compounds that are different from acid anhydrides.
The dehydrating agent is not particularly limited, and known dehydrating agents can be used. Among them, an ortho ester compound is more preferable as the dehydrating agent. Although it does not restrict | limit especially as an ortho ester compound, For example, the compound as described in stage 0039 of Unexamined-Japanese-Patent No. 2012-524759, and a stage 0040 is mentioned.
The content of the dehydrating agent in the curable composition is not particularly limited, but in general, it is preferably 0.01 to 5% by mass with respect to the total solid content in the curable composition.

<Polymerization inhibitor>
The curable composition preferably contains a polymerization inhibitor. The curable composition containing the polymerization inhibitor has more excellent storage stability, and the generation of the residue in the unexposed area is further suppressed. In the present specification, storage stability of the curable composition means storage stability that can be evaluated by the method described in the examples.
The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used.
The content of the polymerization inhibitor in the curable composition is not particularly limited, but in general, 0.1 to 5% by mass is preferable based on the total solid content of the curable composition.
The polymerization inhibitor may be used singly or in combination of two or more. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.

  The polymerization inhibitor is not particularly limited, and known compounds used as a polymerization inhibitor can be used. As a compound used as a polymerization inhibitor, a phenol type compound, a quinone type compound, a hindered amine type compound, a phenothiazine type compound, and a nitrobenzene type compound etc. are mentioned, for example.

  Examples of the above-mentioned phenolic compound include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-diphenol. -Tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, pentaerythritol tetrakis (3,5-di- tert-Butyl-4-hydroxyhydrocinnamate), 4-methoxy-1-naphthol, 1,4-dihydroxynaphthalene and the like.

  As a phenol type compound, the phenol type compound shown by Formula (IH-1) is preferable.

In formula (IH-1), R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group, an amino group, an aryl group, an alkoxy group, a carboxylic acid group, an alkoxycarbonyl group, or an acyl Represents a group. R _{1 to} R ₅ may be linked each other to form a ring.

As R _{1 to} R ₅ in the formula (IH-1), a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group and an ethyl group), an alkoxy group having 1 to 5 carbon atoms (eg, methoxy) And ethoxy group, an alkenyl group having 2 to 4 carbon atoms (e.g., a vinyl group), or a phenyl group is preferable.
Among them, R ₁ and R ₅ are each independently more preferably a hydrogen atom or a tert-butyl group, R ₂ and R ₄ are more preferably a hydrogen atom, and R ₃ is a hydrogen atom, an alkyl having 1 to 5 carbon atoms A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.

  Examples of the quinone compounds include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.

  As a hindered amine compound, the polymerization inhibitor represented by a following formula (IH-2) is mentioned, for example.

R ₆ in the formula (IH-2) represents a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Among them, a hydrogen atom or a hydroxyl group is preferable, and a hydroxyl group is more preferable.
Moreover, R < ₇ > -R < ₁₀ > in Formula (IH-2) respectively independently represents a hydrogen atom or an alkyl group. The alkyl group R ₇ to R ₁₀ represent preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.

<Alkali-soluble resin>
The curable composition preferably contains an alkali-soluble resin. In the present specification, an alkali-soluble resin means a resin containing a group (alkali-soluble group) that promotes alkali solubility.
The content of the alkali-soluble resin in the curable composition is not particularly limited, but in general, 0.1 to 40% by mass is preferable to the total solid content of the curable composition, and the curable composition is more excellent. From the point of having the effect of the present invention, 1 to 20% by mass is more preferable.
The alkali-soluble resin may be used alone or in combination of two or more. 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, and examples thereof include polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic resin. / (Meth) acrylamide copolymer resin, an epoxy resin, and a polyimide resin etc. are mentioned.

Specific examples of the alkali-soluble resin include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
The unsaturated carboxylic acid is 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 acids thereof Anhydrides; Multivalent carboxylic acid monoesters such as phthalic acid mono (2- (meth) acryloyloxyethyl); and the like.

  Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate and the like. Moreover, the compound as described in Unexamined-Japanese-Patent No.2010-97210, Paragraph 0027 and Unexamined-Japanese-Patent No.2015-68893, Paragraph 0036 can also be used, and said content is integrated in this specification.

  Moreover, it is an ethylenically unsaturated compound which can be copolymerized, Comprising: You may use combining the compound containing an ethylenically unsaturated group in a side chain. As the ethylenically unsaturated group, a (meth) acrylic acid group is preferable. An acrylic resin having an ethylenically unsaturated group in a side chain is obtained, for example, by the addition reaction of an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group with a carboxylic acid group of an acrylic resin containing a carboxylic acid group. Can be obtained.

  As an alkali soluble resin, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, 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-59-316, and JP-A-59-71048; European Patent No. 993966, European Patent No. 1204000, and JP-A No. 2001-318463 Acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group described in each publication such as U.S. Pat. No. 3, etc .; polyvinyl pyrrolidone; polyethylene oxide; alcohol-soluble nylon, and 2,2-bis- (4-hydroxyphenyl) -propane Polyether which is a reaction product with epichlorohydrin, etc .; It can be used, and the like; polyimide resin described in JP 08/123097.

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

A polyimide precursor can also be used as an alkali soluble resin. A polyimide precursor is generally 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., and means a compound different from the above acid anhydride.
As a polyimide precursor, resin containing the repeating unit represented by Formula (1) is mentioned, for example. The structure of the polyimide precursor includes, for example, an amic acid structure represented by the following formula (2) and a following formula (3) in which the amic acid structure is partially imide ring-closed and / or all imide ring-closed What contains the imide structure shown by (4) is mentioned.

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

  As specific examples of the polyimide precursor, for example, 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 The compounds described in paragraphs 0061 to 0092 of 2016-68401, and the like can be mentioned, and the above contents are incorporated in the present specification.

The alkali-soluble resin contains at least one selected from the group consisting of a polyimide precursor and a polyimide resin in that the pattern shape of the cured film in a pattern obtained by using the curable composition is more excellent. Is preferred.
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 a resin described in paragraph 0050 of JP-A-2014-137523, a resin described in paragraph 0058 of JP-A-2015-187676, and a resin described in JP-A-2014-106326. The resin etc. which were described in the 0012-0013 paragraph are mentioned, The above-mentioned contents are included in this specification.

<Dispersing agent>
The curable composition preferably contains a dispersant. In the present specification, the dispersant and the alkali-soluble resin described later mean different components.
Although it does not restrict | limit especially as content of the dispersing agent in a curable composition, Generally 5-30 mass% is preferable with respect to the total solid of a curable composition.
The dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably within the above range.

As a dispersing agent, a well-known dispersing agent can be selected suitably and can be used, for example. Among these, high molecular compounds are preferable.
As the dispersant, polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivative etc. can be mentioned.
The polymer compounds can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.

(Polymer compound)
The polymer compound adsorbs to the surface of the metal nitride-containing particles and acts to prevent reaggregation of the material to be dispersed. Therefore, terminal modified polymers, graft polymers, block polymers and the like, which contain anchor sites on the pigment surface, are preferred.

