TW201809868A - Curable composition, cured film, color filter, light blocking film, solid-state imaging element, image display device, and method for producing cured film - Google Patents

Abstract

Provided are: a curable composition which enables the achievement of a cured film that has an excellent pattern shape, while maintaining excellent light blocking properties; a cured film; a color filter; a light blocking film; a solid-state imaging element; an image display device; and a method for producing a cured film. This curable composition contains a coloring agent, a photopolymerization initiator, a polymerizable compound and a polyfunctional thiol compound; and a cured film which is obtained by curing this curable composition has an optical density of 4.0 or more per a film thickness of 1.5 [mu]m in the visible light region.

Description

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

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

A color filter used in a liquid crystal display device is provided with a light-shielding film called a black matrix in order to block light between colored pixels and improve contrast. In addition, a solid-state imaging device is provided with a light-shielding film in order to prevent noise, improve image quality, and the like. At present, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin camera units. These imaging units usually include solid-state imaging elements such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors, as well as A lens that forms a subject image on the imaging element.

Patent Document 1 describes a composition for forming a light-shielding film, "a composition for forming a light-shielding film, comprising a coating film capable of forming a periphery of an effective pixel region (imaging section) of a solid-state imaging element, and A black colorant and resin component having an average particle diameter of 40 nm or less "and" a black colorant contains at least one of carbon black and titanium black ". [Prior Art Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent Laid-Open No. 2006-156801

The present inventors conducted intensive studies on a light-shielding film obtained by curing the composition for forming a light-shielding film described in Patent Document 1, and as a result, it was confirmed that although it has excellent light-shielding properties, the obtained pattern shape exists Room for further improvement. Specifically, it was confirmed that in the light-shielding film obtained by curing the light-shielding film-forming composition described in Patent Document 1, the film thickness at the end portion may be smaller than the film thickness at the center portion.

An object of the present invention is to provide a curable composition that can obtain a cured film that maintains excellent light shielding properties and has an excellent pattern shape. Another object of the present invention is to provide a cured film obtained using the curable composition, a color filter including the cured film, a light-shielding film, a solid-state imaging device and an image display device, and a method for producing a cured film. .

The present inventors have conducted intensive studies in order to achieve the above-mentioned problems. As a result, it has been found that the above-mentioned curable composition can solve the above-mentioned problems and has completed the present invention. The curable composition contains a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound. The optical density of the cured film obtained by curing the sexual composition per 1.5 μm in the visible light region is 4.0 or more. That is, it was found that the above-mentioned problem can be achieved by the following configuration.

[1] A curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, wherein a cured film obtained by curing the curable composition per 1.5 μm in a visible light region The optical density of the film thickness is 4.0 or more. [2] The curable composition according to [1], wherein the content of the colorant is 55% by mass or more based on the total solid content of the curable composition. [3] The curable composition according to [1] or [2], wherein the content of the polyfunctional thiol compound is 1 to 5.5% by mass based on the content of the colorant. [4] The curable composition according to any one of [1] to [3], further comprising a polymerization inhibitor. [5] The curable composition according to [4], wherein the content of the polymerization inhibitor is 0.1 to 1.5% by mass based on the content of the polyfunctional thiol compound. [6] The curable composition according to [4] or [5], wherein the polymerization inhibitor contains a phenolic compound. [7] The curable composition according to any one of [4] to [6], wherein the polymerization inhibitor contains two or more phenolic compounds. [8] The curable composition according to any one of [4] to [7], wherein the polymerization inhibitor contains a hindered amine compound. [9] The curable composition according to any one of [1] to [8], wherein the colorant is an inorganic pigment. [10] The curable composition according to [9], wherein the inorganic pigment comprises a metal pigment selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, a metal pigment containing silver or tin, and silver and tin. At least one of the group consisting of metallic pigments of tin. [11] The curable composition according to any one of [1] to [10], wherein the polyfunctional thiol compound is a compound having two or more groups represented by formula (1). [12] The curable composition according to any one of [1] to [11], wherein the polyfunctional thiol compound is trifunctional or higher. [13] The curable composition according to any one of [1] to [12], wherein the polyfunctional thiol compound is selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and trimethylolpropane tri At least one of the group consisting of (3-mercaptopropionate). [14] The curable composition according to any one of [1] to [13], wherein the content of the photopolymerization initiator is more than 1% by mass and less than the total solid content of the curable composition. 10% by mass. [15] The curable composition according to any one of [1] to [14], wherein the content of the polymerizable compound is more than 3.5% by mass and less than 20% by mass relative to the total solid content of the curable composition. %. [16] The curable composition according to any one of [1] to [15], further containing a dispersant, and the content of the dispersant is 17% by mass or more based on the total solid content of the curable composition. [17] The curable composition according to any one of [1] to [16], wherein the photopolymerization initiator is an oxime compound. [18] A cured film obtained by curing the curable composition according to any one of [1] to [17]. [19] A color filter comprising the cured film according to [18]. [20] A light-shielding film comprising the cured film according to [18]. [21] A solid-state imaging device comprising the cured film according to [18]. [22] An image display device comprising the cured film according to [18]. [23] A method for producing a cured film, comprising using the curable composition according to any one of [1] to [17] to form a curable composition layer on a support to form a curable composition layer. A manufacturing process; and an exposure process for exposing the hardenable composition layer. [24] The method for producing a cured film according to [23], wherein the exposure amount of the curable composition layer in the exposure process is 200 mJ / cm ² or more. [25] The method for producing a cured film according to [23] or [24], wherein the process of forming a hardenable composition layer includes directly applying a hardenable composition on a support to form hardenability on the support. Coating process of the composition layer. [26] The method for producing a cured film according to any one of [23] to [25], further comprising: a developing process of developing the exposed hardenable composition layer; and cleaning the developed hardenability Process for cleaning the composition layer. [Inventive effect]

According to the present invention, it is possible to provide a curable composition capable of obtaining a cured film that maintains excellent light shielding properties and has an excellent pattern shape. According to the present invention, it is also possible to provide a cured film obtained using the curable composition, a color filter including the cured film, a light-shielding film, a solid-state imaging device and an image display device, and a method for producing a cured film.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In addition, in this specification, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In addition, among the marks of a group (atomic group) in the present specification, unlabeled substitutions and unsubstituted marks include those containing no substituents and those containing substituents. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent. In addition, "actinic rays" or "radiation" in this specification means, for example, a bright line spectrum of a mercury lamp, and extreme ultraviolet (EUV: Extreme ultraviolet lithography light), X-ray, and electron beams represented by an excimer laser. Wait. In this specification, "light" means actinic rays and radiation. As long as "exposure" in this manual is not specified, in addition to exposure using the bright-line spectrum of a mercury lamp and far-ultraviolet rays, X-rays, and EUV light represented by an excimer laser, the use of electron beams and Drawing by particle beams such as ion beams. In addition, in this specification, "(meth) acrylate" means an acrylate and a methacrylate. In addition, in this specification, "(meth) acrylic acid" means acrylic acid and methacrylic acid. In the present specification, "(meth) acrylfluorenyl" means acrylfluorenyl and methacrylfluorenyl. In addition, in this specification, "(meth) acrylamide" means acrylamide and methacrylamide. In addition, in this specification, "monomer" and "monomer" have the same meaning. A monomer is different from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound containing a polymerizable group, and may be a monomer or a polymer. A polymerizable group refers to a group that participates in a polymerization reaction.

[Sclerosing composition] The sclerosing composition contains a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, and the cured film obtained by curing the sclerosing composition is 1.5 μm in the visible light region. The optical thickness of the film thickness is 4.0 or more. According to the curable composition having such a structure, a cured film (hereinafter, also referred to as "effect of the present invention") having an excellent pattern shape while maintaining excellent light shielding properties can be obtained. Although the mechanism by which the effect of this invention is obtained with the said hardenable composition is not clear, the present inventors etc. inferred as follows. In addition, the mechanism by which the above-mentioned curable composition exerts the effects of the present invention is not limited by the following estimation.

A conventionally known curable composition containing a colorant such as carbon black and not containing a polyfunctional thiol compound can be used widely because it can obtain a high light-shielding concentration over a wide wavelength region. However, the optical density (also referred to as OD: optical density) of the curable composition layer gradually increases from the long wavelength side to the short wavelength side, and the optical density in the short wavelength region is extremely higher than that in the long wavelength side. Therefore, for example, when pattern-exposing the curable composition layer with light in the ultraviolet region such as g-rays, h-rays, and i-rays, the light may not reach the interior of the curable composition layer, and the exposure may be insufficient and the pattern shape may be deteriorated. Based on the above, the mechanism of the deterioration of the pattern shape will be described using FIGS. 1 to 6 which schematically show the manufacturing process of the cured film for each process. First, FIGS. 1 to 3 are cross-sectional views schematically showing a manufacturing process of a cured film using a curable composition not containing a polyfunctional thiol for each process. First, as shown in FIG. 1, a curable composition layer 102 is formed on a support 101 using a curable composition. Next, the hardening composition layer 102 is exposed through the opening of the photomask 103 (in FIG. 1, arrows indicate the direction of light irradiation, and the line A-B is an extension of one end of the opening of the photomask. The same applies hereinafter.). Next, the curable composition layer 102 after the exposure is developed to form a patterned cured film 201. During the exposure in the above steps, the optical density of the curable composition layer 102 is high. Therefore, light does not easily reach the inside of the curable composition layer 102 during exposure, and the exposure becomes insufficient under the curable composition layer 102. In this way, if development is performed, exposure to the hardenable composition layer 102 is insufficient, and the hardenable composition is dissolved out (FIG. 2). If a baking process is performed after the heat-cured film 201 is heated in this state, a problem called "sags due to heat" occurs in a portion eluted during development. That is, it is presumed that the thickness of the end portion of the cured film 301 after being obtained after baking is reduced compared to the center portion (FIG. 3).

4 to 6 are cross-sectional views schematically showing a manufacturing process of a cured film using the curable composition of the present invention for each process. First, as shown in FIG. 4, a curable composition layer 401 is formed on a support 101 using the curable composition of the present invention. Then, the hardening composition layer 401 is exposed through the opening of the photomask 103. At this time, since the curable composition layer 401 contains a polyfunctional thiol compound, it is presumed to be sufficiently cured to the inside of the curable composition layer 401 for the following reasons. In the exposed hardenable composition layer 401, a radical polymerization reaction is started by a photopolymerization initiator. At this time, radicals generated by the photopolymerization initiator react with oxygen in the hardenable composition layer 401, and peroxy radicals may be generated. The peroxy radical does not have the effect of carrying out the polymerization reaction, so the polymerization reaction stops here. On the other hand, when a polyfunctional thiol compound is present in the hardenable composition layer 401, a thiol group in the polyfunctional thiol compound supplies hydrogen to a peroxy radical, thereby generating sulfur that is not easily deactivated by polymerization due to oxygen. Free radicals, polymerization can proceed. Therefore, it is presumed that the above-mentioned curable composition containing a polyfunctional thiol compound is one which is easily cured sufficiently to the inside of the curable composition layer 401. In addition, the optical density of the cured film obtained by hardening the curable composition per 1.5 μm in the visible light region is 4.0 or more, and the light-shielding property of the curable composition layer 401 is high. Generally, the light irradiated on the hardening composition layer 401 through the opening of the mask 103 is diffracted at the opening of the mask 103 and also irradiates the mask light-shielding portion 402 (referred to as this "Light leak."). When the light-shielding property of the curable composition layer is low, the shape of the pattern is deteriorated due to light leakage and exposure to the hardenable composition layer of the cover light-shielding portion. However, since the light-shielding property of the curable composition layer 401 is high, light leakage is not absorbed by the exposure of the light-shielding portion 402 (FIG. 4). Therefore, if the cured film after the exposure is developed, the cured film is sufficiently cured to the inside and the light diffracted at the opening of the photomask is absorbed, so that a cured film 501 having an excellent pattern shape can be obtained (FIG. 5). It is inferred that in this cured film 501, "heating sagging" does not easily occur even after the post-baking treatment, so the film thickness difference between the central portion and the end portion of the cured film 601 after post-baking is small, and it is excellent Pattern shape (Figure 6).

[Optical Density (OD Value)] The optical density of the cured film obtained by curing the above-mentioned curable composition per 1.5 μm in the visible light region is 4.0 or more. Among these, from the viewpoint of obtaining a curable composition having more excellent effects of the present invention, the optical density is more preferably 4.1 or more, and more preferably 4.3 or more. The upper limit value is not particularly limited, but it is usually preferably 8.0 or less. In addition, in this specification, an optical density means the optical density measured by the method described in an Example, and a visible light area shows the light of wavelength 400-800 nm. Therefore, an optical density of 4.0 or more per 1.5 μm film thickness in the visible light region indicates that the optical density per 1.5 μm of film thickness is 4.0 or more in the entire region with a wavelength of 400 to 800 nm.

Hereinafter, aspects of each component included in the curable composition will be described in detail.

[Colorant] The curable composition contains a colorant. The colorant is at least one selected from the group consisting of a pigment and a dye. The content of the colorant is more preferably 55% by mass or more, more preferably 56% by mass or more, and more preferably 58% by mass or more with respect to the total solid content of the curable composition. When the content of the colorant is 55% by mass or more, the pattern shape of the cured film obtained by curing the curable composition is more excellent. In addition, the upper limit value of the content of the colorant is not particularly limited, and it is usually preferably 70% by mass or less based on the total solid content of the curable composition. When the content of the colorant is equal to or less than the upper limit value, the curable composition has more excellent coatability.

<Pigment> There is no restriction | limiting in particular as a pigment, A well-known inorganic pigment and / or organic pigment can be used. Among these, it is preferable that the pigment is an inorganic pigment from the viewpoint that a curable composition having more excellent effects of the present invention can be obtained.

(Inorganic Pigment) The inorganic pigment is not particularly limited, and a known inorganic pigment can be used. Examples of the inorganic pigment include zinc white, lead white, zinc barium white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead red, iron oxide red, chrome yellow, and zinc yellow (zinc 1 yellow, 2 zinc yellow), ultramarine blue, Prussian blue (ferrous potassium ferrocyanide), zircon gray, ochre yellow, chrome titanium yellow, chrome green, peacock, Victoria green, iron blue (unrelated to Prussian blue ), Vanadium zirconium blue, chrome tin red, manganese red, orange red, etc. In addition, examples of the black inorganic pigment include metals containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Oxides, metal nitrides.

As the inorganic pigment, carbon black, titanium black, and metallic pigments (hereinafter, also referred to as "black pigments") are considered from the viewpoint that a curable composition capable of forming a cured film having a high optical concentration can be obtained even if the content is small. ) Is better. Examples of the metal pigment include one or two or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Metal oxide or metal nitride. As the inorganic pigment, it is preferable to contain at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, a metal pigment containing silver or tin, and a metal pigment containing silver and tin. It is more preferable to contain at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, and vanadium nitride. As the inorganic pigment, carbon black can also be used. Specific examples of carbon black include organic pigments such as C.I. Pigment Black 1 and inorganic pigments such as C.I. Pigment Black 7 which are commercially available products, but are not limited thereto.

In the curable composition, in addition to a pigment described as a black pigment, a pigment having infrared absorption properties can also be used. As the pigment having infrared absorption properties, a tungsten compound, a metal boride, and the like are preferred, and among them, a tungsten compound is preferred from the standpoint of excellent light shielding properties at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint that the light absorption wavelength region and the visible light region of the photopolymerization initiator related to the curing efficiency by exposure are excellent.

These pigments may be used in combination of two or more types, and may be used in combination with dyes described later. For adjusting the color tone and improving the light-shielding property in a desired wavelength region, for example, a color mixture of red, green, yellow, orange, purple, and blue, or a dye to be described later is mixed with a black or infrared-shielding pigment. kind. It is preferable to mix a red pigment or a dye, or a purple pigment or a dye to a black or a pigment having an infrared light blocking property, and it is more preferable to mix a red pigment to a black or a pigment having an infrared light blocking property. Furthermore, a near-infrared absorber and an infrared absorbent described later may be added.

The black pigment preferably contains titanium black and / or niobium oxynitride. Titanium black is black particles containing titanium atoms. Low-order titanium oxide, titanium oxynitride, titanium nitride, and the like are preferred. The titanium black particles can modify the surface as necessary in order to improve dispersibility, suppress cohesion, and the like. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconia, and can also be treated with a water-repellent substance as shown in Japanese Patent Application Laid-Open No. 2007-302836. Titanium black is typically titanium black particles, and the primary particle size and average primary particle size of each particle are preferably smaller. The same is true for niobium oxynitride. Specifically, it is preferable that the average primary particle diameter is in a range of 10 nm to 45 nm.

The average primary particle diameter of the pigment can be measured using a transmission electron microscope (TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used. Measure the maximum length of a particle image obtained with a transmission electron microscope (Dmax: the maximum length of 2 points on the outline of the particle image) and the maximum vertical length (DV-max: using two straight lines parallel to the maximum length) When the image is sandwiched, the shortest length between two straight lines is vertically connected), and the multiplied average value (Dmax × DV-max) ^{1/2 is taken} as the particle size. The particle diameter of 100 particles was measured by this method, and the arithmetic average value was taken as the average particle diameter and the average primary particle diameter of the pigment.