The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
A polymer compound containing a structural unit containing such a graft chain has an affinity to a solvent by the graft chain, and therefore, the dispersibility of the metal nitride-containing particles and the like, and the dispersion stability after aging ( Stability over time). Further, due to the presence of the graft chain, the polymer compound containing a structural unit containing a graft chain has an affinity to a polymerizable compound or other usable resin and the like. As a result, alkaline development is less likely to produce a residue.
The longer the graft chain, the higher the steric repulsion effect, and the dispersibility of the metal nitride-containing particles and the like is improved. On the other hand, when the graft chain is too long, the adsorptive power to the metal nitride-containing particles and the like decreases, and the dispersibility of the metal nitride-containing particles and the like tends to decrease. For this reason, the graft chain preferably has 40 to 10000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms is More preferably, it is 60-500.
Here, the graft chain means from the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure, and as such a polymer structure, for example, poly (meth) acrylate structure (for example, poly (meth) acrylic structure), polyester structure, polyurethane structure, polyurea structure, polyamide And polyether structures and the like.
The graft chain is selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent and thereby enhance the dispersibility of the black pigment etc. Graft chains containing at least one kind are preferable, and graft chains containing at least one of polyester structure and polyether structure are more preferable.

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

  As a commercially available macromonomer which corresponds to a structural unit containing a graft chain contained in a polymer compound and which is suitably used for the synthesis of the polymer compound, AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (Trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, produced by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, produced by Toa Gosei Co., Ltd.), AW -6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, produced by Toa Gosei Co., Ltd.), AY-707 (trade name, produced by Toa Gosei Co., Ltd.), AY-714 (trade name, produced by Toa Gosei Co., Ltd.) AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, Toa Gosei Co., Ltd.), AK-32 (trade name, Toa Gosei Co., Ltd.), Blenmer PP-100 (trade name, NOF Corporation) Brenmer PP-500 (trade name, manufactured by NOF Corporation), Brenmer PP-800 (trade) Name, manufactured by NOF Corporation, BLEMMER PP-1000 (trade name, manufactured by NOF Corporation), BLEMMER 55-PET-800 (trade name, manufactured by NOF Corporation), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation) Blemmer PSE-400 (trade name, manufactured by NOF Corporation), Blemmer PSE-1300 (trade name, manufactured by NOF Corporation), Blemmer 43PAPE-600B (trade name, manufactured by NOF Corporation), and the like. Among them, 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, ToA Synthetic company make) AN-6 (a brand name, the Toa Synthetic company make), and Blenmar PME-4000 (a brand name, the NOF Corporation make) etc. are preferable.

The dispersant preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and cyclic or linear polyesters. More preferably, the dispersant contains at least one structure selected from the group consisting of methyl polyacrylate, methyl polymethacrylate and linear polyesters. 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, a polycaprolactone structure means what contains the structure which ring-opened (epsilon) -caprolactone as a repeating unit. The polyvalerolactone structure refers to one containing a structure in which δ-valerolactone is ring-opened as a repeating unit.

  As specific examples of the above-mentioned dispersant, for example, compounds described in paragraphs 0035 to 0096 of JP 2015-34983 A, compounds described in paragraph 0025 to 0105 of JP 2012-255148 A, JP 2013-249417 A Compounds described in paragraphs 0127 to 0129 of JP-A No. 2010-106268, columns described in paragraphs 0075 to 0133 in corresponding US 2011/0124824, JP-A-2011-153283; A compound containing a component having a side chain structure in which an acidic group in paragraph (corresponding column US Pat. No. 007520 0133, columns of US2011 / 02729759) is bonded via a linking group, 0033 of JP-A-2016-109763. In the use of the compounds described in paragraph 0049 The contents of which are incorporated herein.

<Solvent>
The curable composition preferably contains a solvent. When the curable composition contains a solvent, the content of the solvent is not particularly limited, but it is preferable that the total solid content of the curable composition is adjusted to 5 to 40% by mass.
The solvents may be used alone or in combination of two or more. When using 2 or more types of solvents together, it is preferable to adjust so that the total solid of a curable composition may become in the said range.

The type of solvent is not particularly limited, and known solvents can be used. 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 Ethyl 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 and ethyl lactate.

<Silane coupling agent>
The curable composition may contain a silane coupling agent.
The silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. In addition, hydrolysable groups, such as an alkoxy group, are couple | bonded with the silicon atom.
The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group contains a carbon atom, the carbon number thereof 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.
When a cured film is formed on a substrate, the silane coupling agent improves the adhesion between the substrate and the cured film, so fluorine atoms and silicon atoms (except for silicon atoms to which a hydrolysable group is bonded) Is preferably free of fluorine atoms, silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and carbon It is more preferable not to include several or more branched chain alkyl groups.

The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, and more preferably 0.5 to 8% by mass, with respect to the total solid content in the curable composition. 1.0 to 6% by mass is more preferable.
The said curable composition may contain a silane coupling agent individually by 1 type, and may contain 2 or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum total should just be in the said range.

<UV absorber>
The curable composition may contain a UV absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
As a UV absorber, UV absorbers of salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type and triazine type can be used. As specific examples of these, the compounds of paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding to paragraphs 0251 to 0254 of corresponding US 2012/0068292) can be used, and the contents of these can be incorporated and incorporated herein. .
In addition, diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Kagaku Co., Ltd., trade name: UV-503) and the like are preferably used.
As an ultraviolet absorber, the compound illustrated by Unexamined-Japanese-Patent No.2012-32556, Paragraph 0134-0148 is mentioned.
0.001-15 mass% is preferable with respect to the total solid of a curable composition, as for content of a ultraviolet absorber, 0.01-10 mass% is more preferable, 0.1-5 mass% is further more preferable preferable.
<Surfactant>
The curable composition may contain a surfactant. The surfactant contributes to the improvement of the coatability of the curable composition.

When the said curable composition contains surfactant, as content of surfactant, 0.001-2.0 mass% is preferable with respect to the total solid of a curable composition.
The surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably within the above range.

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

  For example, when the curable composition contains a fluorine-based surfactant, liquid properties (in particular, fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorine-based surfactant, the 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 on the surface to be coated is improved. Therefore, even in the case where a thin film of about several μm is formed with a small amount of liquid, it is effective in that uniform thickness with small thickness unevenness can be easily formed.

  3-40 mass% is preferable, as for the fluorine content rate in a fluorine-type surfactant, 5-30 mass% is more preferable, and 7-25 mass% is still more preferable. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and / or the liquid saving property, and the solubility in the curable composition is also good. .

Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. Same F482, same F554, same F780 (above, DIC Corporation), Florard FC430, same FC431, same FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, same SC-101, same SC- 103, SC-104, SC-105, SC 1068, SC-381, SC-383, S393, KH-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 a fluorine-type surfactant, and the compound described, for example in Unexamined-Japanese-Patent No. 2011-89090 is mentioned as a specific example.

<Adhesive modifier>
The curable composition may contain a silane coupling agent as an adhesion improver. As a silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrietoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane And vinyltrimethoxysilane, and vinyltriethoxysilane.
The content of the adhesion improver is not particularly limited, but preferably 0.02 to 20% by mass with respect to the total solid content of the curable composition.

<Colorant>
The curable composition may contain a colorant. By colorant as used herein is intended a colorant different from metal nitride containing particles.
The content of the colorant in the curable composition is not particularly limited, but generally 30 to 60% by mass is preferable.

As the colorant, various known pigments (colored pigments) and dyes (colored dyes) can be used.
When the coloring agent is contained, the content can be determined according to the optical properties of the light shielding film obtained by curing. The other colorants may be used alone or in combination of two or more.

  As the colorant, for example, colorants described in paragraphs 0027 to 0200 of JP-A-2014-42375, paragraph 0031 of JP-A-2008-260927, and paragraphs 0015 to 0025 of JP-A-2015-68893 can be used. The above content is incorporated herein by reference.

As a coloring agent, a pigment having infrared absorptivity can also be used.
As the pigment having infrared absorptivity, tungsten compounds, metal borides and the like are preferable, and in particular, tungsten compounds are more preferable from the viewpoint of being excellent in the light shielding property at the wavelength in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of being excellent in the light absorption wavelength region of the oxime-based polymerization initiator related to the curing efficiency by exposure and the light transmittance of the visible light region.

These pigments may be used in combination of two or more, and may be used in combination with the dyes described later. In order to adjust the color tone and to enhance the light shielding property in a desired wavelength range, for example, pigments having black color or infrared ray shielding property such as red, green, yellow, orange, purple, and blue chromatic colors The form which mixes a pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye, with a pigment having black or infrared light shielding properties, and more preferable to mix a red pigment with a black or infrared light shielding pigment.
Furthermore, near infrared absorbers and infrared absorbers described later may be added.

-Organic pigment As an organic pigment, color index (CI) pigment yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,18, for example. 20, 24, 31, 32, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37, 1, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7, 168, 169, 170, 171, 172, 173, 174, 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, 13, 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, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 25: 2, 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, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 226, 246, 254, 255, 264, 270, 272, 279, etc .;
C. I. Pigment green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment violet 1,19,23,27,32,37,42 etc;
C. I. Pigment blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Can be mentioned. The pigments may be used alone or in combination of two or more.

(dye)
As the dye, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP-B-2592207 and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,505,950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-6. Dyes disclosed in JP-A-194828 can be used. When classified as chemical structures, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. Also, as the dye, a dye multimer may be used. As a pigment | dye multimer, the compound described in Unexamined-Japanese-Patent No. 2011-213925, Unexamined-Japanese-Patent No. 2013-041097 is mentioned. Moreover, you may use the polymeric dye which has a polymeric property in a molecule | numerator, As a commercial item, Wako Pure Chemical Industries, Ltd. RDW series are mentioned, for example.

(Infrared absorber)
The colorant may further contain an infrared absorber.
An infrared absorber means the compound which has absorption in the wavelength range of infrared region (preferably wavelength of 650-1300 nm). Preferably, the infrared absorbing agent is preferably a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm.
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, quatarylene Compounds, dithiol metal complex compounds, croconium compounds and the like can be mentioned.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squalium compound and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750 may be used, and the contents thereof are described in the present specification. Be incorporated. The cyanine compound can be referred to, for example, "Functional pigment, Shin Ookawara / Ken Matsuoka / Keijiro Kitao / Tsunehiro Hiraiso, Kodansha Scientific", the contents of which are incorporated herein.

  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 as colorants having the above-mentioned spectral characteristics, JP-A 2011-164583 The near infrared ray absorbing particles can be used which are crystallites of oxides containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the gazette and having a number average aggregate particle diameter of 5 to 200 nm.

The compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
Moreover, the compound which melt | dissolves 1 mass% or more in 25 degreeC water is preferable, and the compound which melt | dissolves 10 mass% or more in 25 degreeC water is more preferable as an infrared rays absorber. The solvent resistance is improved by using such a compound.
The pyrrolopyrrole compounds can be referred to in paragraphs [0049] to [0062] of JP-A-2010-222557, the contents of which are incorporated herein. Cyanine compounds and squarylium compounds are described in paragraphs 0022 to 0063 in WO 2014/088063, paragraphs 0053 to 0118 in WO 2014/030628, and paragraphs 0028 to 0074 in JP 2014-59550, International Paragraphs 0013 to 0091 of Publication 2012/169447, Paragraphs 0019 to 0033 of JP-A-2015-176046, Paragraphs 0053 to 0099 of JP-A-2014-63144, Paragraphs of JP-A 2014-52431 Nos. 0085 to 0150, paragraphs 0076 to 0124 of JP 2014-44301, paragraphs 0045 to 0078 of JP 2012-8532, paragraphs 0027 to 0067 of JP 2015-172102, JP 201 Paragraph Nos. 0029 to 0067 of JP-A-2005-194, Paragraph Nos. 0029 to 0085 of JP-A-2015-40895, Paragraphs 0022 to 0036 of JP-A-2014-126642, Paragraph 0011 of JP-A-2014-148567 ~ 0017, paragraphs 0010 to 0025 of JP 2015-157893, paragraphs 0013 to 0026 of JP 2014-095007, paragraphs 0013 to 0047 of JP 2014-80487, and JP 2013- Paragraph No. 0007-0028 grade | etc., Of 227403 gazette can be referred to, and this content shall be integrated in this specification.

The infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following formulas 1 to 3.
Formula 1

In Formula 1, A ¹ and A ² each independently represent an aryl group, a heteroaryl group or a group represented by the following Formula 1-A;
Formula 1-A

Formula 1-A, Z ^1A represents a nonmetallic atomic group forming a nitrogen-containing heterocyclic ring, R ^2A represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, and a wavy line Represents a connecting hand;
Formula 2

In formula 2, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group,
R ^{2 to} R ⁵ each independently represent a hydrogen atom or a substituent, and R ² and R ³ , and R ⁴ and R ⁵ may be respectively bonded to form a ring.
R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^A R ^B , or a metal atom, and R ^A and R ^B are each independently hydrogen Represents an atom or a substituent,
R ⁶ may be covalently bonded or coordinately bonded to R ^1a or R ^3, and R ⁷ may be covalently bonded or coordinately bonded to R ^1b or R ⁵ ; Formula 3

In Formula 3, Z ¹ and Z ² are each independently a nonmetallic atomic group that forms a 5- or 6-membered nitrogen-containing heterocyclic ring that may be fused.
R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L ¹ represents a methine chain consisting of an odd number of methine,
a and b are each independently 0 or 1;
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary to balance the charge, and the site represented by Cy in the formula is an anion moiety Where X ¹ represents a cation, c represents the number necessary to balance the charge, and c is a molecule in which the charge at the site represented by Cy in the formula is neutralized within the molecule It is 0.

(Pigment derivative)
The curable composition may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. As the pigment derivative, from the viewpoint of the dispersibility and the dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferable. Particularly preferred are pigment derivatives having a basic group. The combination of the above-described resin (dispersant) and the pigment derivative is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

Examples of organic pigments for forming the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments And isoindoline based pigments, isoindolinone based pigments, quinophthalone based pigments, srene based pigments, metal complex based pigments and the like.
Moreover, as an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are still more preferable, and a sulfonic acid group is especially preferable. As a basic group which a pigment derivative has, an amino group is preferable and especially a tertiary amino group is preferable.

The above curable composition has an optical density (OD: Optical Dnsity) of 1.5 μm or more in a wavelength range of 400 to 1100 nm, in that the resulting cured film has more excellent light shielding properties. Is preferred, and 3.0 or more is more preferred. The upper limit value is not particularly limited, but generally 5.0 or less. The cured film formed using the curable composition which has the said characteristic can be preferably used as a light shielding film (black matrix).
In the present specification, the optical density means an optical density measured by the method described in the examples. Further, in the present specification, the optical density per film thickness of 1.5 μm in the wavelength region of 400 to 1100 nm is 2.5 or more, the optical density per film thickness of 1.5 μm is in the entire wavelength range of 400 to 1100 nm. It means that it is 2.5 or more.

[Method of producing curable composition]
The curable composition can be prepared by mixing the various components described above by a known mixing method (for example, a stirrer, a homogenizer, a high pressure emulsifying device, a wet crusher, or a mixing method using a wet disperser).
In the preparation of the curable composition, each component may be blended at one time, or each component may be sequentially blended after being dissolved or dispersed in a solvent. In addition, the order of introduction and working conditions at the time of blending are not particularly limited.