The specific surface area of titanium black and niobium oxynitride is not particularly limited. In order to make the water resistance of the titanium black and niobium oxynitride surface treated by the water-repellent agent a predetermined property, it is measured by the BET (Brunauer, Emmett, Teller) method is 5m ² / g or more and 150m ² / g or less is preferred, 20m ² / g or more and 120m ² / g or less is more preferred. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilack D (product Name, manufactured by Ako Kasei Co., Ltd.), titanium nitride 50nm (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), and the like.

As the colorant, titanium oxynitride, titanium nitride, or niobium oxynitride is preferably used. From the reason that the cured film obtained has better moisture resistance, titanium nitride or niobium oxynitride is more preferable, and niobium oxynitride Is even better. This is because these colorants are considered to be hydrophobic.

Moreover, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms. In this form, titanium black is contained as a dispersion in a hardenable composition, and the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is preferably 0.05 or more in terms of mass conversion. 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is more preferable. Here, the to-be-dispersed body includes both those in a state where titanium black is a primary particle and those in a state of an aggregate (secondary particle). In order to change the Si / Ti of the dispersion (for example, 0.05 or more), the following method can be used. First, a dispersion is obtained by dispersing titanium oxide and silicon dioxide particles with a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1,000 ° C), whereby titanium black particles can be obtained as a main component. It contains a dispersion of Si and Ti. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia. Examples of the titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo Kaisha, Ltd.) and the like. Examples of commercially available products of silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik Japan Co., Ltd.), and the like. Dispersants can be used to disperse titanium oxide and silica particles. Examples of the dispersant include those described in the column of dispersant described later. The above dispersion can also be performed in a solvent. Examples of the solvent include water and organic solvents. Examples include those described in the column of organic solvents described later. The titanium black whose Si / Ti is adjusted to, for example, 0.05 or more can be produced, for example, by the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045.

The content ratio (Si / Ti) of the Si atom and the Ti atom in the dispersion containing titanium black and Si atoms is adjusted to a preferable range (for example, 0.05 or more), and the hardening composition containing the dispersion is used When a cured film is formed, residues originating from the curable composition outside the region where the cured film is formed are reduced. The residue is a component containing components derived from a hardening composition such as titanium black particles and resin components. Although the reason for the reduction of the residue is not clear, as described above, the dispersion has a tendency to decrease in particle size (for example, the particle diameter is 30 nm or less), and the component containing Si atoms in the dispersion increases, thereby the entire film Adhesion to the substrate is reduced. It is presumed that this phenomenon contributes to the improvement of the development and removal property of an unhardened curable composition (especially, titanium black) when a cured film is formed. Titanium black has excellent light-shielding properties over light in a wide range of wavelengths from ultraviolet to infrared light, so the above-mentioned dispersion containing titanium black and Si atoms (Si / Ti in mass conversion, more than 0.05 is preferred) ) To form a cured film exhibiting excellent light-shielding properties. The content ratio (Si / Ti) of the Si atom and the Ti atom in the dispersion can be, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of Japanese Patent Application Laid-Open No. 2013-249417. Perform the measurement. For the dispersion contained in the cured film obtained by curing the hardenable composition, to determine whether the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is 0.05 or more, Japanese Patent Application Laid-Open can be used Method (2) described in paragraph 0035 of 2013-249417.

Among the dispersions containing titanium black and Si atoms, titanium black can be used. In this dispersion, in order to adjust dispersibility, colorability, etc., one or two or more kinds of composite oxides including cobalt, Fe, Mn, V, Ni, cobalt oxide, iron oxide, and carbon can be combined with titanium black. Black and aniline black pigments are used. In this case, it is preferable that the dispersion containing titanium black accounts for 50% by mass or more of all the dispersions. In this dispersion, in order to adjust the light-shielding property and the like, other colorants (organic pigments and / or dyes, etc.) may be used together with titanium black, as long as the effects of the present invention are not impaired. Hereinafter, materials used when introducing Si atoms into the dispersion will be described. When introducing Si atoms into the dispersion, a Si-containing substance such as silicon dioxide may be used. Examples of the usable silicon dioxide include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These can be appropriately selected and used. In addition, if the particle diameter of the silicon dioxide particles is a particle diameter smaller than the film thickness when the light-shielding film is formed, the light-shielding property is more excellent. Therefore, it is preferable to use microparticle-type silicon dioxide. In addition, examples of the particulate silica include silicon dioxide described in paragraph 0039 of Japanese Patent Application Laid-Open No. 2013-249417, and the contents are incorporated herein.

As the curable composition, a tungsten compound and / or a metal boride can be used as the pigment. Tungsten compounds and metal borides have higher absorption relative to infrared (light having a wavelength of about 800 to 1200 nm) (that is, higher light shielding (shielding) relative to infrared) and lower absorption relative to visible light. Infrared shielding material. Therefore, the curable composition of the present invention can form a pattern having a high light-shielding property in the infrared region and a high light-transmitting property in the visible light region by containing a tungsten compound and / or a metal boride. Tungsten compounds and metal borides are also less absorbing in light in the visible region than those used in the exposure of high-pressure mercury lamps, KrF, ArF, etc. used for image formation. Therefore, by combining with a polymerizable compound, an alkali-soluble resin, and a photopolymerization initiator to be described later, an excellent pattern can be obtained, and when a pattern is formed, development residue can be more suppressed.

Examples of the tungsten compound include tungsten oxide-based compounds, tungsten boride-based compounds, tungsten sulfide-based compounds, and the like, and tungsten oxide-based compounds represented by the following general formula (compositional formula) (I) are preferred. M _x W _y O _z (I) M represents metal, W represents tungsten, and O represents oxygen. 0.001≤x / y≤1.1 2.2≤z / y≤3.0

Examples of the metal of M include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, Rb, Cs, etc., alkali metals are preferred. The metal of M may be one type or two or more types.

M is preferably an alkali metal, Rb or Cs is more preferred, and Cs is further preferred.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when x / y is 1.1 or less, it is possible to more reliably avoid the formation of an impurity phase in a tungsten compound. When z / y is 2.2 or more, chemical stability as a material can be further improved, and when z / y is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide-based compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _3, and the like, Cs _0.33 WO ₃ or Rb _0.33 WO. ₃ is more preferable, and Cs _0.33 WO ₃ is more preferable.

The tungsten compound is preferably fine particles. The average primary particle diameter of the tungsten particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. When the average primary particle diameter is in this range, the tungsten fine particles are difficult to block visible light due to light scattering, so that the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the better, but for reasons such as ease of handling at the time of production, the average primary particle diameter of the tungsten particles is usually 1 nm or more.

Two or more tungsten compounds can be used.

A tungsten compound can be obtained as a commercial item. When the tungsten compound is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Patent No. 4096205). The tungsten oxide-based compound can also be obtained, for example, as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Examples of the metal boride include lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), and boride Titanium (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), boride One or more types of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), etc., and lanthanum boride (LaB ₆ ) is preferred.

It is preferred that the metal borides be fine particles. The average primary particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. When the average primary particle diameter is in this range, the metal boride fine particles are difficult to block visible light due to light scattering, so that the transmittance in the visible light region can be made more reliable. From the standpoint of avoiding light scattering, the smaller the average primary particle diameter is, the better, but for reasons such as ease of handling during production, the average primary particle diameter of the metal boride fine particles is usually 1 nm or more.

Two or more kinds of metal borides can be used.

The metal boride can be obtained as a commercially available product, for example, it can also be obtained as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.

(Titanium nitride-containing particles) As the inorganic pigment, titanium nitride-containing particles containing Fe atoms can also be used. In the production of titanium nitride-containing particles, a gas-phase reaction method is generally used, and specific examples thereof include an electric furnace method and a thermo-plasma method. Among these production methods, a thermoplasma method is preferred from the viewpoints of a small amount of impurities, a point of easy particle size consistency, and a point of high productivity. Examples of the generation method of the thermo-plasma include direct-current arc discharge, multi-phase arc discharge, high-frequency (RF) plasma, and hybrid plasma. The high-frequency plasma with less impurities from the electrode is preferable. . As a specific manufacturing method of the titanium nitride-containing microparticles based on the thermo-plasma method, for example, titanium powder is evaporated by a high-frequency thermo-plasma, nitrogen is introduced into a device as a carrier gas, and titanium powder nitrogen is cooled by a cooling process. Method to synthesize titanium nitride-containing particles. The pyroplasma method is not limited to the above.

The method for producing titanium nitride-containing particles is not particularly limited, and the production methods described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to. For example, it can be manufactured by replacing the Ag powder of International Publication No. 2010/147098 with a component containing Fe and / or a component containing Si described later, and mixing the component with a titanium powder material (titanium particles) as The raw materials are used to produce titanium nitride-containing particles contained in the composition of the present invention.

The titanium powder material (titanium particles) used in the production of titanium nitride-containing particles is preferably one having high purity. The titanium powder material is not particularly limited, and a titanium element having a purity of 99.99% or more is preferable, and a titanium powder having a purity of 99.999% or more is more preferable.

The titanium powder material (titanium particles) used in the production of titanium nitride-containing particles may contain atoms other than titanium atoms. Examples of other atoms that may be contained in the titanium powder material include Fe atoms and Si atoms. When the titanium powder material contains Fe atoms, the content of Fe atoms is more than 0.001% by mass relative to the total mass of the titanium powder material. When the titanium powder material contains Si atoms, the content of Si atoms is more than 0.002 mass% and less than 0.3 mass% with respect to the total mass of the titanium powder material, more preferably 0.01 to 0.15 mass%, and more preferably 0.02 to 0.1 mass%. good. When the content of Si atoms exceeds 0.002% by mass, the pattern formability of the cured film is further improved. When the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is more stabilized. From this, it is thought that the dispersant when dispersing the titanium nitride-containing particles is optimized for its adsorption to the titanium nitride-containing particles, the amount of undispersed titanium nitride-containing particles is reduced, and generation of particles can be suppressed. The moisture content of the titanium powder material (titanium particles) used in the production of titanium nitride-containing particles is preferably less than 1% by mass and more preferably less than 0.1% by mass, and does not substantially include Further preferred.

By using the pyroplasma method to obtain titanium nitride-containing particles, the diffraction angle 2θ (the details will be described later) originating from the peak of the (200) plane when CuKα rays are used as the X-ray source can be easily adjusted to more than 42.6 ° And in the range of 43.5 ° or less.

The method for making the titanium nitride-containing particles contain Fe atoms is not particularly limited, and examples thereof include a method for introducing Fe atoms at the stage of obtaining titanium particles (titanium powder) used as a raw material of the titanium nitride-containing particles. . In more detail, when titanium is produced by a reduction (Kroll) method or the like, as a reaction vessel, a material composed of a material containing Fe atoms such as stainless steel (SUS), or as a material for a punch and a crusher when crushing titanium is used. Those who contain Fe atoms can adhere Fe atoms to the surface of the titanium particles. When the thermoplasma method is used in the production of titanium nitride-containing particles, in addition to titanium particles as raw materials, components such as Fe particles and Fe oxides are added, and these are nitrided by the thermoplasma method, thereby enabling nitrogen to be contained. The titanium oxide particles contain Fe atoms. In addition, the Fe atoms contained in the titanium nitride-containing particles may be ions, metal compounds (including complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides, and sulfur. Any form such as an oxide is included. The Fe atom contained in the titanium nitride-containing particles may exist as an impurity at an inter-lattice position, or may exist in an amorphous state as an impurity at a grain boundary.

As a result of intensive studies conducted by the present inventors, it was found that the content of Fe atoms in the titanium nitride-containing particles is related to the pattern-forming property and the corrosion resistance of the electrode. The Fe atoms contained in the titanium nitride-containing particles are excellent in adhesion to the electrode and the substrate, and it is considered that the titanium nitride in the titanium nitride-containing particles is attached to the electrode and the substrate via Fe atoms. It is considered that after the formation of a pattern of a hardened film such as a development process, Fe atoms remain on the electrode and the substrate, and titanium nitride is easily removed. Therefore, it is presumed that by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more, the pattern formability of the cured film is improved. On the other hand, if the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrodes and the substrate increases, which is considered to be a cause of electrode corrosion. Therefore, it is inferred that the corrosion resistance of the electrode is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less. The content of Fe atoms in the titanium nitride-containing particles is preferably more than 0.001% by mass and less than 0.4% by mass relative to the total mass of the titanium nitride-containing particles. Among these, 0.01 to 0.2% by mass is more preferred, and 0.02 to 0.1% by mass is even more preferred. When the content of Fe atoms exceeds 0.001% by mass, the pattern formability of the cured film is further improved. When the content of Fe atoms is less than 0.4% by mass, the corrosion resistance of the electrode based on the cured film is further improved (the electrode can be inhibited from being corroded by the cured film). That is, when the content of Fe atoms in the titanium nitride-containing particles is within the above range, it is possible to obtain an excellent pattern formation property of the cured film and an anticorrosive property of the electrode. The content of Fe atoms in the titanium nitride-containing particles can be measured by an ICP (Inductively Coupled Plasma; High Frequency Inductively Coupled Plasma) emission spectroscopic analysis method.

It is preferable that the titanium nitride-containing particles further contain Si atoms (silicon atoms). Thereby, the pattern formation property of a cured film is improved more. The reason why the pattern formability is improved by containing Si atoms is considered to be the same as the aforementioned Fe atoms. The content of Si atoms in the titanium nitride-containing particles is more than 0.002 mass% and less than 0.3 mass% with respect to the total mass of the titanium nitride-containing particles, more preferably 0.01 to 0.15 mass%, and more preferably 0.02 to 0.1 mass%. Better. When the content of Si atoms exceeds 0.002% by mass, the pattern formability of the cured film is further improved. It is considered that when the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles is more stabilized. Thereby, it is considered that the dispersant when dispersing the titanium nitride-containing particles is optimized for its adsorption to the titanium nitride-containing particles, the amount of undispersed titanium nitride-containing particles is reduced, and the generation of particles can be suppressed. The Si atom content in the titanium nitride-containing particles can be measured by the same method as the Fe atom.

The method for making the titanium nitride-containing particles contain Si atoms is not particularly limited, and examples thereof include a method of introducing Si atoms at the stage of obtaining the titanium particles (titanium powder) used as a raw material for the titanium nitride-containing particles. . In more detail, when titanium is produced by a reduction method or the like, it is possible to use a material containing Si atoms as a reaction container, or use a material containing Si atoms as a material for a punch and a crusher when titanium is crushed. Si atoms are attached to the surface of the titanium particles. When the thermoplasma method is used in the production of titanium nitride-containing particles, in addition to titanium particles as raw materials, components such as Si particles and Si oxides are added, and these are nitrided by the thermoplasma method, thereby enabling nitrogen to be contained. The titanium particles contain Si atoms. The Si atoms contained in titanium nitride-containing particles can be ions, metal compounds (including complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides, and sulfur oxides. Either form is included. In addition, the Si atoms contained in the titanium nitride-containing particles may exist as impurities at inter-lattice positions, or may exist as impurities at the grain boundaries in an amorphous state.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass, more preferably 15 to 75% by mass, and 20 to 70% by mass relative to the total mass of the titanium nitride-containing particles. Further preferred. The content of Ti atoms in the titanium nitride-containing particles can be measured by ICP emission spectrometry. The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, and 10 to 40% by mass relative to the total mass of the titanium nitride-containing particles. Further preferred. The nitrogen atom content can be analyzed by an inert gas fusion thermal conductivity method. Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and generally become noticeable when oxygen is mixed during the synthesis and when the particle size is small, but they may also be contained by oxidation of the particle surface, etc. Part of the oxygen atom. The content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass, and still more preferably 5 to 30% by mass relative to the total mass of the titanium nitride-containing particles. The content of oxygen atoms can be analyzed by an inert gas melting infrared absorption method.

From the viewpoint of dispersion stability and light-shielding properties, a specific surface area of titanium nitride-containing particles is 5m ² / g or more and 100m ² / g or less is preferred, 10m ² / g or more and 60m ² / g or less is more preferred. The specific surface area can be determined by the BET (Brunauer, Emmett, Teller) method.

The titanium nitride-containing particles may be composite particles containing titanium nitride particles and metal particles. Composite particles are particles in which titanium nitride particles and metal particles are composited or in a highly dispersed state. Among them, "compositing" indicates that particles are composed of two components, titanium nitride and metal, and "highly dispersed state" indicates that titanium nitride particles and metal particles exist separately, and particles with a small amount of components are not agglomerated and uniform. , The same dispersed. The metal fine particles are not particularly limited, and examples thereof include copper, silver, gold, platinum, vanadium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, and calcium. , Titanium, bismuth, antimony and lead, and at least one of these alloys. Among them, at least one selected from the group consisting of copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, and iridium, and these alloys is preferred, and is selected from copper, silver, gold, platinum, and tin, and the At least one of these alloys is more preferred. From the viewpoint of more excellent moisture resistance, silver is preferred. The content of the metal fine particles in the titanium nitride-containing particles is preferably 5 mass% or more and 50 mass% or less, and more preferably 10 mass% or more and 30 mass% or less with respect to the total mass of the titanium nitride-containing particles.