The curable composition is preferably filtered through a filter for the purpose of removing foreign matter and / or reducing defects. The filter is not particularly limited as long as it is for filtration. For example, a filter based on a fluorine resin such as PTFE (polytetrafluoroethylene); a polyamide resin such as nylon; a polyolefin resin such as polyethylene or polypropylene (PP) (including high density and ultrahigh molecular weight); Among them, polypropylene (including high density polypropylene) or nylon is preferable as the material of the filter.
The pore diameter of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. By setting the amount in this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filter filtration clogging.
When using filters, different filters may be combined. At this time, the filtering with the first filter may be performed only once or twice or more. When combining different filters and filtering two or more times, it is preferable that the second and subsequent pore sizes be the same or larger than the pore size of the first filtering. Moreover, you may combine the 1st filter of the hole diameter which is different within the range mentioned above. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it is possible to select, for example, from various filters provided by Nippon Pall Co., Advantec Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like.
The second filter can be made of the same material as the first filter described above. The diameter of the second filter is preferably about 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and still more preferably 0.3 to 6.0 μm.
The curable composition preferably contains no metal, metal salt containing halogen, acid, and impurities such as 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 not containing it (below the detection limit of the measuring device) Is most preferred.
The above impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

[Cured film and manufacturing method thereof]
The curable composition can form a cured film.
Although the thickness in particular of a cured film is not restrict | limited, 0.2-25 micrometers is preferable.
The thickness is an average thickness, and it is a value obtained by measuring the thickness of any five or more 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 which apply | coats the curable composition mentioned above on a board | substrate, forms a coating film, hardens a coating film, and manufactures a cured film is mentioned. .
The method of curing treatment is not particularly limited, and photo curing treatment or heat curing treatment may be mentioned, and light curing treatment (in particular, curing treatment by irradiation with an actinic ray or radiation) is preferable from the viewpoint of easy pattern formation. .

The cured film according to the embodiment of the present invention is a cured film obtained by curing the curable composition layer formed using the above-mentioned curable composition.
The method for producing the cured film is not particularly limited, but it is preferable to have the following steps.
-Curable composition layer formation process-Exposure process-Development process Hereinafter, each process is demonstrated.

<Step of Forming Curable Composition Layer>
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 the substrate is not particularly limited. However, when used as a solid-state imaging device, for example, a silicon substrate can be mentioned, and when used as a color filter (including a color filter for solid-state imaging device), a glass substrate can be mentioned.
As a coating method of the curable composition on a substrate, various coating methods such as spin coating, slit coating, inkjet method, spray coating, spin coating, cast coating, roll coating, and screen printing can be applied .
The curable composition applied on the substrate is usually dried at 70 to 150 ° C. for 1 to 4 minutes to form a curable composition layer.

<Exposure process>
The exposure step is a step of exposing the curable composition layer formed in the curable composition layer forming step by irradiation with an actinic ray or radiation through a photomask provided with a pattern-like opening.
The exposure is preferably performed by irradiation of radiation. Examples of radiation that can be used for exposure include ultraviolet rays such as g-rays, h-rays and i-rays, and examples of light sources include high-pressure mercury lamps. The irradiation intensity is preferably ^{5~1500mJ / cm 2, 10~1000mJ / cm} 2 is more preferable.

<Development process>
Subsequent to the exposure step, development processing (development step) is performed to elute a light non-irradiated portion in the exposure step into a developer. This leaves only the light-cured portion.
An alkaline developer may be used as the developer. In that case, it is preferable to use an organic alkali developer. As development temperature, 20-30 degreeC is preferable normally, and 20 to 90 second of development time is preferable.
As an alkaline aqueous solution (alkali developer), for example, as an inorganic developer, the concentration of an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, etc. An aqueous alkali solution dissolved to have 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass, may be mentioned.
Moreover, as an organic alkali developing solution, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline And alkaline compounds such as pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene in a concentration of 0.001 to 10% by mass, preferably 0.005 to 0.5% It includes an aqueous alkali solution dissolved to a percentage.
An appropriate amount of, for example, a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the alkaline aqueous solution. In addition, when using the developing solution which consists of such aqueous alkali solution, generally the cured film is wash | cleaned (rinsed) with a pure water after image 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.
As another process, the surface treatment process of a base material, a preheating process (prebaking process), a postheating process (postbaking process) etc. are mentioned, for example.
As for the heating temperature in the said pre-heating process and a post-heating process, 80-300 degreeC is preferable.
The upper limit is more preferably 220 ° C. or less. The lower limit is preferably 90 ° C. or more.
The heating time in the preheating step and the postheating step is preferably 30 to 300 seconds.

[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 above-described cured film. The form in which the solid-state imaging device contains a cured film is not particularly limited, and, for example, a plurality of photodiodes, polysilicon, etc. constituting the light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate The cured film of the present invention is provided on the light receiving element forming surface side of the support (for example, a portion other than the light receiving portion and / or a pixel for color adjustment) or the opposite side of the forming surface. Are listed.
The solid-state imaging device contains the above-described solid-state imaging device.

A configuration example of a solid-state imaging device and a solid-state imaging device will be described with reference to FIGS. In addition, in FIG. 1-FIG. 2, in order to clarify each part, the mutual thickness and / or the ratio of the width | variety are disregarded, and it exaggerates and displays in part.
As shown in FIG. 1, the solid-state imaging device 100 includes a rectangular solid-state imaging device 101, and a transparent cover glass 103 held above the solid-state imaging device 101 and sealing the solid-state imaging device 101. There is. Furthermore, on the cover glass 103, a lens layer 111 is provided so as to overlap via a spacer 104. The lens layer 111 is composed of a support 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, light diffusion reduces the light condensing effect of the lens material 112, and the light reaching the imaging unit 102 is reduced. In addition, the generation of noise due to stray light also occurs. Therefore, a light shielding film 114 is provided to shield the peripheral region of the lens layer 111 from light. 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 the light receiving surface and outputs the image 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 is composed of a rectangular chip substrate 106 and a circuit substrate 107 of 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 known materials can be used.

  An imaging unit 102 is provided at the center of the surface of the chip substrate 106. In addition, when stray light enters the peripheral region of the imaging unit 102, a dark current (noise) is generated from the circuit in the peripheral region, and the peripheral region is shielded by the light shielding film 115 provided. 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 at 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) (which may be a bonding wire) provided on the surface of the chip substrate 106.

  On the back surface of the circuit board 107, external connection terminals 109 are provided substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to the electrode pad 108 through the penetration electrode 110 which penetrates the lamination substrate 105 perpendicularly. Further, each external connection terminal 109 is connected to a control circuit that controls the driving of the solid-state imaging device 101, an image processing circuit that performs image processing on an imaging signal output from the solid-state imaging device 101, etc. It is done.

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

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

  A vertical transfer path 208 formed of an n-type layer is formed on one side of the light receiving element 201 via the readout gate portion 207 on the surface layer of the p well layer 206. Further, 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 formed of a p-type layer. The read gate unit 207 is a channel region for reading out the signal charge stored in the light receiving element 201 to the vertical transfer path 208.

  On the surface of the substrate 204, a gate insulating film 210 formed of an ONO (Oxide-Nitride-Oxide) film is formed. On the gate insulating film 210, a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed so as to cover the vertical transfer path 208, the read gate portion 207, and the element isolation region 209 almost immediately. 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 a signal charge. The signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path and an output unit (floating diffusion amplifier) not shown, 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 immediately above the light receiving element 201, and shields the other regions. 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, a transparent intermediate layer formed of an insulating film 213 made of borophosphosilicate glass (BPSG), an insulating film (passivation film) 214 made of P-SiN, and a planarizing film 215 made of a transparent resin or the like is provided. ing. The color filter 202 is formed on the intermediate layer.