・ The peak diffraction angle 2θ of titanium nitride-containing particles When CuKα rays are used as the X-ray source, the diffraction angle 2θ of the peaks originating from the (200) plane of titanium nitride-containing particles is more than 42.6 ° and less than 43.5 ° . A hardened film (for example, a black matrix, etc.) obtained using a hardenable composition containing titanium nitride particles having such characteristics can achieve a high OD value.

When CuKα ray is used as the X-ray source to measure the X-ray diffraction spectrum of a titanium compound, as the strongest peak, the peak originating from the (200) plane of TiN appears near 2θ = 42.5 °, and the TiO originates from ( 200) The peak of the plane appears around 2θ = 43.4 °. On the other hand, although not the strongest peak intensity, but on anatase type TiO _2, in the vicinity of 2θ = 48.1 ° derived from the observed (200) plane of the peak near about the rutile type TiO _2, at 2θ = 39.2 ° A peak originating from the (200) plane was observed. Thereby, as the crystal state containing a large amount of oxygen atoms, the peak position shifts toward the high-angle side with respect to 42.5 °.

From the viewpoint of particle stability over time, it is preferable that the diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles exceeds 42.6 ° and is less than 43.5 °, and from the process margin at the time of manufacture From an excellent point of view, 42.7 ° or more and less than 43.5 ° is more preferable, and from the viewpoint of excellent reproducibility of particle performance, 42.7 ° or more and less than 43.4 ° is more preferable. When titanium oxide TiO ₂ is contained as a subsidiary component, as the strongest peak, a peak derived from anatase TiO ₂ (101) appears near 2θ = 25.3 °, and a peak derived from rutile TiO ₂ (110) appears. Now around 2θ = 27.4 °. However, since TiO ₂ is white, it is a factor that reduces the light-shielding property of the black matrix. Therefore, it is preferable to reduce it to such an extent that it cannot be observed as a peak.

The crystallite size of the titanium nitride-containing particles can be calculated from the half-width of the X-ray diffraction peak, and calculated using the Scherrer formula.

The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm. By forming a black matrix with titanium nitride-containing particles having a crystallite size of 20 nm or more, the transmitted light of the hardened film is blue to blue-violet as its peak wavelength is 475 nm or less, which can achieve both high light shielding and ultraviolet sensitivity. Black matrix. With a crystallite size of 20 nm or more, the ratio of the surface of active particles to the volume of the particles becomes small, which becomes a good balance, and becomes more excellent in heat resistance and / or durability of titanium nitride-containing particles.

(Metal-Nitride Particles Containing Atomic A) As the inorganic pigment, metal-nitride-containing particles can also be used, and a predetermined atom A is contained in the metal-nitride-containing particles. Examples of the metal in the metal-containing nitride particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re. The above-mentioned curable composition has more excellent effects of the present invention. From the perspective of consideration, Nb or V is more preferable. Examples of the atom A include B, Al, Si, Mn, Fe, Ni, and Ag. When the metal-containing nitride particle contains the atom A, the content is not particularly limited, and the content of the atom A in the metal-containing nitride particle is preferably 0.00005 to 10% by mass.

The method for producing the metal-containing nitride particles containing the atom A is not particularly limited, and a known method can be used. In the production of metal-containing nitride particles, a gas-phase reaction method is generally used, and specifically, an electric furnace method and a thermo-plasma method are mentioned. Among these production methods, a thermoplasma method is preferred from the viewpoints of a small amount of impurities, a point of easy particle size consistency, and a point of high productivity. As a specific manufacturing method of the metal nitride-containing particle based on the pyroplasma method, for example, a metal particle manufacturing device (the same device as the "black composite particle manufacturing device" described later) can be used. The metal particle manufacturing device includes, for example, a plasma torch that generates a thermal plasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber containing a cooling function, a cyclone separator that classifies the generated metal particles, and The collection part which collects metal fine particles is comprised. In addition, in this specification, a metal fine particle means the particle | grains which have a primary particle diameter containing a metal element of 20 nm-40 micrometers.

The manufacturing method of the metal nitride-containing particle using a metal particle manufacturing apparatus is not specifically limited, A well-known method can be used. Among them, from the viewpoint of improving the yield of the metal nitride-containing particles having a predetermined average primary particle diameter as described below, it is preferable that the method for producing metal nitride-containing particles using a metal microparticle manufacturing apparatus includes a process shown below. Process A: A process of supplying a plasma torch without an inert gas containing nitrogen as a plasma gas to generate a thermoplasma flame. Process B: A process of supplying a metal raw material powder containing a transition metal to a thermoplasma flame in a plasma torch to evaporate the metal raw material powder to obtain a gas phase raw metal. Process C: a process of cooling the gas-phase raw metal to obtain metal particles containing a transition metal. Process D: A process of supplying a plasma torch containing an inert gas containing nitrogen as a plasma gas to generate a thermoplasma flame. Process E: A process of supplying metal particles containing a transition metal to a thermoplasma flame in a plasma torch to evaporate the metal particles, thereby obtaining a gas-phase raw metal. Process F: a process of cooling the gas-phase raw metal to obtain metal nitride-containing particles. In addition, the method for manufacturing metal-containing nitride particles may include the following process G as required after the process C and / or process F described above. Process G: a process of grading the obtained particles. In addition, the following process A2 may be included before the process A, between the process A and the process B, between the process C and the process D, or between the process D and the process E. Process A2: A process in which atom A is mixed into a metal raw material powder containing a transition metal. In addition, the following processes A3-1 to A3-3 may be included before the aforementioned process A2. Process A3-1: A process of supplying a plasma torch without an inert gas containing nitrogen as a plasma gas to generate a thermoplasma flame. Process A3-2: A process in which a raw material powder containing atom A is supplied to a thermoplasma flame in a plasma torch to evaporate the raw material powder to obtain a gas phase atom A process. Process A3-3: A process of cooling the above-mentioned gas phase atom A to obtain atomized atom A in a micronized form. In addition, process G may be included after process A3-3. In this specification, the atomized atom A means particles having a primary particle diameter of the atom A of 20 nm to 40 μm.

In addition, it is preferable that the method for manufacturing the metal nitride-containing particle described above further includes the following process H after the process F (when the process G is included, after the process G after the process F). Process H: a process in which metal nitride-containing particles obtained in process F (or process G) are subjected to a nitriding treatment by exposing them to a mixed atmosphere of water vapor and nitrogen. In addition, according to need, the manufacturing method of the metal-containing nitride particles may further include a process G after the process H. Hereinafter, a preferred embodiment of each process will be described in detail.

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

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

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

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

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

・ Process E Process E is a process of supplying metal particles containing a transition metal to a thermoplasma flame in a plasma torch to evaporate the metal particles, thereby obtaining a raw material metal in a gas phase. As a method for supplying the metal particles to the plasma flame in the plasma torch, as described above, as the carrier gas, an inert gas containing nitrogen is preferred. The state of the inert gas containing nitrogen is as described above. In the process E, the raw metal that becomes the metal particles by the process A to the process C is supplied to the thermoplasma flame, so it is easy to obtain the raw metal in the gas phase, and the state of the raw metal in the gas phase becomes more uniform.

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

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

・ Process H Process H is a process in which metal nitride-containing particles are exposed to a mixed atmosphere of water vapor and nitrogen to perform a nitriding treatment. By this process, the content of the metal nitride in the metal-containing nitride particles can be increased. The method for exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen is not particularly limited. For example, the method may be such that the metal nitride-containing particles are introduced into a thermostatic bath filled with a gas mixed with water vapor and nitrogen. The method of standing or stirring for a predetermined period of time is more preferable from the standpoint that the surface and grain boundary of the metal nitride-containing particles are more stable. As a mixing ratio of water vapor and nitrogen, if the relative humidity is 25 to 95% in the atmosphere, it is preferable. The time for standing or stirring is preferably 0.5 to 72 hours, and the temperature at this time is preferably 10 to 40 ° C.

・ Process A3-1 ～ A3-3 Process A3-1 ～ A3-3 is a process (A3-1) for supplying a plasma flame to an inert gas that does not contain nitrogen as a plasma gas to generate a plasma flame. The thermoelectric plasma flame in the plasma torch supplies a raw material powder containing atom A to evaporate the raw material powder to obtain a gas phase atom A (A3-2), and cooling the gas phase atom A to obtain particles containing atom A The manufacturing process (A3-3). The states in each process are as follows: in the above process A, process B (instead of the metal raw material powder containing the transition metal, using the raw material powder containing the atom A), and process C (instead of the metal particles containing the transition metal, the atomized atom is obtained A.). Through the above process, atom A is atomized, and in process E, atom A becomes easy to evaporate. In addition, by the above-described process, impurities (metal components other than atom A, etc.) contained in the raw material powder containing atom A can be removed.

・ Preferred aspect of the manufacturing method of the atomic A containing metal nitride particle As a preferable aspect of the manufacturing method of the atomic A containing metal nitride particle, the method which has the following manufacturing processes in order is mentioned.・ Process A: A process of supplying a plasma flame to a plasma flame by supplying an inert gas that does not contain nitrogen as a plasma gas. • Process B: A process of supplying a raw metal powder containing a transition metal to a pyroplasma flame in a plasma torch to evaporate the raw metal powder to obtain a raw metal in a gas phase. • Process C: a process of cooling the raw metal in the gas phase to obtain metal particles containing a transition metal.・ Process G: The process of classifying the obtained particles.・ Process A3-1: A process of supplying a plasma flame torch without a nitrogen gas as a plasma gas to generate a thermoplasma flame. Process A3-2: Supplying a plasma flame containing a plasma A Process A3-3 to obtain the atom A of the gas phase by evaporating the raw material powder to obtain the atomic A of the gas phase. Process A3-3 of cooling the atom A of the gas phase to obtain the atomized A atomized. Process G: Particles are classified. • Process A2: A process of mixing atom A (in this case, atomized A) into a metal raw material powder (in this case, metal particles) containing a transition metal.・ Process D: A process of supplying a plasma torch containing an inert gas containing nitrogen as a plasma gas to generate a thermoplasma flame.・ Process E: A process of supplying metal particles containing a transition metal to a thermoplasma flame in a plasma torch to evaporate the metal particles, thereby obtaining a raw material metal in a gas phase. • Process F: a process of cooling the gas-phase raw metal to obtain metal nitride-containing particles.・ Process G: The process of classifying the obtained particles. • Process H: a process in which the metal nitride-containing particles obtained in process G are exposed to a mixed atmosphere of water vapor and nitrogen to perform a nitriding treatment. In the above series of processes, the order of processes A to C and processes A3-1 to A3-3 can be replaced. That is, the processes A to C can be performed after the processes A3-1 to A3-3.

According to a preferred aspect of the method for producing metal-containing nitride particles containing atom A, the metal raw material powder and impurities contained in the raw material particles can be removed, and metal nitride-containing particles having a desired average primary particle diameter can be manufactured. . As a reason therefor, it is presumed that the transition metal and / or the atom A are ionized by plasma treatment, and when the ions are cooled, the transition metal, the atom A, and the impurity reflect the melting point and become micronized. At this time, the atomization of the lower melting point is faster, and the atomization of the higher melting point is slower. Therefore, as mentioned above, it is inferred that the particles (processes B and C, and processes A3-2 and A3-3) that have undergone a single plasma treatment are likely to be a single component (single crystal). By classifying the single-component particles obtained as described above, the particles of the transition metal and / or the particles of the atom A and the particles of the impurities have a difference in density and / or particle diameter to remove the particles of the impurities. The classification can be performed using, for example, a cyclone or the like and appropriately setting classification conditions.

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

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

The manufacturing method of the metal nitride-containing particle may include the following process A0 before the process B (when the process A2 is included, before the process A2). Process A0: a process for removing impurities from metal raw material powder and / or raw material powder.

・ Process A0 In process A0, the method (separation and purification method) of removing impurities from the raw metal powder and / or raw material powder is not particularly limited. For example, for niobium, paragraph 0013 of Japanese Patent Application Laid-Open No. 2012-211048 can be used. The method described in ~ 0030 can also be used for other raw material metal powders and / or raw material powders.

• Coating of metal nitride-containing particles The metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, the coated metal nitride-containing particles may include a metal nitride-containing particle and a coating layer formed using an inorganic compound that coats the metal nitride-containing particle. The curable composition containing metal nitride-containing particles coated with an inorganic compound has more excellent dispersion stability. The inorganic compound is not particularly limited, and examples thereof include oxides such as SiO ₂ , ZrO ₂ , TiO ₂ , GeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ and P ₂ O ₅ , and aluminum hydroxide and zirconium hydroxide. And other hydroxides. Among them, aluminum hydroxide is preferred from the viewpoint of easily forming a thinner film and easily forming a film with a higher coverage. When the refractive index of the metal-containing nitride particles is intended to be controlled, silicon oxide is preferred as a low refractive index coating, and zirconium hydroxide is preferred as a high refractive index coating. The method for coating the metal nitride-containing particles with an inorganic compound is not particularly limited, and the method for producing a metal nitride-containing particle preferably includes the following inorganic compound coating process.

・ Inorganic compound coating process The inorganic compound coating process is a process in which the above-mentioned metal-containing nitride particles are coated with an oxide and / or a hydroxide. The coating method is not particularly limited, and examples thereof include the following wet coating methods.

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

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

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

(Organic Pigment) Examples of the organic pigment include: Colorimetric Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc .; CI Pigment Orange 2,5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc .; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1,49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc .; CI Pigment Green 7, 10, 36, 37, 58, 59, etc .; CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc .; and CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 and so on. The pigment may be used alone or in combination of two or more.

<Dye> For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, and Japanese Patent Application No. No. 2592207, U.S. Patent No. 4885501, U.S. Patent No. 5,667,920, U.S. Patent No. 505950, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115 And pigments disclosed in Japanese Patent Application Laid-Open No. 6-194828. When distinguished by chemical structure, pyrazole azo compounds, pyrrole methylene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxacyanine compounds, and pyrazolotriazoles An azole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole imine compound, and the like. As the dye, a pigment multimer can also be used. Examples of the pigment multimer include compounds described in Japanese Patent Application Laid-Open No. 2011-213925 and Japanese Patent Application Laid-Open No. 2013-041097. As a commercially available product, a polymerizable dye having polymerizability in a molecule can be used, and for example, an RDW series manufactured by Wako Pure Chemical Industries, Ltd. can be used.

<Infrared absorbing agent> The coloring agent may further contain an infrared absorbing agent. The infrared absorber means a compound having absorption in a wavelength region of an infrared region (wavelength of 650 to 1,300 nm is preferable). The infrared absorber is preferably a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm. Examples of the coloring agent having such a spectroscopic property include a pyrrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an ammonium compound, a thiol complex compound, a transition metal oxide compound, Squaric acid cyanine compounds, naphthalocyanine compounds, quartrenene compounds, dithiol metal complex compounds, ketonium compounds, and the like. The phthalocyanine compound, naphthalocyanine compound, immonium compound, cyanine compound, squarocyanine compound, and ketonium compound can use the compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Laid-Open No. 2010-111750, and the contents are incorporated herein. In the manual. The cyanine compound can be referred to, for example, "functional pigments, edited by Ogawara Shinzo / Matsuoka Ken / Hiro Kitahiro / Hirakuri Hiroshi, kodansha Scientific Ltd.", and this content is incorporated into this specification.

As the coloring agent having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Laid-Open No. 07-164729 and / or compounds disclosed in paragraphs 0027 to 0061 of Japanese Patent Application Laid-Open No. 2002-146254, Near-infrared absorbing particles containing microcrystals of Cu and / or P-containing oxides and having a number-average agglomerated particle diameter of 5 to 200 nm, which are disclosed in paragraphs 0034 to 0066 of Japanese Patent Application Laid-Open No. 2011-164583.

As a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm, at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squaraine compound, a phthalocyanine compound, and a naphthalocyanine compound is more preferable. good. The infrared absorber is preferably a compound that dissolves 1% by mass or more in water at 25 ° C, and more preferably that a compound that dissolves 10% by mass or more in water at 25 ° C. By using this compound, the solvent resistance is optimized. The pyrrolopyrrole compounds can be referred to Japanese Patent Application Laid-Open No. 2010-222557, paragraph numbers 0049 to 0061, and the contents are incorporated herein. For cyanine compounds and cyanocyanine compounds, refer to paragraph numbers 0022 to 0063 of International Publication No. 2014/088063, paragraph numbers 0053 to 0118 of International Publication No. 2014/030628, and paragraph number 0028 of Japanese Patent Application Publication No. 2014-59550. ~ 0074, Paragraph Nos. 0013 to 0091 of International Publication No. 2012/169447, Paragraph Nos. 0019 to 0033 of Japanese Patent Laid-Open No. 2015-176046, Paragraph Nos. 0053 to 0099 of Japanese Patent Laid-Open No. 2014-63144, Paragraph Nos. 0085 to 0150 of 2014-52431, Paragraph Nos. 0076 to 0124 of Japanese Patent Laid-Open No. 2014-44301, Paragraph Nos. 0045 to 0078 of Japanese Patent Laid-Open No. 2012-8532, and Japanese Patent Laid-Open No. 2015-172102 Paragraph number 0027-0067, paragraph number 0029-0067 of Japanese Patent Laid-Open No. 2015-172004, paragraph number 0029-0085 of Japanese Patent Laid-open No. 2015-40895, paragraph number 0022- of Japanese Patent Laid-open No. 2014-126642 0036, Japanese Patent Application Laid-Open No. 2014-148567, paragraph numbers 0011 to 0017, Japanese Patent Application Laid-open No. 2015-157893, paragraph numbers 0010 to 0025, Japanese Patent Application Laid-open No. 2014-095007, paragraph numbers 0013 to 0026, Japanese Patent Laid-Open 2014-80487 The paragraph numbers 0013 to 0047 and the paragraph numbers 0007 to 0028 of Japanese Patent Application Laid-Open No. 2013-227403 are incorporated in this description.