[Black matrix]
The black matrix contains the cured film according to the embodiment of the present invention. The black matrix may be contained in color filters, solid-state imaging devices, and liquid crystal displays.
As the black matrix, those already described above; black edges provided on the periphery of a display device such as a liquid crystal display device; grids between red, blue and green pixels and / or stripes Black portions; dot-like and / or linear black patterns for light shielding of TFT (thin film transistor); and the like. For the definition of the black matrix, see, for example, Taiho Ogino, "Glossary of Liquid Crystal Display Manufacturing Device Dictionary", Second Edition, Nikkan Kogyo Shimbun, 1996, p. 64.
The black matrix has a high light-shielding property (optical density OD) in order to improve the display contrast, and in the case of an active matrix drive liquid crystal display device using thin film transistors (TFTs), to prevent image quality deterioration due to light current leak It is preferable to have three or more.

  The method for producing the black matrix is not particularly limited, but it can be produced by the same method as the method for producing a cured film described above. Specifically, a curable composition can be applied to a substrate to form a curable composition layer, exposed, and developed to produce a patterned cured film (black matrix). In addition, as a film thickness of the cured film used as a black matrix, 0.1-4.0 micrometers is preferable.

  The material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more to visible light (wavelength: 400 to 800 nm). As such a material, specifically, for example, glass such as soda lime glass, non-alkali glass, quartz glass, and borosilicate glass; plastics such as polyester resin and polyolefin resin; From the viewpoint of chemical resistance and heat resistance, alkali-free glass, quartz glass and the like are preferable.

[Color filter]
The color filter according to the embodiment of the present invention contains a cured film.
Although it does not restrict | limit especially as a form in which a color filter contains a cured film, A color filter provided with a board | substrate and said black matrix is mentioned. That is, a color filter including red, green and blue colored pixels formed in the opening of the black matrix formed in a substrate shape can be exemplified.

The color filter containing the black matrix (cured film) can be produced, for example, by the following method.
First, a coating (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in the opening of a patterned black matrix formed in a substrate. In addition, it does not restrict | limit especially as a resin composition for each color, Although a well-known resin composition can be used, in the curable composition concerning embodiment of this invention, metal nitride containing particle | grains respond | correspond to each pixel It is preferable to use one that has been replaced by the above-mentioned colorant.
Next, the resin composition layer is exposed to light through a photomask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed area by development, a baking process can be performed to form colored pixels in the opening of the black matrix. A color filter having red, green and blue pixels can be manufactured by performing a series of operations using, for example, resin compositions for respective colors containing red, green and blue pigments.

[Liquid crystal display device]
The liquid crystal display device according to the embodiment of the present invention contains a cured film. The form in which the liquid crystal display device contains the cured film is not particularly limited, but the form containing the color filter containing the black matrix (cured film) described above can be mentioned.

  As a liquid crystal display device concerning this embodiment, a form provided with a pair of substrates arranged facing, and a liquid crystal compound enclosed between those substrates is mentioned, for example. The substrate is as described above for the black matrix.

  As a specific form of the liquid crystal display device, for example, from the user side, polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) A laminate including an element / substrate / polarizer / backlight unit in this order may be mentioned.

  The liquid crystal display device according to the embodiment of the present invention is not limited to the above, and, for example, “Electronic display device (authored by Akio Sasaki, published by Industry Research Association 1990)”, “Display device (Susumu Ibuki) Authors, "Industrial Books, Inc., published in Heisei 1983") and the like. In addition, for example, a liquid crystal display device described in “Next-Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Inc., Industrial Research Association, Inc. 1994)” may be mentioned.

[Infrared sensor]
An infrared sensor according to an embodiment of the present invention contains the above-mentioned cured film.
The infrared sensor according to the above embodiment will be described with reference to FIG. In the infrared sensor 300 shown in FIG. 3, reference numeral 310 denotes a solid-state imaging device.
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 range (for example, light with a wavelength of 400 to 700 nm) and light in the infrared range (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm) The curing according to the embodiment of the present invention, which is preferably a film that shields light having a wavelength of 900 to 1000 nm, and contains an infrared absorber (as described in the form of the infrared absorber) as a colorant. Membranes 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, and for example, red (R), green (G), and blue (B) pixels are formed. The color filter or the like is used, and the form is as described above. A resin film 314 (for example, a transparent resin film or the like) capable of transmitting light of the wavelength transmitted through the infrared transmission filter 313 is disposed between the infrared transmission filter 313 and the solid-state imaging device 310.
The infrared transmission filter 313 is a filter having visible light shielding properties and transmitting infrared light of a specific wavelength, and is a colorant (for example, a perylene compound and / or bisbenzo) which absorbs light in the visible light range. A cured film according to an embodiment of the present invention can be used which contains a furanone compound and the like) and an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound). 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 1,300 nm.
A microlens 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 to cover the microlenses 315.
Although the resin film 314 is disposed in the embodiment shown in FIG. 3, the infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared ray transmission filter 313 may be formed on the solid-state imaging device 310.
Further, 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 thicknesses of both may be different.
Further, in the embodiment shown in FIG. 3, the color filter 312 is provided closer to the incident light hv than the infrared absorption filter 311, but the infrared absorption filter 311 and the color filter 312 are interchanged in order to absorb infrared light. The 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, but the filters do not necessarily have to be adjacent to each other, and another layer is provided between them. It is also good.
According to this infrared sensor, it is possible to simultaneously capture image information, so that it is possible to perform motion sensing in which an object whose motion is to be detected is recognized. Furthermore, since distance information can be acquired, it is also possible to capture an image including 3D information.

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. In addition, about each structure of a solid-state imaging device, Paragraph 0032-0036 of Unexamined-Japanese-Patent No. 2011-233983 can be referred to, and this content is integrated in this-application specification.

  The cured film is a portable computer such as a personal computer, a tablet, a cellular phone, a smart phone, and a digital camera; a printer complex machine, an OA (Office Automation) equipment such as a scanner; a surveillance camera, a barcode reader, cash Industrial equipment such as an automated teller machine (ATM), a high speed camera, and a device having an identity authentication function using face image authentication; automotive camera devices; endoscopes, capsule endoscopes, And medical camera devices such as catheters; biometric sensors, biosensors, cameras for military reconnaissance cameras, cameras for stereoscopic maps, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for astronomical and deep space targets in space Of optical filters and modules used in space equipment, etc. Light member and the light-shielding film, further is suitable for anti-reflection member and the antireflection film.

The said cured film can be used also for uses, such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The said cured film is suitable for the member which provides a light shielding function or an antireflection function other than the optical filter and optical film which are used for micro LED and micro OLED.
Examples of micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.

The said cured film is suitable as an optical and optical film used for a quantum dot display. Moreover, it is suitable as a member which provides a light shielding function and a reflection preventing function.
Examples of quantum dot displays are disclosed in U.S. Patent Application Publication No. 2013/0335657, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960 Those mentioned are mentioned.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples. In the following,% and parts are by mass unless otherwise specified.

[Preparation of metal nitride-containing particles]
The metal nitride-containing particles were respectively produced by the following method.

[Preparation of Titanium Nitride-Containing Particles TiN-1]
Titanium nitride-containing particles TiN-1 were produced using each component described in Table 1.
First, Ti particles described in Table 1 were plasma-treated in Ar gas to obtain Ti nanoparticles. After leaving the above Ti nanoparticles in an Ar gas atmosphere for 24 hours under the conditions of an O ₂ concentration of 50 ppm or less and 30 ° C., a state where O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration is 100 ppm. The Ti nanoparticles were allowed to stand at 30 ° C. for 24 hours (this is referred to as “pre-treatment of Ti particles”).
Thereafter, the Ti nanoparticles obtained were classified using a Hosokawa Micron TTSP separator under conditions of a yield of 10% to obtain a powder of Ti nanoparticles. The primary particle diameter of the obtained powder was determined by determining the particle diameter of 100 particles by TEM (Transmission Electron Microscope) observation, and further, by the arithmetic average of these, it was 120 nm.
The titanium nitride-containing particles TiN-1 were produced using an apparatus according to the apparatus for producing black composite particles described in FIG. 1 of WO 2010/147098.
Specifically, in the black composite particle production apparatus, high frequency voltages of about 4 MHz and about 80 kVA are applied to the high frequency oscillation coil of the plasma torch, and argon gas 50 L / min and nitrogen as plasma gas from the plasma gas supply source. A mixed gas of 50 L / min was supplied to generate an argon-nitrogen thermal plasma flame in the plasma torch. Moreover, 10 L / min of carrier gas (Ar gas) was supplied from the spray gas supply source of the material supply apparatus.
Then, the Ti nanoparticles obtained as described above and the additive particles described in Table 1 are mixed so as to have the composition described in Table 1, and heat in the plasma torch is obtained together with Ar gas as a carrier gas. During the plasma flame, the supplied particles were evaporated in a thermal plasma flame and dispersed highly in the gas phase.
In addition, nitrogen gas was used as the gas supplied into the chamber by the gas supply device. The flow rate of nitrogen gas in the chamber at this time was 5 m / sec, and the supply amount of nitrogen gas was 1000 L / min. The pressure in the cyclone was 50 kPa, and the feed rate of each material from the chamber to the cyclone was 10 m / s (average value).
Thus, titanium nitride-containing particles TiN-1 were obtained.

The contents of titanium (Ti) atoms, Fe (iron) atoms, and silicon (Si) atoms were measured for the obtained titanium nitride-containing particles TiN-1 by ICP (Inductively Coupled Plasma) emission spectroscopy. . The results are shown in Table 1. For ICP emission spectroscopy, an ICP emission spectrometer "SPS 3000" (trade name) manufactured by Seiko Instruments Inc. was used.
Moreover, about content of nitrogen atom, it measured using the inert gas melting-thermal conductivity method, using the oxygen and nitrogen analyzer "EMGA-620W / C" (brand name) by Horiba, Ltd. make. The results are shown in Table 1.
The contents of Ti atoms, Fe atoms, silicon atoms, and nitrogen atoms in titanium nitride-containing particles TiN-2 to TiN-4 to be described later are the same as in the case of titanium nitride-containing particles TiN-1. It was measured. The results are shown in Table 1.

The powder sample was packed in a standard sample holder made of aluminum, and the X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name "RU-200R" manufactured by Rigaku Denki Co., Ltd.). As measurement conditions, the X-ray source is CuKα radiation, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min.
Then, the diffraction angle of the peak derived from the TiN (200) plane observed near the diffraction angle 2θ (42.6 °) was measured. Further, from the half width of the peak derived from the (200) plane, the crystallite size constituting the particles was determined using Scheller's equation.
In the following titanium nitride-containing particles TiN-2 to TiN-4, the diffraction angle 2θ and the crystallite size were measured in the same manner as for the titanium nitride-containing particles TiN-1. The results are shown in Table 1. Incidentally, no X-ray diffraction peak attributable to TiO ₂ was observed at all for any of the titanium nitride-containing particles.

[Preparation of Titanium Nitride-Containing Particles TiN-2 to TiN-4]
Titanium nitride-containing particles TiN-2 to TiN-4 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials and the compositions were as shown in Table 1.

In the table, "wt%" means mass%. Also, in the Table, "TiN particles" intends titanium nitride-containing particles.

[Preparation of metal nitride-containing particle dispersions 1 to 11]
The metal nitride-containing particles, the dispersant, and the organic solvent were mixed for 15 minutes with a stirrer (EUROSTAR manufactured by IKA) to obtain the compositions shown in Table 2 to obtain a mixed solution. Next, the obtained mixed solution was subjected to dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises, Ltd. to obtain a metal nitride-containing particle dispersion.

<Distribution condition>
· Bead diameter: φ 0.05 mm, (Nikkato zirconia beads, YTZ)
・ Bead packing rate: 65% by volume
・ Mill circumferential speed: 10 m / sec
・ Separator circumferential speed: 13 m / s
・ The amount of mixed liquid to be dispersed: 15 kg
Circulating flow rate (pump supply rate): 90 kg / hour
Processing solution temperature: 19 to 21 ° C.
・ Cooling water: Water ・ Processing time: About 22 hours

  In addition, each symbol in Table 2 shows the following components.

(Metal nitride-containing particles)
· ZrN: Zirconium nitride-containing particles, manufactured by Nippon New Metal Co., Ltd., trade name "ZrN-01"
・ VN: Vanadium nitride-containing particles, manufactured by Nippon Shinkin Kabushiki Kaisha
・ NbN: Niobium nitride-containing particles, manufactured by Nippon Shin Metal Co., Ltd., trade name "NbN-O"

(Dispersant)
Dispersant 1: manufactured by BYK, trade name "BYK-111"

Dispersant 2: Dispersant represented by the following formula

In addition, "Mw" intends a weight average molecular weight.

Dispersant 3: Dispersant represented by the following formula

Dispersant 4: Dispersant represented by the following formula (weight-average molecular weight: 240000)

(solvent)
PGMEA: propylene glycol 1-monomethyl ether 2-acetate

[Examples 1 to 26 and Comparative Examples 1 to 5: Preparation of Curable Composition]
Next, the other components were mixed with the metal nitride-containing particle dispersion liquid so as to have the composition described in Table 3, to obtain each curable composition. In addition, as for content of each component in Table 3, all intend mass%.
In addition, the final solid content of each curable composition was adjusted with the organic solvent so that it might be 30 mass%. In addition, PGMEA (propyleneglycol mono methyl ether acetate) was used as a solvent for solid content adjustment.

  In addition, each number in Table 3 represents the following components.

(Acid anhydride)
· Acid anhydride 1: Maleic anhydride · Acid anhydride 2: Phthalic anhydride

Acid anhydride 3: 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride (4,4′-biphthalic acid anhydride) (containing two acid anhydride groups in one molecule). )

Acid anhydride 4: 4, 4'- oxydiphthalic anhydride (containing two acid anhydride groups in one molecule)

Acid anhydride 5: 3,4′-carbonyldiphthalic acid anhydride (containing two acid anhydride groups in one molecule)

(Alkali-soluble resin)
Alkali-soluble resin 1: benzyl methacrylate / acrylic acid copolymer [composition ratio: benzyl methacrylate / acrylic acid copolymer = 80/20 (% by mass), Mw: 25000]

· Alkali-soluble resin 2: Polyimide precursor synthesized by the following method (polyamic acid)

  The polyimide precursor (polyamic acid) was synthesized by the following method. First, 4,4'-diaminobenzanilide (0.475 molar equivalent), 3,3'-diaminodiphenylsulfone (0.475 molar equivalent), and bis (3-aminopropyl) tetramethyldisiloxane (0. 0). 05 molar equivalents) together with 1700 g of N-methyl-2-pyrrolidone were placed in a reaction vessel to obtain a mixture. To the above mixture, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride (0.98 molar equivalent) was added, and reacted at 70 ° C for 3 hours to obtain a reaction liquid. Phthalic anhydride (0.04 molar equivalent) is added to the above reaction solution, and the mixture is further reacted at 70 ° C. for 1 hour, polyamic acid A-1 (polymer concentration 17% by weight, imide ring ratio 13%, molecular weight of repeating unit 532) A solution was obtained. Here, the molecular weight of the repeating unit of polyamic acid A-1 is calculated in the following manner.