The infrared absorbing agent is preferably at least one selected from the group consisting of compounds represented by the following general formulae 1 to 3. Formula 1 [Chemical 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 [Chemical Formula 2] In Formula 1-A, Z ^1A represents a non-metal 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 bonding bond. Formula 2 [Chemical Formula 3] 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 , R ⁴ and R ⁵ May be 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 each independently represent a hydrogen atom Or a substituent, R ⁶ may be covalently bonded or coordinated to R ^1a or R ³ , and R ⁷ may be covalently bonded or coordinated to R ^1b or R ⁵ . Formula 3 [Chemical Formula 4] In Formula 3, Z ¹ and Z ² are each independently a non-metallic atomic group forming a nitrogen-containing heterocyclic ring of 5 or 6 members, and R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, and an alkyne group. Group, aralkyl group or aryl group, L ¹ represents a methine chain containing an odd number of methine groups, a and b are independently 0 or 1, and when a is 0, a carbon atom and a nitrogen atom are bonded by a double bond When b is 0, the carbon atom and nitrogen atom are bonded by a single bond. When the site represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c represents the number required to maintain the balance of the charge. When the site represented by Cy is an anion site, X ¹ represents a cation, and c represents a number required to maintain the balance of the charge. When the charge of the site represented by Cy is neutralized in the molecule, c 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 replaced by an acidic group, a basic group, or an iminomethyl phthalate. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferred from the viewpoint of dispersibility and dispersion stability of the colorant A. It is particularly preferred that the pigment derivative has a basic group. The combination of the 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 the organic pigment used to constitute the pigment derivative include dioxopyrrolopyrrole-based pigments, azo-based pigments, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, and dioxazine-based pigments. , Ringone-based pigments, fluorene-based pigments, thioindigo-based pigments, isoindolinone-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, Shihlin-based pigments, and metal complex-based pigments. As the acidic group of the pigment derivative, a sulfonic acid group, a carboxylic acid group, and a salt thereof are preferred, a carboxylic acid group and a sulfonic acid group are more preferred, and a sulfonic acid group is further preferred. As the basic group possessed by the pigment derivative, an amine group is preferable, and a tertiary amine group is more preferable.

When the curable composition contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass relative to the mass of the pigment. The pigment derivative may be used singly or in combination of two or more kinds.

[Photopolymerization initiator] The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of a polymerizable compound, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, those having photosensitivity in the ultraviolet region to the visible light region are preferred. In addition, it may be an active agent that has some effect with a photosensitized sensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of polymerizable compound. The photopolymerization initiator preferably contains at least one compound having a light absorption coefficient of at least about 50 moles in a wavelength region of about 300 nm to 800 nm (more preferably 330 nm to 500 nm.).

The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, and more than 1% by mass based on the total solid content of the curable composition. Particularly preferred, 30% by mass or less is preferred, 20% by mass or less is more preferred, 10% by mass or less is further preferred, and less than 10% by mass is particularly preferred. When the content of the photopolymerization initiator is more than 1% by mass and less than 10% by mass relative to the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent. The photopolymerization initiator may be used singly or in combination of two or more kinds. When two or more photopolymerization initiators are used at the same time, the total amount thereof is preferably within the above range.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton and those having an oxadiazole skeleton), fluorenylphosphine compounds such as fluorenylphosphine oxide, hexaarylbisimidazole, Oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and p-hydroxyacetophenone. Examples of the halogenated hydrocarbon compound containing the triazine skeleton include a compound described in Wakabayashi et al., A compound described in Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1384492, and Japan Compounds described in JP 53-133428, compounds described in German Patent No. 3370024, compounds based on FC Schaefer et al. J. Org. Chem .; 29, 1527 (1964), Japanese Patent Laid-Open Compounds described in JP 62-58241, compounds described in JP 5-281728, compounds described in JP 5-34920, compounds described in US Patent No. 4212976, and the like.

From the viewpoint of exposure sensitivity, it is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, fluorenylphosphine compounds, and phosphine oxides. Compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron Compounds and their salts, halogenated methyloxadiazole compounds, and 3-aryl-substituted coumarin compounds are preferred.

Among them, trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzophenone compounds, or acetophenone More preferably, the compound is at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an oxime compound, a triallyl imidazole dimer, and a benzophenone compound. Better.

In particular, when a curable composition is used in the production of a light-shielding film, it is necessary to develop a fine pattern into a clear shape, so that it is not only curable but also developed in a non-exposed area without leaving a residue. From such a viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when forming a fine pattern, exposure is performed using a stepper for curing exposure. However, the exposure machine may be damaged by halogen, and it is also necessary to suppress the addition amount of the photopolymerization initiator to be low. Considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator when forming a fine pattern. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and the contents are incorporated into this specification.

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

<Oxime compound> As a photopolymerization initiator, an oxime compound (oxime type initiator) is mentioned more preferably. In particular, an oxime compound is preferable because it has high sensitivity and high polymerization efficiency, and can harden the hardenable composition layer regardless of the concentration of the colorant, and it is easy to design the concentration of the colorant to be high. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, or a compound described in JP 2006-342166 can be used. Examples of the oxime compound include 3-benzyloxyiminobutane-2-one, 3-acetamidoiminobutane-2-one, and 3-propanyloxyimine Butan-2-one, 2-ethoxyloxyiminopentane-3-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4- Tosylsulfonyloxy) iminobutane-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and the like. In addition, JCSPerkinII (1979) pp. 1653-1660, JCSPerkinII (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, and Japanese Patent Application Laid-Open No. 2000- Compounds described in Japanese Unexamined Patent Publication No. 66385, Japanese Unexamined Patent Publication No. 2000-80068, Japanese Unexamined Patent Publication No. 2004-534797, and Japanese Unexamined Patent Publication No. 2006-342166. Commercially available products can also use IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF). Also, TR-PBG-304 (manufactured by Changzhou Qiangli Electronics New Material Co., Ltd.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) or N-1919 (containing carbazoxime ester backbone light from Initiator (manufactured by ADEKA CORPORATION)).

As the oxime compound other than the above description, a compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole may be used; and US Patent No. 7626957 in which a heterosubstituent is introduced into a benzophenone site. Compounds described in the Gazette; compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a pigment part; ketoxime compounds described in International Publication No. 2009-131189; A compound described in US Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule; a compound described in Japanese Patent Application Laid-Open No. 2009-221114 that has a maximum absorption at 405 nm and a good sensitivity to a g-ray light source Wait. Preferably, for example, paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and the contents are incorporated into this specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. In addition, the oxime compound may be an oxime compound having an N-O bond of the (E) form, or an oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[Chemical Formula 5]

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

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

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

[Chemical Formula 6]

[Chemical Formula 7]

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

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

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

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

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

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

[Chemical Formula 8]

The oxime compound is preferably one having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably one having a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and one having a higher absorbance at 365 nm and 405 nm is particularly preferable. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured by a known method. For example, it can be measured with a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian Corporation) using an ethyl acetate solvent at a concentration of 0.01 g / L. A photopolymerization initiator can be used in combination of 2 or more types as needed.

[Polymerizable Compound] The curable composition contains a polymerizable compound. The content of the polymerizable compound is preferably 0.1 to 40% by mass based on the total solid content of the curable composition. The lower limit is, for example, more preferably 1.0% by mass or more, more preferably 3.5% by mass or more, and particularly preferably more than 3.5% by mass. The upper limit is, for example, preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably less than 20% by mass. When the content of the polymerizable compound is more than 3.5% by mass and less than 20% by mass based on the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent. The polymerizable compound may be used singly or in combination of two or more kinds. When two or more polymerizable compounds are used at the same time, the total amount thereof is preferably within the above range.

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

The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and such polymers, and monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 3,000, and more preferably 250 to 1,500. The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and more preferably a 3 to 6-functional (meth) acrylate compound. Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amidines. And their multimers are preferably esters of unsaturated carboxylic acid and aliphatic polyhydric alcohol compounds, amidines of unsaturated carboxylic acid and aliphatic polyamine compounds, and these multimers. In addition, it is also suitable to use unsaturated carboxylic acid esters or amidoamines containing nucleophilic substituents such as hydroxyl, amine, and mercapto groups, addition reaction products with monofunctional or polyfunctional isocyanates or epoxy compounds, and the aforementioned unsaturated Dehydration condensation reactants of carboxylic acid esters or amidines with monofunctional or polyfunctional carboxylic acids, and the like. In addition, unsaturated carboxylic acid esters or amidoamines containing electrophilic substituents such as isocyanate groups and epoxy groups, and reactants of monofunctional or polyfunctional alcohols, amines, thiols, or halogenated groups or Also suitable are reactants of unsaturated carboxylic acid esters or amidoamines having detachable substituents such as tosylsulfonyloxy group and monofunctional or polyfunctional alcohols, amines or thiols. Further, instead of the unsaturated carboxylic acid, a group of compounds substituted with an vinyl benzene derivative such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, or the like can be used. As their specific compounds, the compounds described in paragraphs 0095 to 0108 of Japanese Patent Application Laid-Open No. 2009-288705 can also be suitably used in the present invention.

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

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; Nippon Kayaku Co. , Ltd.) dipentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product) KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structure of these (meth) acrylfluorenyl groups via diethanol residues or propylene glycol residues (For example, SR454 to SR499 commercially available from Sartomer Company) is more preferred. Their oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used. The aspect of a preferable polymerizable compound is shown below.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or 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 an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to polymerize the acid group. The sexual compound is more preferable, and the aliphatic polyhydroxy compound in the ester is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include ARONIX TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

The preferable acid value of the polymerizable compound containing an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing and dissolving characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous for production and / or processing. Moreover, when it exists in the said range, a photopolymerization property is favorable and hardenability is excellent.

A compound containing a caprolactone structure is also a preferable aspect of the polymerizable compound. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include trimethylolethane, di-trimethylolethane, and trimethylolethane. Polyols such as methylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, and trimethylol melamine are esterified with (meth) acrylic acid and ε-caprolactone. The obtained ε-caprolactone modified polyfunctional (meth) acrylate. Among them, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferred.

[Chemical Formula 9]

In formula (Z-1), 6 R are all groups represented by the following formula (Z-2), or 1 to 5 of 6 R are groups represented by the following formula (Z-2), and the rest Is a group represented by the following formula (Z-3).

[Chemical Formula 10]

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

[Chemical Formula 11]

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

The polymerizable compound containing a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., Ltd. Examples include DPCA-20 (where m is 1 in formulas (Z-1) to (Z-3)) The number of groups represented by the formula (Z-2) is 2, and R ¹ is a compound having a hydrogen atom), DPCA-30 (in the formula, m is 1, the group of the group represented by the formula (Z-2) Compounds whose number is 3 and R ¹ is a hydrogen atom) CADPCA-60 (in the formula, m is 1, the number of groups represented by formula (Z-2) is 6, and R ¹ is a compound of hydrogen atom ), DPCA-120 (in the formula, m is 2, a compound having the number of groups represented by formula (Z-2) of 6, and R ¹ is a hydrogen atom), and the like.

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

[Chemical Formula 12]

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

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

The compound represented by the formula (Z-4) or the formula (Z-5) may be used singly or in combination of two or more kinds. In particular, in the formula (Z-5), the six Xs are all acrylfluorenyl groups, the compound in which (6) X is acrylfluorenyl compounds and at least one of the six Xs is a hydrogen atom. The mixture is preferred. With such a structure, developability can be further improved.

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

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

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

[Chemical Formula 13]

[Chemical Formula 14]

Examples of commercially available polymerizable compounds represented by the formulae (Z-4) and (Z-5) include SR-494, a four-functional acrylate containing four ethoxyl chains, manufactured by Sartomer Company. , DPCA-60, a 6-functional acrylate containing 6 pentamyloxy chains, TPA-330, etc., containing 6 isopentyloxy chains, manufactured by Nippon Kayaku Co., Ltd.

As the polymerizable compound, Polyurethanes described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Acrylic esters; those disclosed in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Urethane compounds are also preferred. In addition, by using an addition of an amine structure and / or a thioether structure described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238, It becomes a polymerizable compound and can obtain a hardenable composition which is very excellent in the speed of light. Examples of commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) , DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Co., Ltd.) and the like.

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

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

Formula (Q3) [Chemical Formula 15]

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

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

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

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

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

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

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

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

[Polyfunctional thiol compound] The curable composition contains a polyfunctional thiol compound. In this specification, a polyfunctional thiol compound means a thing which contains two or more thiol groups (namely, the group represented by -SH) in the same molecule. The content of the polyfunctional thiol compound is not particularly limited, and it is usually 1 to 10% by mass based on the content of the colorant. Among these, from the viewpoint that the curable composition has more excellent effects of the present invention, 1 to 5.5% by mass is more preferable, and 1.5 to 3.5% by mass is more preferable. The content of the polyfunctional thiol compound is more preferably 0.55 to 3.5% by mass, and even more preferably 0.8 to 2.0% by mass based on the total solid content of the curable composition. A polyfunctional thiol compound may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used at the same time, it is preferable that the total amount is within the above range.

The polyfunctional thiol compound is preferably a low-molecular compound having a molecular weight of 100 or more, specifically, a molecular weight of 100 to 1,500 is preferable, and a molecular weight of 150 to 1,000 is more preferable. The polyfunctional thiol compound contains two or more thiol groups in the molecule, preferably three or more, more preferably contains ten or less, more preferably contains six or less, and further contains four or less. good. Among them, the polyfunctional thiol compound is preferably trifunctional or more, and trifunctional or tetrafunctional is more preferred. When the polyfunctional thiol compound is trifunctional or more, the curable composition has more excellent effects of the present invention.

The polyfunctional thiol compound is preferably a compound having two or more groups represented by the following formula (1).

[Chemical Formula 16]

In formula (1), L ¹ represents a single bond or -CO-, and L ² represents a single bond or a divalent linking group. As the polyfunctional thiol compound, a compound containing 2 to 6 groups represented by formula (1) in each molecule is preferable, a compound containing 2 to 4 is more preferable, and a compound containing 3 or 4 Is even better. Examples of the divalent linking group in L ² in formula (1) include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, and an alkylene group). , Substituted alkynyl), divalent aromatic group (for example, arylene, substituted arylene), divalent heterocyclic group, oxygen atom (-O-), imino group (-NH-), Substituted imino group (-NR ^31- , wherein R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), a combination thereof, and the like. When the divalent linking group is an alkylene group, the carbon number of the alkylene group is preferably from 1 to 5, and more preferably from 1 to 2.

As the polyfunctional thiol compound, a compound represented by the following formula (2) having two or more groups represented by the formula (1) is more preferred.

[Chemical Formula 17]

In formula (1), L ¹ represents a single bond or -CO-, and L ² represents a single bond or a divalent linking group. X represents an n-valent linking group, and n represents an integer of 2 to 6. The plurality of L ¹ and L ² may be the same as or different from each other.

The states L of L ¹ and L ² in the formula (2) are the same as those in the formula (1). In formula (2), n is preferably 2 to 4, and 3 or 4 is more preferable. Examples of the n-valent linking group in formula (2), that is, X, include, for example:-(CH ₂ ) _m- (m represents an integer of 2 to 6.) Equivalent bivalent linking groups; having three trihydroxy groups A trivalent linking group such as a methylpropane residue and-(CH ₂ ) _p- (p represents an integer of 2 to 6.); a tetravalent linking group such as a pentaerythritol residue; or a pentavalent linking group. A hexavalent linking group such as a dipentaerythritol residue.

Specific examples of the polyfunctional thiol compound include 1,4-butanediol bis (mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate), and trimethylolpropane tri (3- Mercaptopropionate), pentaerythritol tetra (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetra (mercaptoacetate) , Pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutoxy) butane and 1,4-bis (3- Mercaptobutoxy) butane, 1,3,5-tris (3-mercaptobutoxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Wait. Among them, from the viewpoint that the curable composition has more excellent effects of the present invention, the polyfunctional thiol compound is selected from pentaerythritol tetrakis (3-mercaptopropionate) and trimethylolpropane tris (3-mercaptopropionate). More preferably, at least one of the groups consisting of esters is used.

[Optional component] <Polymerization inhibitor> The curable composition preferably contains a polymerization inhibitor. By containing a polymerization inhibitor, the curable composition has more excellent stability over time. In addition, in this specification, stability over time means that a cured film having an excellent pattern shape can be obtained even when stored for a predetermined period after the production of the curable composition. The polymerization inhibitor has a function of inhibiting the reaction between the polyfunctional thiol compound and the polymerizable compound in the hardening composition during storage, and it is estimated that the above-mentioned effect can be obtained. The content of the polymerization inhibitor relative to the content of the polyfunctional thiol compound is preferably 0.1 to 1.5% by mass, and more preferably 0.3 to 1.0% by mass. When the content of the polymerization inhibitor is within the above range, the curable composition has more excellent stability over time. In addition, the content of the polymerization inhibitor is preferably 0.00055 to 0.055 mass%, and more preferably 0.0015 to 0.01 mass% with respect to the total solid content of the curable composition.

The polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used. Examples of the compound used as a polymerization inhibitor include phenol-based compounds, quinone-based compounds, hindered amine-based compounds, phenothiazine-based compounds, and nitrobenzene-based compounds. These compounds may be used individually by 1 type, and may use 2 or more types together.

Examples of the phenol-based compound include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butylcatechol, and 2,6 -Di-tertiary-butylphenol, 2,6-di-tertiary-butyl 4-methylphenol, 2,6-di-tertiary-butyl 4- and phenol, 4-hydroxymethyl-2,6- Di-Third-Butylphenol, Pentaerythritol Tetrakis (3,5-Di-Third-Butyl 4-Hydroxyphenylpropionate), 4-methoxy-1-naphthol, and 1,4-dihydroxynaphthalene Wait.

As the phenolic compound, a phenolic compound represented by the formula (IH-1) is preferable.

[Chemical Formula 18]

In the formula (IH-1), R ₁ to R ₅ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group, an amine group, an aryl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a fluorenyl group. R ₁ to R ₅ may be connected to each other to form a ring.

As R ₁ to R ₅ in formula (IH-1), a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, methyl and ethyl), and an alkoxy group having 1 to 5 carbon atoms (for example, methyl An oxy group, an ethoxy group, etc.), an alkenyl group (for example, a vinyl group, etc.) having 2 to 4 carbon atoms, or a phenyl group is preferred. Among them, R ₁ and R ₅ are each preferably a hydrogen atom or a third butyl group, R ₂ and R ₄ are more preferably a hydrogen atom, R ₃ is a hydrogen atom, or an alkyl group or carbon having 1 to 5 carbon atoms. An alkoxy group having a number of 1 to 5 is more preferred.

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

Examples of the hindered amine-based compound include a polymerization inhibitor represented by the following formula (IH-2).

[Chemical Formula 19]

R ₆ in formula (IH-2) represents a hydrogen atom, a hydroxyl group, an amine group, an alkoxy group, an alkoxycarbonyl group, or a fluorenyl group. Among them, a hydrogen atom or a hydroxyl group is preferable, and a hydroxyl group is more preferable. R ₇ to R ₁₀ in the formula (IH-2) each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R ₇ to R ₁₀ is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.

As the polymerization inhibitor, each of the above-mentioned compounds may be used alone or in combination of two or more of them. The polymerization inhibitor preferably contains a phenolic compound. Among them, the polymerization inhibitor preferably contains two or more phenolic compounds. The curable composition containing different phenolic compounds has more excellent effects of the present invention. The polymerization inhibitor preferably contains a phenol-based compound and a hindered amine-based compound. The curable composition containing a phenol-based compound and a hindered amine-based compound has more excellent effects of the present invention.

<Solvent> The curable composition preferably contains a solvent. Examples of the solvent include water and organic solvents. The curable composition preferably contains an organic solvent. When the curable composition contains a solvent, the solid content of the curable composition is preferably 10 to 40% by mass. When the solid content of the curable composition is at least the lower limit value, the viscosity is low, and the coatability is optimized. Furthermore, as the concentration of the more reactive compound becomes lower, the stability over time is optimized. When the solid content of the curable composition is equal to or less than the upper limit value, the viscosity is kept low, and the coatability is optimized. Moreover, the coloring agent with a heavy specific gravity is difficult to settle, and the stability over time is optimized.

(Organic Solvent) When the curable composition contains an organic solvent, the content of the organic solvent is preferably 60 to 90% by mass based on the total mass of the curable composition. The organic solvents may be used alone or in combination of two or more. When two or more organic solvents are used at the same time, the total amount thereof is preferably within the above range.

The organic solvent is not particularly limited, and examples thereof include acetone, methyl ethyl ketone, cyclohexane, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ether acetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamidine, dimethylmethylene , Γ-butyrolactone, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl 3-methoxypropionate, 2-heptanone , Ethyl carbitol acetate, butyl carbitol acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and the like.

When two or more organic solvents are contained, it is selected from the group consisting of the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol It is preferable that two or more types of the group consisting of monomethyl ether and propylene glycol monomethyl ether acetate are constituted.

(Water) The curable composition may contain water. Water may be intentionally added, or may be unavoidably contained in the hardening composition by adding each component contained in the hardening composition. The content of water is preferably 0.01 to 1% by mass based on the total mass of the curable composition. When the content of water is within the above range, pinholes are suppressed from being produced when the cured film is produced, and the moisture resistance of the cured film is improved.

<Dispersant> The curable composition preferably contains a dispersant. The dispersant helps improve the dispersibility of the colorant. In this specification, a dispersant is a component different from the binder resin mentioned later.

When the hardening composition contains a dispersant, the content of the dispersing agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 5% by mass or more relative to the total solid content of the hardening composition. A mass% or more is particularly preferable, and a mass of 17% or more is best. The upper limit of the content of the dispersant is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 22% by mass or less with respect to the total solid content of the curable composition. When the content of the dispersant is 17% by mass or more, the pattern shape of the cured film obtained by curing the curable composition is more excellent. The dispersant may be used singly or in combination of two or more kinds. When two or more dispersants are used simultaneously, the total amount is preferably within the above range.

As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Among them, a polymer compound is preferred. Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acids and their salts, high-molecular-weight unsaturated esters, modified polyurethanes, modified polyesters, Modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and pigment derivatives. Based on their structure, polymer compounds can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers.

(Polymer Compound) The polymer compound is adsorbed on the surface of the dispersion such as a colorant (for example, an inorganic pigment), and plays a role of preventing re-aggregation of the dispersion. Therefore, it is preferable to include a terminally modified polymer, a graft polymer, and a block polymer that are fixed to the pigment surface.

The polymer compound preferably contains a structural unit including a graft chain. In this specification, "structural unit" has the same meaning as "repeating unit". This polymer compound containing a structural unit containing a graft chain has an affinity with a solvent through the graft chain, so it is a dispersibility of a colorant such as a black pigment and a dispersion stability over time (stability over time) Outstanding. A polymer compound containing a structural unit containing a graft chain has an affinity with a polymerizable compound or other resins that can be used together due to the presence of the graft chain. As a result, residues are less likely to occur in alkaline development. When the graft chain becomes longer, the steric repulsion effect increases and the dispersibility of a black pigment or the like improves. On the other hand, if the graft chain is too long, the adsorption force to a colored pigment such as a black pigment decreases, and the dispersibility of the black pigment or the like tends to decrease. Therefore, it is preferable that the number of atoms other than hydrogen atoms is 40 to 10,000, the number of atoms other than hydrogen atoms is 50 to 2,000, and the number of atoms other than hydrogen atoms is 60 to 500. good. Herein, the graft chain represents the root of the main chain of the copolymer (the atom bonded to the main chain from the main chain branched group) to the end of the main chain branched group.

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

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

Corresponding to the structural unit containing the graft chain contained in the polymer compound, examples of commercially available macromonomers suitable for the synthesis of the polymer compound include AA-6 (trade name, Toagosei Company, Limited.), AA -10 (trade name, manufactured by Toagosei Company, Limited.), AB-6 (trade name, manufactured by Toagosei Company, Limited.), AS-6 (trade name, Toagosei Company, Limited.), AN-6 (trade name, Toagosei Company, Limited.), AW-6 (trade name, manufactured by Toagosei Company, Limited.), AA-714 (trade name, manufactured by Toagosei Company, Limited.), AY-707 (trade name, Toagosei Company, Limited. (Manufactured), AY-714 (trade name, manufactured by Toagosei Company, Limited.), AK-5 (trade name, manufactured by Toagosei Company, Limited.), AK-30 (trade name, manufactured by Toagosei Company, Limited.), AK- 32 (trade name, manufactured by Toagosei Company, Limited.), Blemmer PP-100 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-500 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-800 (trade name, NOF CORPORATION.), B lemmer 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 (product Name, NOF CORPORATION.), Blemmer PSE-1300 (trade name, manufactured by NOF CORPORATION.), Blemmer 43PAPE-600B (trade name, manufactured by NOF CORPORATION.), Etc. Among them, AA-6 (trade name, manufactured by Toagosei. Company, Limited.), AA-10 (trade name, manufactured by Toagosei Company, Limited.), AB-6 (trade name, manufactured by Toagosei Company, Limited.), And AS- 6 (trade name, Toagosei Company, Limited.), AN-6 (trade name, manufactured by Toagosei Company, Limited.), And Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.) Are preferred.

The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. It is further preferred that 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 dispersant may include the above-mentioned structure alone in one dispersant, or may include a plurality of such structures in one dispersant. Among them, the polycaprolactone structure refers to a structure containing a ring-opening of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing, as a repeating unit, a ring opening of δ-valerolactone. Specific examples of the dispersant containing a polycaprolactone structure include those in which j and k in the following formula (1) and the following formula (2) are five. Further, specific examples of the dispersant containing a polyvalerolactone structure include those in which j and k are 4 in the following formula (1) and the following formula (2). Specific examples of the dispersant containing a polymethyl acrylate structure include those in which X ⁵ in the following formula (4) is a hydrogen atom and R ⁴ is a methyl group. Further, as a specific example of polymethyl methacrylate containing structures of the dispersing agent include the following formula (4) X ⁵ is methyl and R ⁴ is methyl persons.

・ The structural unit containing the graft chain The polymer compound as the structural unit containing the graft chain preferably contains a structural unit represented by any one of the following formulae (1) to (4), and contains the following formula (1A) The structural unit represented by any one of the following formula (2A), the following formula (3A), the following formula (3B), and the following (4) is more preferable.

[Chemical Formula 20]

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

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

[Chemical Formula 21]

In Formulas (1) to (4), Z ¹ , Z ² , Z ^3, and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group. And amine groups. Among these, as the organic group represented by Z ¹ , Z ² , Z ^3, and Z ⁴ , especially from the viewpoint of improving dispersibility, it is preferable to include a stereorepulsive effect, and each independently has a carbon number of 5 to 24. Alkyl or alkoxy groups are more preferred, in which branched alkyl groups having 5 to 24 carbon atoms, cyclic alkyl groups with 5 to 24 carbon atoms, or alkoxy groups with 5 to 24 carbon atoms, respectively, are further preferred. good. The alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic groups.

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

In the formula (3), R ³ represents a branched or linear alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 2 or 3 carbon atoms is more preferred. When p is 2 to 500, a plurality of R ³ may be the same as each other or different from each other. In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferred. A linear alkyl group is more preferred, and a linear alkyl group having 1 to 6 carbon atoms is more preferred. In formula (4), when q is 2 to 500, a plurality of X ⁵ and R ^{4 in the} graft copolymer may be the same as each other or different from each other.

The polymer compound may contain two or more different structural units having a structural unit of a graft chain. That is, the molecules of the polymer compound may include structural units represented by formulas (1) to (4), which are different from each other. In formulas (1) to (4), n, m, p, and q are respectively When an integer of 2 or more is represented, in the formulae (1) and (2), a structure in which j and k are different from each other may be included in the side chain. In the formulae (3) and (4), a plurality of molecules exist in the molecule. R ³ , R ⁴ and X ⁵ may be the same as each other or different from each other.

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

[Chemical Formula 22]

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

As the structural unit represented by the formula (3), a structural unit represented by the following formula (3A) or formula (3B) is more preferred from the viewpoint of the stability over time and developability of the curable composition.

[Chemical Formula 23]

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

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

In the polymer compound, the structural unit containing the graft chain (for example, the structural unit represented by the above formula (1) to formula (4)) is 2 to 90% by mass conversion with respect to the total mass of the polymer compound. The range is preferable, and the range of 5 to 30% is more preferable. When the structural unit containing a graft chain is included in this range, the dispersibility of a black pigment is high, and the developability at the time of forming a hardened film is favorable.

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

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

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

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

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

[Chemical Formula 24]

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

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

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

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

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

L is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethyl structure or an oxypropyl structure. L may contain a polyoxyalkylene structure which repeatedly contains two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, where n is an integer of 2 or more is preferred, and an integer of 2 to 10 is more preferred.

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

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 10. The aliphatic group also includes a ring group hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the ring group hydrocarbon group include dicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the crosslinked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, and bicyclic octane ring (bicyclic [2.2.2] Octane ring and bicyclic [3.2.1 octane ring, etc.) and other bicyclic hydrocarbon rings, homoblane (homobledane), adamantane, tricyclic [5.2.1.0 ^{2 , 6} ] decane and tricyclic [4.3. cyclic hydrocarbon ring 3 1.1 ^{2, 5]} undecane ring, and tetracyclo ^{[4.4.0.1 2, 5 .1 7,} 10] dodecane and perhydro-1,4--5,8 -4-ring hydrocarbon rings such as a methylene naphthalene ring and the like. Crosslinked cyclic hydrocarbon rings also include condensed cyclic hydrocarbon rings, such as perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydrofluorene, perhydrofluorene, perhydroindene, and perhydrofluorene rings Isocondensation has multiple 5 to 8-membered cycloalkane rings. It is more preferable that the aliphatic group is a saturated aliphatic group than the unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

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

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

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

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

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

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

・ Functional groups that can interact with colorants such as black pigments Polymer compounds can introduce functional groups that can interact with colorants such as black pigments. Among them, the polymer compound preferably contains a structural unit containing a functional group capable of interacting with a colorant such as a black pigment. Examples of the functional group that can interact with a colorant such as the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group. When a polymer compound contains an acid group, a basic group, a coordinating group, or a reactive functional group, it contains a structural unit containing an acid group, a structural unit containing a basic group, and a structural unit containing a coordination group, respectively. Or a reactive structural unit is preferable. In particular, the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, whereby the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound serving as a dispersant that facilitates the dispersion of a colorant such as a black pigment in the curable composition has alkali-solubility. The curable composition containing such a polymer compound becomes an excellent light-shielding property of the exposed portion, and the alkali developability of the unexposed portion is improved. Since the polymer compound has a structural unit containing an acid group, the polymer compound tends to be easily integrated with a solvent, and the coatability is also improved. This is presumably because the acid group in the structural unit containing the acid group easily interacts with the coloring agent such as a black pigment, the polymer compound stably disperses the coloring agent such as the black pigment, and the polymer compound dispersing the coloring agent such as the black pigment. The viscosity becomes low, and the polymer compound itself is easily and stably dispersed.

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

As the functional group that can interact with colorants such as black pigments, that is, acid groups, for example, there are carboxylic acid groups, sulfonic acid groups, phosphate groups, or phenolic hydroxyl groups. At least one of them is preferable, and from the viewpoints of good adsorption of a colorant such as a black pigment and high dispersibility of the colorant, a carboxylic acid group is more preferable. That is, the polymer compound preferably has a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or two or more kinds of structural units containing an acid group. The polymer compound may or may not contain a structural unit having an acid group. When it is contained, the content of the structural unit having an acid group is expressed in terms of mass. It is preferably 5 to 80% relative to the total mass of the polymer compound. From the viewpoint of damage to the image strength of alkali development, 10 to 60% is more preferable.

As a functional group that can interact with a colorant such as a black pigment, that is, a basic group, there are, for example, a primary amine group, a secondary amine group, a tertiary amine group, a heterocyclic ring containing an N atom, and amidino group. A tertiary amine group is preferable from the viewpoints that a colorant such as a black pigment has good adsorption and a high dispersibility of the pigment. The polymer compound may contain one or more of these basic groups. The polymer compound may or may not contain a structural unit having a basic group. When contained, the content of the structural unit having a basic group is calculated in terms of mass, and is 0.01% or more and 50% or less with respect to the total mass of the polymer compound. Preferably, from the viewpoint of suppressing the development resistance, 0.01% or more and 30% or less are more preferable.

Examples of the functional group that can interact with a colorant such as a black pigment, that is, a coordinating group and a reactive functional group include, for example, ethanoylacetoxy, trialkoxysilyl, Isocyanate groups, acid anhydrides, fluorenyl chloride, etc. From the standpoint of good adsorption of colorants such as black pigments and high dispersibility of pigments, ethanoylacetoxy is preferred. The polymer compound may have one or two or more of these groups. The polymer compound may contain a structural unit having a coordinating group or a reactive functional group, or may not contain it. When contained, the content of these structural units is calculated in terms of mass and is 10% relative to the total mass of the polymer compound. It is more preferable that it is more than 80%, and it is more preferable that it is 20% or more and 60% or less from the viewpoint of suppressing the obstructive development property.