Molecular weight of repeating unit = 2 × (227 × 0.475 + 248 × 0.475 + 249 × 0.05 + 294 × 0.98) / (0.475 + 0.475 + 0.05 + 0.98) = 532
The molecular weight M1 of the repeating unit of the polyimide resin obtained by imidizing the polyamic acid A-1 is 496, and the number n1 of moles of imino and / or iminocarbonyl group contained in the repeating unit of the polyimide resin is 0. 475 moles.

(Polymerizable compound)
Polymerizable compound represented by the following formula

(Oxime-based polymerization initiator)
· Oxime-based polymerization initiator 1: IRGACURE OXE-02 (manufactured by BASF)
-Oxime-based polymerization initiator 2: Adeka Arkles NCI-831 (made by Adeka, containing a nitro group)

(Polymerization inhibitor)
Polymerization inhibitor: 4-methoxyphenol

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

-Surfactant 2: "LC 951", manufactured by Enomoto Chemical Co., Ltd.

[Evaluation]
Each of the above curable compositions was evaluated by the following method.

[Measurement of optical density (OD: Optical density)]
The curable composition was applied onto a glass substrate such that the film thickness after drying was 1.5 μm, to obtain a curable composition layer. The resulting curable composition layer was placed on a hot plate with the glass substrate down, heated at 100 ° C. for 2 minutes, and dried.
The curable composition layer after drying was exposed to a dose of 500 mJ / cm ² to obtain a cured film.
About the said cured film, the optical density (OD) in wavelength 380-1100 nm was measured using V-7200F (made by JASCO Corporation). The results are shown in Table 3 (Table 1 (Part 1) to Table 3 (Part 3)).
In addition, obtained OD is the minimum OD in wavelength 400-1100 nm. That is, the said cured film (film thickness: 1.5 micrometers) has OD more than OD shown to Table 3 (the 1st-Table 3 (the 3)) in the whole wavelength 400-1100 nm.

[Evaluation of storage stability]
<1. Exposure sensitivity of curable composition (initial)>
Each curable composition immediately after preparation was applied onto a glass substrate using spin coating, and dried to form a curable composition layer having a film thickness of 1.0 μm. The conditions for spin coating were first 5 seconds at 300 rpm (rotation per minute) and then 20 seconds at 800 rpm. The drying conditions were 100 ° C. and 80 seconds.
With respect to the coating film obtained as described above, light of wavelength 365 nm is passed through a pattern mask having a line and space of 1 μm to 10 to 1600 mJ /, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.) It was irradiated at an exposure dose of cm ^2. Next, using a 60% CD-2000 (manufactured by Fujifilm Electronics Materials Co., Ltd.) developer, the curable composition layer after exposure is developed under conditions of 25 ° C. for 60 seconds, and a patterned cured film is formed. I got Thereafter, the patterned cured film was rinsed with running water for 20 seconds and then air-dried.
In the exposure step, the minimum exposure amount at which the pattern line width after development in the region irradiated with light becomes 1.0 μm or more is defined as the exposure sensitivity, and this exposure sensitivity is defined as the initial exposure sensitivity.

<2. Exposure sensitivity of the curable composition (after aging: after 30 days at 45 ° C.)>
The curable composition immediately after preparation was sealed in a closed vessel, held in a thermostat (EYELA / LTI-700) whose internal temperature was set at 45 ° C., and taken out after 30 days. Using the curable composition taken out, a test similar to that performed using the curable composition immediately after preparation was conducted to determine the exposure sensitivity. This was taken as the exposure sensitivity after aging.

<Evaluation>
From the initial exposure sensitivity and the exposure sensitivity after aging, the fluctuation rate (%) of the exposure sensitivity obtained by the following equation was calculated. The smaller the value of the fluctuation rate (%), the better the storage stability.
(Formula) fluctuation rate = (exposure sensitivity after time-initial exposure sensitivity) / initial exposure sensitivity × 100

[Evaluation of unexposed area residue]
Above <1. In the test of exposure sensitivity (initial) of the curable composition, the cured film obtained with the minimum exposure amount at which the pattern line width after development becomes 1.0 μm or more in an oven at 220 ° C. for 1 hour Heated. After heating the cured film, the number of residues present in a region (unexposed area) not irradiated with light in the exposure step on a glass substrate is observed with a scanning electron microscope (magnification: 20000 times). The unexposed area residue was evaluated. Evaluation was performed according to the following criteria, and the results are shown in Table 3 (Table 1 (Part 1) to Table 3 (Part 3)). In addition, evaluation "3 or more" is preferable practically, and 4 and 5 are evaluated as having the outstanding performance.

-Evaluation criteria-
5: A pattern was formed, and no residue was observed in the unexposed area.
4: A pattern was formed, and 1 to 3 residues were observed in an unexposed area of 1.0 μm.
3: A pattern was formed, and 4 to 10 residues were observed in an unexposed area of 1.0 μm.
2: A pattern was formed, and 11 or more residues were observed in an unexposed area of 1.0 μm.
1: No pattern formation due to development failure.

[Evaluation of pattern edge shape]
The pattern edge shape of the pattern-like cured film formed using each curable composition was evaluated by the following method.

<Step of Forming Curable Composition Layer>
A curable composition layer was formed on a silicon wafer such that the film thickness after drying was 1.5 μm. The formation of the curable composition layer was performed using spin coating. The number of rotations of the spin coat was adjusted to obtain the above film thickness. The curable composition layer after application was placed on a hot plate with the silicon wafer down and dried. The surface temperature of the hot plate was 100 ° C., and the drying time was 120 seconds.

<Exposure process>
The resulting curable composition layer was exposed under the following conditions.
The exposure was performed using an i-line stepper (trade name "FPA-3000iS +", manufactured by Canon Inc.). The curable composition layer was irradiated (exposed) at a dose of 400 mJ / cm ² (irradiation time: 0.5 seconds) through a mask having a linear size of 20 μm (width 20 μm, length 4 mm).

<Heating process>
Next, the curable composition layer after exposure was placed on a hot plate and dried with the silicon wafer down. The surface temperature of the hot plate was 100 ° C., and the drying time was 120 seconds. The film thickness of the curable composition layer after drying was 1.5 μm.

<Development process>
The curable composition layer after drying was developed under the following conditions to obtain a patterned cured film.
The curable composition layer after drying was subjected to 5 cycles of paddle development for 60 seconds at 23 ° C. using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), and the cured film was patterned. Obtained. Thereafter, the patterned cured film was rinsed using a spin shower and further washed with pure water.

<Post-baking process>
The patterned cured film obtained above was heated at 220 ° C. for 300 seconds using a clean oven CLH-21 CDH (manufactured by Koyo Thermo Co., Ltd.).
Furthermore, the patterned cured film after heating was placed on a hot plate with a surface temperature of 220 ° C. and heated for 300 seconds.

<Evaluation>
The cured film in the pattern form was photographed by a scanning electron microscope, and the angle formed by the edge portion (short side) of the 20 μm pattern cross section and the glass substrate (hereinafter simply referred to as “edge angle”) was measured. The shape of the pattern edge was evaluated according to the following criteria, and the results are shown in Table 3 (Table 1 (Part 1) to Table 3 (Part 3)). In addition, evaluation "3 or more" is preferable practically.