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

[Chemical Formula 25]

In the formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkane having 1 to 6 carbon atoms. (For example, methyl, ethyl, propyl, etc.). In the formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each of them is independently a hydrogen atom or a methyl group. good. In the general formula (iv), R ¹² and R ¹³ are each preferably a hydrogen atom.

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

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

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

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

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

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

In the formulae (iv) to (vi), Z ₁ represents a functional group capable of interacting with a coloring agent such as a black pigment other than the graft chain. A carboxylic acid group and a tertiary amine group are preferred, and a carboxylic acid group is more preferred. good.

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

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

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

From the viewpoints of interaction with a coloring agent such as a black pigment, dispersion stability, and permeability to a developing solution, the content of the structural unit containing a functional group that can interact with the coloring agent such as a black pigment is higher than that of the polymer compound Of the total mass, 0.05% to 90% by mass is more preferred, 1.0% to 80% by mass is more preferred, and 10% to 70% by mass is even more preferred.

・ Other structural units In addition, in order to improve various properties such as image strength, polymer compounds can be added before the effects of the present invention are impaired, and further contain structural units containing graft chains, hydrophobic structural units, and containing black pigments. The structural units such that the functional groups that the colorant forms interact with are different from other structural units having various functions (for example, structural units having functional groups that have an affinity with the dispersion medium used for the dispersion, etc.). Examples of such other structural units include structural units derived from a radical polymerizable compound selected from acrylonitrile and methacrylonitrile. The polymer compound can use one or two or more of these other structural units, and its content is expressed in terms of mass, and relative to the total mass of the polymer compound, 0% to 80% is preferred, and 10% to 60% is preferred. The following is better. When the content is within the above range, sufficient pattern-formability can be maintained.

・ Physical properties of the polymer compound The acid value of the polymer compound is preferably in a range of 0 mgKOH / g to 250 mgKOH / g, more preferably in a range of 10 mgKOH / g to 200 mgKOH / g, and in a range of 20 mgKOH / g to 120 mgKOH / The range below g is more preferable. When the acid value of the polymer compound is 160 mgKOH / g or less, the pattern peeling during development when forming a cured film is more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH / g or more, alkali developability is further improved. In addition, if the acid value of the polymer compound is 20 mgKOH / g or more, it is possible to further suppress sedimentation of a colorant such as a black pigment, reduce the number of coarse particles, and further improve the stability of the curable composition over time.

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

When the light-shielding film is formed, the weight average molecular weight of the polymer compound in the present invention is aggregated by a GPC (Gel Permeation Chromatography) method from the viewpoints of suppression of pattern peeling at the time of development and developability. The styrene conversion value is preferably from 4,000 to 300,000, more preferably from 5,000 to 200,000, more preferably from 6,000 to 100,000, and even more preferably from 10,000 to 50,000. The GPC method is based on a method using HLC-8020GPC (manufactured by TOSOH CORPORATION.) As a column using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID × 15cm), and using it THF (tetrahydrofuran).

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

Specific examples of the polymer compound include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., and "Disperbyk-101 (polyamidamine phosphate)", 107 (carboxylic acid ester), and 110 (contained by BYK Chemie). Acid-based copolymers), 111 (phosphoric acid-based dispersant), 130 (polyamidamine), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymers), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA4047, 4050-4010 to 4165 (polyurethane type), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (modified polymer) manufactured by EFKA Corporation Acrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fine- "AJISPER PB821, PB822, PB880, PB881" manufactured by Techno Co., Inc., "Flowlen TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., Ltd., "polyflow No. 50E, No. .300 (acrylic copolymer) "," disparon KS-860, 87 "manufactured by Kusumoto Chemicals, Ltd. 3SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "," DEMOL RN, N (naphthalenesulfonic acid) manufactured by Kao Corporation Formalin polycondensate), MS, C, SN-B (formalin polycondensate of aromatic sulfonic acid) "," HOMOGENOL L-18 (polymeric polycarboxylic acid) "," EMULGEN920, 930, 935, 985 (polyoxygen Ethylene Nonyl Phenyl Ether) "," ACETAMIN86 (Stearamine Acetate) "," Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) manufactured by Lubrizol Japan Limited, 3000, 12000, 17000, 20000, 27000 (polymers with functional parts at the ends), 24000, 28000, 32000, 38500 (graft copolymers) "," NIKKOL T106 (Polymer) manufactured by Nikko Chemicals Co., Ltd. Oxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene stearate) "," HINOACT T-8000E "manufactured by Kawaken Fine Chemicals Co., Ltd., etc., Shin-Etsu Chemical Co. ,, Ltd. manufactures "organosiloxane polymer KP341" and Yusho Co., Ltd. manufactures "W001: cationic surfactant" , Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol laurate, polyethylene Non-ionic surfactants such as glycol distearate and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017", "EFKA-46, manufactured by Morishita Sangyo Co., Ltd. EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", manufactured by SAN NOPCO LIMITED" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 " Polymer dispersants such as ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 manufactured by ADEKA CORPORATION , And "Ionet (trade name) S-20" manufactured by Sanyo Chemical Industries, Ltd. and the like. In addition, Acrylic base FFS-6752, Acrylic base FFS-187, Akurikuya-RD-F8, and Cyclomer P can also be used. Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, manufactured by BYK Chemie GmbH, and the like. DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822, and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. and the like. These polymer compounds may be used individually by 1 type, and may use 2 or more types together.

As specific examples of the polymer compound, reference may be made to the polymer compound described in paragraphs 0127 to 0129 of Japanese Patent Application Laid-Open No. 2013-249417, which are incorporated herein.

As the dispersant, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of Japanese Patent Application Laid-Open No. 2010-106268 (corresponding to the columns of paragraphs 0075 to 0133 of US2011 / 0124824) can be used. The contents can be referred to and incorporated into this manual. In addition to the above, paragraphs 0028 to 0084 of Japanese Patent Application Laid-Open No. 2011-153283 (corresponding to the columns of paragraphs 0075 to 0133 of US2011 / 0279759) containing side chain structures containing acidic groups bonded through a linking group can also be used. The polymer compounds constituting the constituents can be referred to and incorporated in this specification.

<Adhesive resin> It is preferable that the curable composition contains an adhesive resin. The content of the binding resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, more preferably 0.9% by mass or more, particularly preferably 1.9% by mass or more, and 30% by mass of the total solid content of the curable composition. % Or less is preferred, 25% by mass or less is more preferred, 18% by mass or less is further preferred, and 10% by mass or less is particularly preferred. When the content of the binder resin is 1.9% by mass or more and 10% by mass or less, the pattern shape of the cured film obtained by curing the curable composition is more excellent. The adhesive resin can be used singly or in combination of two or more kinds. When two or more types of adhesive resins are used at the same time, the total amount is preferably within the above range.

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

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

Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable ethylene monomers as necessary] copolymers and [allyl (meth) acrylate / (meth) acrylic acid] / Other addition polymerizable ethylene monomers according to need] The copolymer has excellent film strength, sensitivity, and developability, and it is preferable. Examples of commercially available products include Acrylic base FF-187, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.), Akurikuya-RD-F8 (NIPPON SHOKUBAI CO., LTD.), And DAICEL-ALLNEX LTD. Manufacture of Cyclomer P (ACA) 230AA, etc.

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

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

(Constitution unit containing an acid group) As the constitutional unit containing an acid group, it is preferable to contain one or more kinds of constitutional units selected from constitutional units derived from monomers represented by the following formulae (vii) to (ix).

[Chemical Formula 26]

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

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

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

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

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

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

L ₂ is preferably a divalent linking group containing a single bond, an alkylene group, or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethyl structure or an oxypropyl structure. L ₂ may include a polyoxyalkylene structure which repeatedly includes two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, where n is an integer of 2 or more is preferred, and an integer of 2 to 10 is more preferred.

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

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

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

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

The adhesive resin may have one or two or more kinds of structural units containing an acid group. The content of the structural unit containing an acid group is calculated in terms of mass, and is preferably 5 to 95% relative to the total mass of the adhesive resin. From the viewpoint of suppressing damage to image strength caused by alkali development, 10 to 90% is more preferable. .

<Surfactant> The curable composition preferably contains a surfactant. The surfactant helps improve the coatability of the curable composition.

When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass relative to the total mass of the curable composition. The surfactant can be used singly or in combination of two or more kinds. When two or more surfactants are used simultaneously, the total amount is preferably within the above range.

Examples of the surfactant include a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.

For example, when the curable composition contains a fluorine-based surfactant, the liquid characteristics (in particular, the fluidity) of the curable composition are further improved. That is, when a film is formed using a curable composition containing a fluorine-based surfactant, by reducing the interfacial tension between the surface to be coated and the coating liquid, the wettability to the surface to be coated is improved, The coatability of the coated surface is improved. Therefore, even when a thin film having a thickness of several μm is formed with a small amount of liquid, it is more effective to form a thin film with less thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content ratio within 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 hardening composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac F475, Megafac F475, Megafac F475, Megafac F482, Megafac F554, Megafac F780 (above, manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC- 104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, a block polymer can also be used. As a specific example, for example, a compound described in Japanese Patent Application Laid-Open No. 2011-89090 can be mentioned. Examples of the fluorine-based surfactant include a compound (F-1) represented by the following formula. In the compound (F-1), the 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, b, and c satisfy the relationships of a + c = 14 and b = 17, respectively. The weight average molecular weight of the following compound is, for example, 15,311.

[Chemical Formula 27]

Specific examples of the non-ionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates such as glycerol propoxylate and glycerol. Ethoxylates, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901 manufactured by BASF) , 904, 150R1), Solsperse 20000 (manufactured by Japan Lubrizol Corporation), and the like. In addition, Pionin D-6112-W manufactured by TAKEMOTO OIL & FAT CO., LTD, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

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

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

Examples of the silicone-based surfactants include "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA" manufactured by Dow Corning Toray Co., Ltd. , "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray Silicone SH8400", Momentive Performance Materials Inc. manufacture "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", " TSF-4452 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Chemical Co., Ltd.," BYK307 "," BYK323 "," BYK330 ", etc. manufactured by BYK Chemie GmbH.

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

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

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

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

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

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

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

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

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

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

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

The curable composition may contain one type of silane coupling agent alone, or may contain two or more types. When the curable composition contains two or more kinds of silane coupling agents, the total amount may be within the above range.

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

[Manufacturing method of curable composition] The manufacturing method of the curable composition includes the following mixing and dispersion processes. It is preferred to include a static process and / or a filtration process. Hereinafter, preferred aspects of each process will be described in detail.

[Mixing and Dispersing Process] The mixing and dispersing process is a process for obtaining a hardenable composition by mixing the above components by a known mixing method (for example, a mixer, a homogenizer, a high-pressure emulsification device, a wet pulverizer, and a wet disperser). . In the mixing and dispersing process, the components constituting the hardenable composition may be blended at one time, or the components may be blended sequentially after being dissolved or dispersed in an organic solvent. The input sequence and operating conditions at the time of cooperation are not particularly limited. The mixing and dispersion process may include a process for making a dispersion.

(Manufacturing Process of Dispersion Liquid) The manufacturing process of the dispersion liquid is a process of mixing a colorant, a dispersant, and a solvent, and dispersing the colorant by the method described above to prepare a dispersion liquid. A hardening composition can be manufactured by mixing other components with the produced dispersion liquid. In the manufacturing process of the dispersion liquid, as the mechanical force for dispersing the pigment, compression, pressing, impact, cutting, or pitting can be mentioned. Specific examples of these processes include bead milling, sand mixing, roll milling, high-speed impeller, sand milling, jet flow mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, it is possible to appropriately use "Comprehensive Dispersion Technology, Issued by Information Corporation, July 15, 2005" and "Distribution technology centered on suspension (solid / liquid dispersion system) and practical comprehensive information on industrial applications Collected and distributed by the Publishing Department of the Operation and Development Center, October 10, 1978 ". In the production process of the dispersion liquid, the pigment can be miniaturized by the salt milling process. The raw materials, equipment, and processing conditions used in the salt milling process can be, for example, those described in Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application No. 2012-046629. It is preferable that the manufacturing method of a hardenable composition contains the manufacturing process of the said coloring agent by a thermo-plasma method. The process of obtaining a coloring agent is performed before mixing each said component. The state of the specific manufacturing process of the toner based on the thermoplasma method is as described above.

<Standing process> The colorant may be subjected to the following standing process before being supplied to a mixing and dispersion process or a process for preparing a dispersion. The stationary process is a process in which the toner obtained by the thermoelectric plasma method is not exposed to the atmosphere after it is manufactured, but in a sealed container whose oxygen concentration is controlled, and is allowed to stand for a predetermined time (12 to 72 hours is preferred, 12 ~ 48 hours is more preferred, and 12 to 24 hours is more preferred). At this time, it is preferable to control the content of moisture in the sealed container.

At this time, the oxygen (O ₂ ) concentration and the moisture content in the sealed container are preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. The oxygen (O ₂ ) concentration and the water content in the sealed container can be adjusted by adjusting the oxygen concentration and the amount of water in the inert gas supplied into the sealed container. As the inert gas, nitrogen and argon are preferred, and nitrogen is more preferred. After the above-mentioned standing process, the surface and grain boundaries of the colorant become stable. This makes it possible to suppress the occurrence of pinholes in the cured film obtained by curing the curable composition. In addition, the above-mentioned standing process can be replaced by the process H described in the method for producing a colorant. From the viewpoint that the curable composition has more excellent effects of the present invention, it is preferable to replace the process H.

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

[Curable film (light-shielding film)] The cured film is obtained by curing the above-mentioned curable composition. The cured film contains a colorant. The cured film is suitably used as a light-shielding film, and specifically, it is suitably used as a light-shielding portion around the light-receiving portion of the image sensor. Hereinafter, a case where a cured film is used as a light-shielding film in a peripheral portion of a light-receiving portion of an image sensor will be described as an example.

The film thickness of the light-shielding film is not particularly limited. In view of the fact that the light-shielding film has more excellent effects of the present invention, the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and 0.3 μm or more and 10 μm. The following is more preferred, and more preferably 0.3 μm to 5 μm. The above-mentioned curable composition has a high optical density per unit volume (high light-shielding property), and therefore it is possible to further reduce the film thickness compared with conventional curable compositions using black pigments. As the size of the light-shielding film (the length of one side of the light-shielding film provided around the light-receiving portion of the sensor), from the standpoint that the light-shielding film has more excellent effects of the present invention, 0.001 mm or more and 10 mm or less is preferred, and 0.05 mm It is more preferable that it is 7 mm or more, and it is more preferable that it is 0.1 mm or more and 3.5 mm or less.

[Manufacturing method of cured film] Next, a manufacturing method of the cured film (light-shielding film) will be described. Hereinafter, the manufacturing method will be described in detail for each process.

The manufacturing method of a cured film contains the following curable composition layer formation process and exposure process. It is preferable that the manufacturing method of a cured film also contains a developing process. Hardening composition layer forming process: a process of forming a hardening composition layer on a support. Exposure process: a process of exposing the curable composition layer. Development process: A process of developing the cured curable composition layer to form a patterned cured film (light-shielding film).

Specifically, the curable composition is applied directly or via another layer on a substrate to form a curable composition layer (curable composition layer forming process), is exposed through a predetermined mask pattern, and is exposed only to light. The irradiated coating film is partially cured (exposure process), and developed using a developer (development process), whereby the cured film can be produced. Each of the above processes will be described below.

<Curable composition layer formation process> The curable composition layer formation process is a process of forming a curable composition layer on a support (hereinafter, also referred to as a "substrate"). Among them, a coating process including applying a hardenable composition on a support to form a hardenable composition layer is preferred, and directly including applying a hardenable composition on a support to form a hardenable composition on the support. The coating process is better. As the substrate, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, and photoelectric conversion element substrates for those having a transparent conductive film attached thereto and used for solid-state imaging elements, etc. (Eg, silicone substrate, etc.), CCD (Charge Coupled Device) substrate, and CMOS (Complementary Metal-Oxide Semiconductor) substrate. In order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate, an undercoat layer may be provided on these substrates as needed.

As a method of applying a hardenable composition to a substrate, various coating methods such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, and a screen printing method can be applied.

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

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

<Exposure Process> The exposure process is a process of exposing the curable composition layer (coating film) formed in the curable composition layer forming process through a mask, and curing only a part of the coating film irradiated with light. The exposure is preferably performed by irradiation with actinic rays or radiation. In particular, ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably used, and a high-pressure mercury lamp is more preferable. Exposure amount is not particularly limited, 200mJ / cm ² or more is preferred, 200 ~ 1,500mJ / cm ² is more preferably, 200 ~ 1,000mJ / cm ² is further preferred, 200 ~ 500mJ / cm ² is particularly preferred. When the exposure amount is within the above range, the method for producing a cured film has more excellent stability and productivity. From the viewpoint of improving the resolution, in the formation of a light-shielding film for a solid-state imaging element, exposure by an i-ray stepper is preferable.

<Developing Process> The developing process is a process of developing the exposed curable composition layer. Through the development process, a patterned cured film can be obtained. It is preferable that the manufacturing method of the said hardened film contains a developing process and the following washing process. During the development process, an alkaline development process (development process) is performed to dissolve the light-irradiated part in the exposure process into an alkaline aqueous solution. Thereby, only the light-hardened portion (the portion of the coating film irradiated with light) remains. As the developing solution, when a light-shielding color filter containing a black matrix for a solid-state imaging element is produced, an organic alkaline developing solution that does not damage the circuit of the substrate or the like is preferable. The developing temperature is usually preferably 20 to 30 ° C, and the developing time is preferably 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. Examples of the inorganic developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, or sodium metasilicate, and the concentration thereof is 0.001 to 10% by mass, and preferably 0.01 to 1% by mass alkaline aqueous solution. Examples of the organic developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8- An organic basic compound such as diazabicyclo- [5.4.0] -7-undecene is dissolved into an alkaline aqueous solution having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. To the alkaline aqueous solution, for example, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant can be added. In addition, as the development method, for example, a spin-on immersion development and a shower development method can be used.

<Washing Process> The washing process is a process of washing (rinsing) the developed curable composition layer with pure water or the like. The cleaning method is not particularly limited, and a known cleaning method can be used.

In addition, the method for manufacturing a cured film may include a baking process after heating the cured film and / or a curing process of exposing the entire surface of the cured film after the development process.

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

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

[Image display device] The cured film is suitable for an image display device (for example, a liquid crystal display device and an organic electroluminescence display device).

The definition of image display devices and the details of each image display device are described in, for example, "Electronic Display Device (by Sasaki Akio, Kogyo Chosakai Publishing Co., Ltd. 1990)" and "Display Device (Ibuki Junaki Book, industry book (published in the 1st year of Heisei) ". The liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994). The cured film is suitable for, for example, a liquid crystal display device according to the method described in the "second generation liquid crystal display technology".

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

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

The color filter containing the cured film is suitable for a color TFT (Thin Film Transistor) liquid crystal display device. A color TFT-type liquid crystal display device is described in, for example, "color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD., 1996)". Moreover, the above color filters are also suitable for lateral electric field driving methods such as IPS (In Plane Switching); pixel division methods such as MVA (Multi-domain Vertical Alignment); etc. Expanded liquid crystal display devices, STN (Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer) )), FFS (fringe field switching) and R-OCB (Reflective Optically Compensated Bend).

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

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

The liquid crystal display device includes, in addition to the color filter, various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle protective film. The above-mentioned color filter can be applied to a liquid crystal display device including these known members. These components are described in, for example, "'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Shimadaro CMC-Group. Issued in 1994)" and "2003 Status and Future Outlook of the Liquid Crystal Related Market (Vol. 2) (Table Ryoji Fuji Chimera Research Institute, Inc., 2003) ". The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et.al) and / or Monthly Display December 2005, pages 18 to 24 (Island Kangyu), and SID meeting Digest 1380 (2005) 25 ~ 30 pages (Yaki Taki).

The hardened film is suitable for portable devices such as personal computers, tablets, mobile phones, smart phones, and digital cameras; OA (Office Automation) equipment such as multifunction printers and scanners; surveillance cameras, bar code readers, and Industrial teller machines such as automatic teller machine (ATM), high-speed cameras and personal authentication using face image authentication; camera equipment for vehicles; medical camera equipment such as endoscopes, capsule endoscopes, and catheters ; Space sensors such as biometric sensors, biosensors, military reconnaissance cameras, stereo map cameras, meteorological and ocean observation cameras, land resource reconnaissance cameras, and space astronomy and deep space target exploration cameras The light-shielding members and light-shielding layers of optical filters and modules used in such applications are further suitable for anti-reflection members and anti-reflection layers.

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

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

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limitedly limited by the examples shown below.

[Colorant] Each colorant was produced by the following method.

<Titanium Nitride-Containing Particles (TiN-1)> First, Ti particles (TC-200, manufactured by TOHO TECHNICAL SERVICE CO., LTD.) Were subjected to a plasma treatment in Ar gas, thereby performing Ti nanoparticle granulation. . The Ti nano particles after the plasma treatment were allowed to stand for 24 hours in an Ar gas atmosphere under conditions of an O ₂ concentration of 50 ppm or less and 30 ° C. After that, the O ₂ concentration was set to 100 ppm, and the O ₂ gas was introduced into the Ar atmosphere, and then left to stand at 30 ° C. for 24 hours (pretreatment of Ti particles). Then, using a TTSP separator manufactured by Hosokawa Micron Corporation, the obtained Ti nano particles were classified with a yield of 10%, thereby obtaining Ti particle powder. The primary particle diameter of the obtained powder was observed by TEM, and the average particle diameter of 100 particles was calculated by arithmetic mean. As a result, it was 120 nm. Titanium nitride-containing particles TiN-1 were produced using a device for producing a black composite fine particle according to FIG. 1 according to International Publication No. 2010/147098. Specifically, in a black composite particle manufacturing apparatus, a high-frequency voltage of about 4 MHz and about 80 kVA is applied to a high-frequency oscillation coil of a plasma torch, and 50 L / min of argon gas is supplied as a plasma gas from a plasma gas supply source. And nitrogen 50L / min mixed gas, argon-nitrogen plasma flame is generated in the plasma torch. A carrier gas of 10 L / min was supplied from a spray gas supply source of the material supply device. For the Ti particles obtained as described above, Fe powder (JIP270M, manufactured by JFE Steel Corporation) and Si powder (Silicon powder SI006031) were mixed so that each mass ratio became Ti / Fe / Si = balance / 0.05 / 0.05. . This mixture is supplied together with argon as a carrier gas into a thermoplasma flame in a plasma torch, and is allowed to evaporate in the thermoplasma flame to be highly dispersed in a gas phase state. Further, nitrogen was used as a gas supplied into the chamber by a gas supply device. The flow velocity in the chamber at this time was set to 5 m / sec, and the supply amount was set to 1,000 L / min. The pressure in the cyclone was set to 50 kPa, and the feed rate of each raw material from the chamber to the cyclone was set to 10 m / s (average value). In this way, TiN-1 containing titanium nitride particles was obtained.

With respect to the obtained titanium nitride-containing particles TiN-1, the contents of titanium (Ti) atoms, iron (Fe) atoms, and silicon (Si) atoms were measured by ICP emission spectrometry. In the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analysis device "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used. The nitrogen atom content was measured by an oxygen and nitrogen analyzer "EMGA-620W / C" (trade name) manufactured by HORIBA, Ltd. and calculated by an inert gas fusion thermal conductivity method. As a result of the above, the mass ratio of each atom contained in the titanium nitride-containing particles TiN was Ti / N / Fe / Si = 57/34 / 0.0030 / 0.0020.

For X-ray diffraction of titanium nitride-containing particles TiN-1, a powder sample was filled in an aluminum standard sample holder, and a wide-angle X-ray diffraction method (manufactured by Rigaku Corporation, trade name "RU-200R") was used. ). As the measurement conditions, the X-ray source was set to CuKα rays, the output was set to 50kV / 200mA, the slit system was set to 1 ° -1 ° -0.15mm-0.45mm, the measurement step (2θ) was set to 0.02 °, and the scanning speed was set to 2 ° / min. Then, a diffraction angle 2θ of a peak originating from the TiN (200) surface observed near the diffraction angle 2θ (42.6 °) was measured. Then, the half-width of the peak originating from the (200) plane was used to determine the crystallite size of the particles using the Scherrer formula. As a result, the diffraction angle of the peak was 42.62 °, and the crystallite size was 10 nm. In addition, no X-ray diffraction peak caused by TiO _{2 was} observed at all.

<Titanium nitride-containing particles TiN-2> As Ti particles, instead of "TC-200" manufactured by TOHO TECHNICAL SERVICE CO., LTD., And "578347" manufactured by Sigma-Aldrich Co. LLC. The method was the same as TiN-1 except that Fe / Si = remaining amount / 0.5 / 1 was mixed with Fe powder and Si powder, and TiN-2 containing titanium nitride particles was obtained. The diffraction angle of the peak measured by X-ray diffraction was 42.81 °, and the crystallite size was 12 nm.

<TiN-3 containing titanium nitride particles> The same method as TiN-1 is used except that Fe powder and Si powder are mixed so that each mass ratio becomes Ti / Fe / Si = balance / 1/2. TiN-3 containing titanium nitride particles was obtained. The diffraction angle of the peak measured by X-ray diffraction was 43.1 °, and the crystallite size was 12 nm.

<Production of Titanium Black A-1> A titanium oxide MT-150A (trade name, manufactured by TAYCA CORPORATION) with an average particle diameter of 15 nm was weighed to 100 g, and a BET (Brunauer, Emmett, Teller) specific surface area of 300 m ² / g of silicon dioxide was weighed. Particles AEROSIL300 (registered trademark) 300/30 (manufactured by Evonik Japan Co., Ltd.) was weighed 25 g, and Disperbyk 190 (trade name, manufactured by BYK Chemie GmbH) was weighed 100 g, and these were added to 71 g of ion-exchange water, thereby A mixture was obtained. Then, MAZERSTAR KK-400W manufactured by KURABO was used, and the mixture was treated at a revolution speed of 1,360 rpm and a rotation speed of 1,047 rpm for 30 minutes to obtain a homogeneous aqueous solution of the mixture. This mixture aqueous solution was filled in a quartz container, and heated to 920 ° C. in an oxygen atmosphere using a small rotary furnace (manufactured by MOTOYAMA CO., LTD). Thereafter, the inside of the small rotary furnace was replaced with nitrogen, and ammonia gas was flowed at 100 mL / min for 5 hours at the same temperature, thereby performing a nitriding reduction treatment. The powder recovered after completion was pulverized in a mortar to obtain titanium black [a dispersion containing titanium black particles and Si atoms] containing powdered specific surface area of 73 m ² / g containing Si atoms (hereinafter, designated as "titanium Black A-1 ").

<Production of Fe atom-containing niobium nitride-containing particles (NbN)> Niobium nitride-containing particles containing Fe atoms were produced by the following method. First, niobium (powder) <100-325mesh> manufactured by Mitsuwa Chemicals Co., Ltd was prepared as a raw material (hereinafter, also referred to as "metal raw material powder"). Next, the metal raw material powder was subjected to a plasma treatment in Ar gas, thereby performing Nb nanoparticle granulation. The conditions of the above-mentioned plasma treatment are in accordance with the following plasma treatment (1).

(Plasma Treatment (1)) The plasma treatment (1) was performed by the following method. Using the apparatus based on the above-mentioned black composite particle manufacturing apparatus, plasma treatment was performed under the following conditions (1).・ High-frequency voltage applied to the coil for high-frequency oscillation: frequency about 4MHz, voltage about 80kVA ・ plasma gas: argon (supply amount 100L / min) ・ carrier gas: argon (supply amount 10L / min) ・ in the chamber Atmosphere: Argon (supply amount 1,000L / min, flow velocity in the chamber 5m / sec) • Atmosphere in cyclone separator: argon, internal pressure 50kPa • Material supply speed from the chamber to the cyclone separator: 10m / s (average value)

Next, Fe powder (JIP270M, manufactured by JFE Steel Corporation) was prepared, and plasma treatment was performed under the conditions of the plasma treatment (1) to perform Fe nanoparticle granulation.

Next, the Nb nano particles and Fe nano particles obtained as described above were mixed to obtain a raw metal powder. This raw metal powder was subjected to a plasma treatment in nitrogen to obtain niobium nitride-containing particles. The conditions of the above-mentioned plasma treatment are in accordance with the following plasma treatment (2).

(Plasma treatment (2)) Plasma treatment (2) was performed by the following method. The device uses the same one as the plasma treatment (1).・ High-frequency voltage applied to the coil for high-frequency oscillation: frequency is about 4MHz, voltage is about 80kVA ・ plasma gas: argon and nitrogen (supply amounts are 50L / min) ・ carrier gas: nitrogen (supply amount: 10L / min)・ Atmosphere in the chamber: Nitrogen (supply amount 1,000L / min, flow velocity in the chamber 5m / sec) ・ Atmosphere in the cyclone: Nitrogen, internal pressure 50kPa ・ Supply rate of material from the chamber to the cyclone: 10m / s ( average value)

The particles after the plasma treatment (2) were finished, Ar gas was used, and a split-type humidity supply device SRH was manufactured by NIHON SHINTECH CO., LTD. To introduce 95% relative humidity in the atmosphere, and nitrogen at 20 ° C was introduced. And let stand for 24 hours. Thereafter, a TTSP separator manufactured by Hosokawa Micron Corporation was used to classify the obtained particles under the condition that the yield was 10%, thereby obtaining niobium nitride-containing particles (NbN). In addition, nitrogen was supplied to the separator. The content of iron (Fe) atoms in the obtained niobium nitride-containing particles was measured by ICP emission spectrophotometry, and it was 50 mass ppm.

<Production of Fe atom-containing vanadium nitride-containing particles (VN)> In the production of Fe atom-containing niobium nitride-containing particles, Niobium (powder) <100-325mesh> manufactured by Mitsuwa Chemicals Co., Ltd was used. A vanadium nitride-containing particle (VN) containing Fe atoms was produced by the same method except that metal vanadium powder VHO was produced by TAIYO KOKO Co., LTD. The content of iron (Fe) atoms in the obtained vanadium nitride-containing particles was measured by ICP emission spectrometry, and the result was 50 mass ppm.

[Polyfunctional thiol compound] As the polyfunctional thiol compound, the following SH-4, SH-3, and SH-2 were used.

・ SH-4 (Pentaerythritol tetra (3-mercaptopropionate), which is equivalent to a 4-functional thiol compound.) [Chemical Formula 28]

・ SH-3 (trimethylolpropane tri (3-mercaptopropionate), which is equivalent to a trifunctional thiol compound.) [Chemical Formula 29]

・ SH-2 (1,4 butanediol bis (thioglycolate), which is equivalent to a bifunctional thiol compound.) [Chemical Formula 30]

[Dispersant] As the dispersant, a dispersant A having the following structure was used. The numerical value described in each structural unit represents the mass% of each structural unit with respect to all structural units.

・ Dispersant A [Chemical Formula 31]

[Adhesive resin] As the adhesive resin, the following resin A was used. The numerical value described in each structural unit represents the mole percentage of each structural unit with respect to all structural units. In the formula of Resin A, each abbreviation indicates the following. BzMA: benzyl methacrylate MMA: methyl methacrylate

・ Resin A [Chemical Formula 32]

[Polymerizable Compound]-Polymerizable Compound M1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD", see formula below) [Chemical Formula 33]

[Photopolymerization initiator]-OXE-01: Irgacure OXE01 (trade name, manufactured by BASF JAPAN LTD.) [Chemical Formula 34]

・ OXE-02: Irgacure OXE02 (trade name, manufactured by BASF JAPAN LTD.) [Chemical Formula 35]

・ PI-3: Photopolymerization initiator with the following structure

[Chemical Formula 36]

・ NCI-831 (trade name, manufactured by ADEKA CORPORATION) [Chemical Formula 37]

・ IRG-379: IRGACURE 379 (trade name, manufactured by BASF JAPAN LTD.) [Chemical Formula 38]

[Polymerization inhibitor] Ih-1: 4-methoxyphenol Ih-2: 2,6-di-tertiary-butyl-4-methylphenol Ih-3: 4-hydroxy-2, 2, 6, 6 -Tetramethylpiperidine 1-oxyl radical

[Surfactant] ・ F-1: Compound represented by the following formula (weight average molecular weight (Mw) = 15,311) In the following formula, the structural units represented by formulas (A) and (B) are 62 mole%, 38 mole%. In the structural unit represented by formula (B), a, b, and c satisfy the relationships of a + c = 14 and b = 17, respectively.

[Chemical Formula 39]

[Organic solvents] • PGMEA: propylene glycol monomethyl ether acetate • Cyclopentanone • Butyl acetate

[Preparation of Colorant Dispersion Liquid] First, a coloring agent, a dispersant, and an organic solvent were mixed for 15 minutes using a stirrer (EURO manufactured by IKA Corporation) to obtain a mixed liquid of the above components. Next, the obtained mixed liquid was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by SHINMARU ENTERPRISES CORPORATION to obtain a colorant dispersion liquid.