-Evaluation criteria-
5: The edge angle was more than 85 ° and less than 90 °.
4: The edge angle was more than 80 ° and less than 85 °.
3: The edge angle was more than 75 ° and less than 80 °.
2: The edge angle was more than 70 ° and less than 75 °.
1: The edge angle was less than 70 °.

From the results shown in Table 3, the curable compositions of Examples 1 to 26 containing the metal nitride-containing particles, the oxime-based polymerization initiator, the polymerizable compound, and the acid anhydride were as described in the present invention. It had an effect. On the other hand, the curable composition of the comparative example did not have the effect of the present invention.
Moreover, the curable composition of Example 2 whose content mass ratio of content of an acid anhydride is 0.005-0.5 with respect to content of the oxime type polymerization initiator in a curable composition is implemented. It turned out that the cured film which has a pattern shape more excellent compared with the curable composition of Example 4, Example 24, and Example 25 is obtained.
In addition, the curable composition of Example 2 in which the acid anhydride contains two or more acid anhydride groups in one molecule is more excellent as compared with the curable compositions of Examples 8 and 9. A cured film having the following pattern shape was obtained, and the generation of residues in the unexposed area was further suppressed.
In addition, the curable composition of Example 5 containing a polymerization inhibitor has superior storage stability as compared with the curable composition of Example 2, and generation of a residue in the unexposed area. Was more restrained.
In addition, the curable composition of Example 2 in which the metal nitride-containing particles contain titanium nitride produces a cured film having a more excellent pattern shape as compared with the curable compositions of Examples 15 to 17. And the generation of residues in the unexposed area was further suppressed.
In addition, the curing of Example 2 in which the metal nitride-containing particles contain titanium nitride and the diffraction angle 2θ of the peak derived from the (200) plane of the particles measured under predetermined conditions is 42.5 to 42.8. The cured film obtained as compared with the curable composition of Example 19 and Example 20 had a more excellent light shielding property (high OD value).
In addition, the curable composition of Example 13 in which the content of the metal nitride-containing particles in the curable composition is 40% by mass or more is a cured film obtained in comparison with the curable composition of Example 14. Had better light shielding properties.
In addition, the curable composition of Example 12 in which the oxime-based polymerization initiator contained a nitro group, a cured film having a more excellent pattern shape was obtained as compared to the curable composition of Example 2. .

[Preparation of Metal Nitride-Containing Particle Dispersions 12 and 13]
Instead of titanium nitride-containing particles TiN-1, a mixture of titanium nitride-containing particles TiN-1 and carbon black (containing mass ratio (35/5 mass contained titanium nitride-containing particles TiN-1 / carbon black)) is used The metal nitride-containing particle dispersion liquid 12 was manufactured in the same manner as the method for manufacturing the metal nitride-containing particle dispersion liquid 1 except for the above.
Also, instead of titanium nitride-containing particles TiN-1, a mixture of titanium nitride-containing particles TiN-1 and an organic pigment (Irgaphor Black S0100CF, manufactured by BASF) (content mass ratio (titanium nitride-containing particles TiN-1) The metal nitride-containing particle dispersion 13 was produced in the same manner as the method for producing the metal nitride-containing particle dispersion 1, except that (organic pigment) was 35/5).

[Examples 2-12, 2-13: Preparation of Curable Composition]
A curable composition 2-12 was prepared in the same manner as in Example 2, except that the metal nitride-containing particle dispersions 12 and 13 were used instead of the metal nitride-containing particle dispersion 1. And when 2-13 was produced and the same evaluation as described above was carried out, the same result as Example 2 was obtained.

A curable composition was prepared and evaluated in the same manner as in Example 5 except that PIGA represented by the following formula was used instead of IRGACURE OXE-02 (manufactured by BASF Corporation). The same results as in Example 5 were obtained except that the pattern edge shape was changed to 5.
PI-03 (corresponding to a compound represented by the following formula, and an oxime polymerization initiator)

A curable composition was prepared and evaluated in the same manner as in Example 5 except that PI-04 represented by the following formula was used instead of IRGACURE OXE-02 (manufactured by BASF Corporation). On the other hand, similar results were obtained except that the storage stability was 1 and the pattern edge shape was 5.
PI-04 (compound represented by OE 74 of WO2015 / 036910, corresponding to an oxime-based polymerization initiator)

  A curable composition was prepared and evaluated in the same manner as in Example 5 except that the surfactant was not used, and the same results as in Example 5 were obtained.

100: solid-state imaging device 101: solid-state imaging device 102: imaging unit 103: cover glass 104: spacer 105: laminated substrate 106: chip substrate 107: circuit substrate 108 ... electrode pad 109 ... external connection terminal 110 ... penetrating electrode 111 ... lens layer 112 ... lens material 113 ... support 114, 115 ... light shielding film 201 ... light receiving element 202: color filter 201: light receiving element 202: color filter 203: microlens 204: substrate 205b: blue pixel 205r: red pixel 205g: green pixel 205bm,. Black matrix 206 p well layer 207 read gate portion 208 vertical transfer path 209 element isolation region 210 Over gate insulating film 211 ... vertical transfer electrodes 212 ... light shielding film 213 ... insulating film 215 ... flattening film 53 ... lens layer 54, 55 ... light shielding pattern

Claims (18)

  A curable composition comprising metal nitride-containing particles, an oxime-based polymerization initiator, a polymerizable compound, and an acid anhydride.   The curable composition according to claim 1, wherein the content mass ratio of the content of the acid anhydride to the content of the oxime-based polymerization initiator in the curable composition is 0.005 to 0.5. Composition.   The curable composition according to claim 1, wherein the acid anhydride contains two or more acid anhydride groups in one molecule.   Furthermore, the curable composition as described in any one of Claims 1-3 containing a polymerization inhibitor.   The curable composition according to any one of claims 1 to 4, wherein the metal nitride-containing particles contain titanium nitride.   The curable composition according to claim 5, wherein a diffraction angle 2θ of a peak derived from the (200) plane of the metal nitride-containing particle when the CuKα ray is an X-ray source is 42.5 to 42.8 °. object.   Furthermore, the curable composition as described in any one of Claims 1-6 containing alkali-soluble resin.   The curable composition according to claim 7, wherein the alkali-soluble resin contains at least one selected from the group consisting of a polyimide precursor and a polyimide resin.   The content of the said metal nitride containing particle | grains in the said curable composition is 40 mass% or more with respect to the total solid of the said curable composition to any one of Claims 1-8. Curable composition as described.   The content mass ratio of the content of the oxime-based polymerization initiator to the content of the metal nitride-containing particles in the curable composition is 0.03 to 0.2. The curable composition as described in any one.   The curable composition according to any one of claims 1 to 10, wherein the oxime-based polymerization initiator contains a nitro group.   The curable composition according to any one of claims 1 to 11, further comprising a solvent.   The cured film obtained by hardening | curing the curable composition as described in any one of Claims 1-12.   A color filter comprising the cured film according to claim 13.   A solid-state imaging device comprising the cured film according to claim 13.   An infrared sensor containing the cured film according to claim 13. A curable composition layer forming step of forming a curable composition layer using the curable composition according to any one of claims 1 to 12,
Exposing the curable composition layer through exposure to an actinic ray or radiation through a photomask provided with a pattern-like opening;
And developing the curable composition layer after the exposure to form a cured film. The manufacturing method of a color filter containing the manufacturing method of the cured film of Claim 17.