<Dispersion conditions> ・ Bead diameter: φ0.05mm, (zirconia beads manufactured by NIKKATO CORPORATION, YTZ) ・ Bead filling rate: 65% by volume ・ Grinding peripheral speed: 10m / sec ・ Separator peripheral speed: 13m / s ・ Dispersion Amount of mixed liquid to be processed: 15kg • Circulating flow rate (supply amount of pump): 90kg / hour • Temperature of processing liquid: 19 to 21 ° C • Cooling water: water • Processing time: about 22 hours

[Preparation of hardenable composition] Next, the above-mentioned colorant dispersion liquid, polyfunctional thiol compound, adhesive resin, polymerizable compound, polymerization initiator, polymerization inhibitor, and surfactant were mixed and stirred to obtain the following table. Each of the curable compositions of Examples and Comparative Examples shown in 1-1, Tables 1-2, and Table 2 was used. In addition, the content of each component in Table 1-1, Table 1-2, and Table 2 is mass%. Moreover, it adjusted with the organic solvent so that the final solid content of each hardenable composition might become the solid content concentration shown in Table 1-1, Table 1-2, and Table 2. An organic solvent was also used so that the mass ratio in each curable composition was PGMEA / butyl acetate / cyclohexanone = 27/18/27.

[Evaluation] The following evaluation tests were performed on each curable composition of Examples and Comparative Examples. The results are shown in Table 1-1 and Table 1-2.

[OD value] A coating film was formed by spin coating on a glass plate (EagleXG, manufactured by Corning Incorporated) with a thickness of 0.7 mm and 10 cm square, using each curable composition. At this time, the rotation speed was adjusted to obtain a cured film having a film thickness of 1.5 μm. The formed coating film was dried on a hot plate by heat treatment at 100 ° C. for 2 minutes, and exposed at an exposure amount of 500 mJ / cm ² to obtain a cured film. The OD value of the glass substrate containing the obtained cured film was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation.). The larger the OD value, the more excellent the light-shielding property of the cured film. The results are shown in Table 1-1, Table 1-2, and Table 2. The OD values shown in Tables 1-1, 1-2, and 2 are the minimum values at a wavelength of 400 to 800 nm. That is, the cured film (film thickness of 1.5 μm) of each example has an OD value greater than or equal to the OD values shown in Table 1-1, Table 1-2, and Table 2 over the entire region of a wavelength of 400 to 800 nm.

[Pattern shape] A coating film was formed by a spin coating method by adjusting the rotational speed so that a cured film having a film thickness of 1.5 μm was obtained using each curable composition on a Si substrate. The formed coating film was dried on a hot plate by a heat treatment at 100 ° C for 2 minutes to obtain a cured film. For the Si substrate containing the obtained cured film, and for the substrate with a coating film after the pre-baking described above, an i-ray stepper (FPA3000i5 + manufactured by Canon Inc.) was used to form a 200 μm × 20 μm line pattern The photomask was exposed to the above-mentioned coating film at the exposure amounts described in the table. The coated film after exposure was subjected to spin-on immersion development using Coater Developer ACT8 manufactured by Tokyo Electron Limited as a developing solution using tetramethylammonium hydroxide for 30 seconds. After the development, a spray rinse process was performed with pure water for 20 seconds. The developed coating film was post-baked (temperature: 220 ° C, time: 300 seconds). The pattern shape of the coating film after the post-baking was measured by a scanning electron microscope (Scanning Electron Microscope). Specifically, the film thickness at the end portion of the line pattern and the film thickness at the center portion were measured, and the ratio (film thickness at the end portion of the pattern / film thickness at the center portion) was calculated and evaluated based on the following criteria. The results are shown in Table 1-1, Table 1-2, and Table 2. In addition, the evaluation "2" or more is a practical use range. • 7: When the ratio exceeds 0.98 and 1.00 or less, no difference in film thickness between the central portion and the end portion of the pattern is observed in the observation by SEM.・ 6: When the ratio exceeds 0.96 to 0.98, a slight difference in film thickness between the central portion and the end portion of the pattern is observed.・ 5: When the ratio exceeds 0.94 to 0.96, a difference in film thickness between the central portion and the end portion of the pattern is observed.・ 4: When the ratio exceeds 0.92 and 0.94 or less, the film thickness at the end portion is thin and slight deformation occurs, but it is a level that is not a problem in practical use.・ 3: When the ratio exceeds 0.90 and 0.92 or less, the thickness of the end portion is thin and deformed, but it is a level that is not a problem in practical use.・ 2: When the ratio exceeds 0.80 and 0.90 or less, the film thickness at the end is thin, but it is a level that can be used practically.・ 1: The ratio is 0.80 or less, and the film thickness at the end is thin, which is outside the allowable range.

[Stability over time] Each of the hardenable compositions after the preparation was sealed in a 100 cc Bloom bottle, and stored in a thermostat at 45 ° C. for 7 days. Thereafter, the pattern shape was evaluated by the same method as described above. The results are shown in Table 2.

[Table 1-1]

[Table 1-2]

[Table 2]

Based on the results shown in Tables 1-1 and 1-2, the curable composition of each example is a curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound. The optical density of the cured film obtained by curing the curable composition per 1.5 μm in the visible light region is 4.0 or more. The cured film obtained by curing the curable composition of each example has an excellent pattern shape. On the other hand, the curable composition of the comparative example does not have a desired effect. The hardening composition of Example 48 in which the content of the coloring agent was 55 mass% or more with respect to the total solid content of the hardening composition was the same as that in the dispersant and the content of the coloring agent in Example 49 was 53% The pattern shape of the obtained hardened | cured material is more excellent than a hardenable composition. The curable compositions of Example 1, Example 2 and Example 3 in which the content of the polyfunctional thiol compound is 1 to 5.5% by mass based on the content of the colorant are higher than those of the curable composition of Example 4. The pattern shape of the obtained hardened | cured material was more excellent. The curable composition of Example 45 containing two or more phenolic compounds as a polymerization inhibitor hardened at a lower exposure amount than the curable composition of Example 36, and the pattern shape of the cured product was excellent. The curable composition of Example 46 containing a phenol-based compound and a hindered amine-based compound as a polymerization inhibitor was cured at a lower exposure than the curable composition of Example 36, and the pattern shape of the cured product was excellent. The polyfunctional thiol compound was a trifunctional curable composition of Example 5, and the pattern shape of the cured product was more excellent than that of the curable composition of Example 9. The polyfunctional thiol compound is a four-functional curable composition of Example 1, and the pattern shape of the cured product is more excellent than that of the curable compositions of Examples 9 and 5. The photopolymerization initiator was the curable composition of Example 34, which was an oxime compound, and the pattern shape of the cured product was more excellent than that of the curable composition of Example 25. The hardening composition of Examples 13 and 48 of the content of the photopolymerization initiator with respect to the total solid content of the hardening composition of more than 1% by mass and less than 10% by mass, and the hardening of Examples 50 and 51 The pattern shape of the cured product is more excellent than that of the sexual composition. The hardenable composition of Examples 13 and 48 of the content of the polymerizable compound with respect to the total solid content of the hardenable composition is more than 3.5% by mass and less than 20% by mass, and the hardenable composition of Examples 50 and 51 The pattern shape of the cured product is more excellent than that of the cured product. The curable compositions of Examples 2 and 48 in which the content of the dispersant was 17% by mass or more were more excellent in the pattern shape of the cured product than the curable compositions of Examples 13 and 54.

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

[Preparation of Carbon Black Dispersion (CB Dispersion) and Evaluation of Hardening Composition] In the preparation of the above-mentioned coloring agent dispersion, carbon black (trade name "Color Black S170", Degussa-Hüls AG A carbon black dispersion (CB dispersion liquid) was obtained by the same method except for manufacturing, carbon black having an average primary particle diameter of 17 nm, a BET specific surface area of 200 m ² / g, and a gas black method.

In the preparation of the curable composition of Example 1, instead of the colorant dispersion liquid added so that the curable composition contained 58% by mass of titanium nitride-containing particles TiN-1, TiN containing titanium nitride-containing particles was used. -1 mixture of the colorant dispersion liquid and the CB dispersion liquid (titanium nitride-containing particles in the hardenable composition TiN-1: carbon black in the hardenable composition = 45:13 (mass ratio), the hardenability Except that the total content of the titanium nitride-containing particles TiN-1 and carbon black in the composition was 58% by mass.), A hardenable composition was prepared by the same method and evaluated using this. As a result of the evaluation, it was found that the same light-shielding property and pattern shape as in Example 1 were obtained.

[Preparation of Color Pigment Dispersion (PY Dispersion) and Evaluation of Hardening Composition] In the preparation of the above-mentioned colorant dispersion, the colorant was Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., A color pigment dispersion (PY dispersion liquid) was obtained by the same method except that the product name was 6150 Pigment Yellow 5GN).

In the preparation of the curable composition of Example 1, instead of the colorant dispersion liquid added so that the curable composition contained 58% by mass of titanium nitride-containing particles TiN-1, TiN containing titanium nitride-containing particles was used. -1 mixture of the colorant dispersion liquid and the PY dispersion liquid (containing titanium nitride particles in the hardenable composition TiN-1: Pigment Yellow in the hardenable composition 150 = 45: 13 (mass ratio), hardenability The total content of the titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the composition was 58% by mass.) Except that, a hardenable composition was prepared by the same method and evaluated using this. As a result of the evaluation, it was found that the same light-shielding property and pattern shape as in Example 1 can be obtained, and a film having a thicker black can be obtained.

[Preparation of Color Pigment Dispersion (PR Dispersion Liquid)] In the preparation of the above-mentioned colorant dispersion liquid, except that the colorant was CIPigment Red 254 (manufactured by Ciba Specialty Chemicals), a color was obtained by the same method. Pigment dispersion (PR dispersion).

[Preparation of Color Pigment Dispersion (PB Dispersion Liquid)] In the preparation of the above-mentioned colorant dispersion liquid, except that the colorant was CIPigment Blue 15: 6 (manufactured by DIC Corporation), it was obtained by the same method. Color pigment dispersion (PB dispersion).

[Preparation of Color Pigment Dispersion (PV Dispersion Liquid)] In the preparation of the above-mentioned colorant dispersion liquid, except that the colorant was CIPigment Violet 23 (manufactured by Clariant), a color pigment dispersion was obtained by the same method. (PV dispersion).

In the preparation of the curable composition of Example 1, the above-mentioned titanium nitride-containing particles TiN were used instead of the colorant dispersion liquid added so that the curable composition contained 58% by mass of titanium nitride-containing particles TiN-1. -1, a mixture of PY, PR, PB, and PV dispersions (ratio of titanium nitride-containing particles TiN-1, PY, PR, PB, and PV in the hardening composition; titanium nitride-containing particles TiN-1: PY : PR: PB: PV = 70: 17: 37: 36: 10 (mass ratio), the total content of titanium nitride-containing particles TiN-1, PY, PR, PB, and PV in the hardening composition is 58% by mass )), And a curable composition was prepared in the same manner and evaluated using this method. As a result of the evaluation, it was found that the same light-shielding property and the same pattern shape as those of Example 1 can be obtained, and a film having excellent light-shielding properties in the infrared region can be obtained.

In the preparation of the curable composition of Example 1, the above-mentioned titanium nitride-containing particles TiN were used instead of the colorant dispersion liquid added so that the curable composition contained 58% by mass of titanium nitride-containing particles TiN-1. -1 and a compound SQ-23 shown below (ratio of titanium nitride-containing particles TiN-1 and compound SQ-23 in the hardening composition; titanium nitride-containing particles TiN-1: compound SQ-23 = 50: 8 (mass ratio), the total content of the titanium nitride-containing particles TiN-1 and the compound SQ-23 in the hardening composition was 58% by mass.), Except for this, a hardening composition was prepared in the same manner. , And used this to evaluate. As a result of the evaluation, it was found that the same light-shielding property and the same pattern shape as those of Example 1 can be obtained, and a film having excellent light-shielding properties in the infrared region can be obtained.

In the preparation of the curable composition of Example 1, the above-mentioned titanium nitride-containing particles TiN were used instead of the colorant dispersion liquid added so that the curable composition contained 58% by mass of titanium nitride-containing particles TiN-1. -1 with the following compound A-52 (ratio of titanium nitride-containing particles TiN-1 and compound A-52 in the hardening composition; titanium nitride-containing particles TiN-1: compound A-52 = 50: 8 (mass ratio), the total content of the titanium nitride-containing particles TiN-1 and the compound A-52 in the hardenable composition was 58% by mass.) Except for this, a hardenable composition was prepared by the same method and used This was evaluated. As a result of the evaluation, it was found that the same light-shielding property and the same pattern shape as those of Example 1 can be obtained, and a film having excellent light-shielding properties in the infrared region can be obtained.

Compound SQ-23 [Chemical Formula 40]

Compound A-52 [Chemical Formula 41]

101‧‧‧ support
102‧‧‧hardening composition layer
103‧‧‧Mask
201‧‧‧hardened film
301‧‧‧Post-baking hardened film
401‧‧‧curable composition layer
402‧‧‧Mask part
501‧‧‧hardened film
601‧‧‧Post-bake hardened film

FIG. 1 is a cross-sectional view schematically showing a manufacturing process of a cured film using a curable composition that does not include a polyfunctional thiol compound for each process. FIG. 2 is a cross-sectional view schematically showing a production process of a cured film using a curable composition containing no polyfunctional thiol compound for each process. FIG. 3 is a cross-sectional view schematically showing a production process of a cured film using a curable composition that does not contain a polyfunctional thiol compound for each process. 4 is a cross-sectional view schematically showing a manufacturing process of a cured film using a curable composition according to an embodiment of the present invention for each process. 5 is a cross-sectional view schematically showing a manufacturing process of a cured film using a curable composition according to an embodiment of the present invention for each process. 6 is a cross-sectional view schematically showing a manufacturing process of a cured film using a curable composition according to an embodiment of the present invention for each process.

101‧‧‧ support

102‧‧‧hardening composition layer

103‧‧‧Mask

Claims (26)

A curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, wherein a film thickness per 1.5 μm in a visible light region of a cured film obtained by curing the aforementioned curable composition is cured. The optical density is 4.0 or more. The curable composition according to item 1 of the scope of patent application, wherein the content of the colorant is 55% by mass or more based on the total solid content of the curable composition. The curable composition according to item 1 of the scope of patent application, wherein the content of the polyfunctional thiol compound is 1 to 5.5% by mass based on the content of the colorant. The hardenable composition according to any one of claims 1 to 3 of the scope of patent application, further comprising a polymerization inhibitor. The curable composition according to item 4 of the scope of patent application, wherein the content of the polymerization inhibitor is 0.1 to 1.5% by mass based on the content of the polyfunctional thiol compound. The curable composition according to item 4 of the scope of patent application, wherein the polymerization inhibitor contains a phenolic compound. The curable composition according to item 4 of the scope of application, wherein the polymerization inhibitor contains two or more phenolic compounds. The hardenable composition according to item 4 of the patent application, wherein the polymerization inhibitor contains a hindered amine compound. The curable composition according to any one of claims 1 to 3, wherein the colorant is an inorganic pigment. The hardenable composition according to item 9 of the scope of the patent application, wherein the inorganic pigment comprises a material selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, metallic pigments containing silver or tin, and silver and tin. At least one of the group consisting of metallic pigments of tin. The hardenable composition according to any one of claims 1 to 3 in the scope of the patent application, wherein the aforementioned polyfunctional thiol compound is a compound having two or more groups represented by formula (1), In formula (1), L ¹ represents a single bond or -CO-, and L ² represents a single bond or a divalent linking group. The curable composition according to any one of claims 1 to 3 in the scope of the patent application, wherein the polyfunctional thiol compound is trifunctional or more. The hardenable composition according to any one of claims 1 to 3, wherein the polyfunctional thiol compound is selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and trimethylolpropane tri At least one of the group consisting of (3-mercaptopropionate). The hardenable composition according to any one of claims 1 to 3, wherein the content of the photopolymerization initiator is more than 1% by mass based on the total solid content of the hardenable composition, and Less than 10% by mass. The hardenable composition according to any one of claims 1 to 3, wherein the content of the polymerizable compound is more than 3.5% by mass and less than 20 with respect to the total solid content of the hardenable composition. quality%. The hardenable composition according to any one of claims 1 to 3 in the patent application scope, further comprising a dispersant, and the content of the dispersant is 17% by mass based on the total solid content of the hardenable composition. the above. The curable composition according to any one of claims 1 to 3 in the scope of application for a patent, wherein the photopolymerization initiator is an oxime compound. A hardened film obtained by hardening the hardenable composition described in any one of claims 1 to 17 of the scope of patent application. A color filter includes the hardened film described in claim 18 of the scope of patent application. A light-shielding film containing the hardened film described in claim 18 of the scope of patent application. A solid-state imaging device includes the hardened film described in claim 18 of the scope of patent application. An image display device includes the hardened film described in claim 18 of the scope of patent application. A method for producing a cured film, comprising: forming a curable composition layer using the curable composition described in any one of claims 1 to 17 to form a curable composition layer on a support; A manufacturing process; and an exposure process for exposing the curable composition layer. The method for manufacturing a cured film according to item 23 of the scope of patent application, wherein the exposure amount of the curable composition layer in the exposure process is 200 mJ / cm ² or more. The method for manufacturing a cured film according to item 23 of the scope of application, wherein the process of forming the hardenable composition layer includes directly coating the hardenable composition on the support, thereby forming the hardenability on the support. Coating process of the composition layer. The method for manufacturing a cured film according to any one of claims 23 to 25, further comprising: a development process for developing the exposed curable composition layer; and cleaning the developed image. Cleaning process of hardening composition layer.