TWI740942B - Curable composition, cured film, color filter, light-shielding film, solid-state imaging element, image display device, and manufacturing method of cured film - Google Patents

Abstract

The present invention provides a curable composition, a cured film, a color filter, a light-shielding film, a solid-state imaging element, an image display device, and a production of a cured film capable of obtaining a cured film that maintains excellent light-shielding properties and has an excellent pattern shape method. The curable composition is a curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound. The cured film obtained by curing the curable composition is a film of 1.5 μm in the visible light region The thick optical density is 4.0 or more.

Description

Curable composition, cured film, color filter, light-shielding film, solid-state imaging element, image display device, and manufacturing method of 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 element, 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 shield light between colored pixels and improve contrast. In addition, the solid-state imaging element is provided with a light-shielding film in order to prevent the generation of noise, improve image quality, and the like. Currently, 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 have solid-state imaging elements such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors, and are used in solid-state imaging devices. The lens that forms the image of the subject on the imaging element.

Patent Document 1 describes a composition for forming a light-shielding film, "a composition for forming a light-shielding film characterized by including a coating film that can be formed on the periphery of an effective pixel region (imaging part) of a solid-state imaging element, and The black colorant and resin component with an average particle size of 40nm or less" and "the black colorant contains at least one of carbon black and titanium black". [Prior Technical Documents] [Patent Documents]

[Patent Document 1]: Japanese Patent Application Publication No. 2006-156801

The inventors of the present invention conducted intensive studies on a light-shielding film obtained by curing the composition for forming a light-shielding film described in Patent Document 1. As a result, it was confirmed that although it has excellent light-shielding properties, there are patterns in the obtained pattern shape. There is room for further improvement. Specifically, it has been confirmed that in a light-shielding film obtained by curing the composition for forming a light-shielding film described in Patent Document 1, the film thickness of the end portion may be smaller than the film thickness of the center portion.

The subject of the present invention is to provide a curable composition capable of obtaining a cured film that maintains excellent light-shielding properties and has an excellent pattern shape. In addition, the subject of the present invention is to provide a cured film obtained by using the curable composition, a color filter including the cured film, a light-shielding film, a solid-state imaging element and an image display device, and a method of manufacturing a cured film .

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

[1] A curable composition containing a coloring agent, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, wherein the cured film obtained by curing the curable composition is in the visible light region per 1.5 μm 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 with respect to 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 relative to the content of the coloring agent. [4] The curable composition according to any one of [1] to [3], which further contains 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 relative to 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 includes a metallic pigment selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver or tin-containing metallic pigments, and silver and At least one of the group consisting of tin metal pigments. [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 more. [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 tris 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 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], which further contains a dispersant, and the content of the dispersant is 17% by mass or more with respect to 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 described in [18]. [20] A light-shielding film containing the cured film described in [18]. [21] A solid-state imaging device comprising the cured film described in [18]. [22] An image display device comprising the cured film described in [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 Manufacturing process; and exposure process for exposing the curable 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 curable composition layer forming process includes directly coating the curable composition on the support to form a curable film on the support. The coating process of the composition layer. [26] The method for producing a cured film as described in any one of [23] to [25], further comprising: a development process of developing the exposed curable composition layer; and washing the developed curability The cleaning process of the composition layer. [Effects of the invention]

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 above-mentioned curable composition, a color filter including the above-mentioned cured film, a light shielding film, a solid-state imaging device and an image display device, and a method of manufacturing a cured film.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In addition, in this specification, the numerical range indicated by "~" means the range including the numerical value described before and after "~" as the lower limit and the upper limit. In addition, in the labeling of the group (atomic group) in the present specification, the label not labeling substituted and unsubstituted refers to those that do not contain substituents and those that contain substituents. For example, the "alkyl group" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In addition, the term "actinic rays" or "radiation rays" in this manual means, for example, the bright-ray spectrum of mercury lamps and the extreme ultraviolet, extreme ultraviolet (EUV: Extreme ultraviolet lithography), X-rays, and electron beams represented by excimer lasers. Wait. In addition, in this specification, "light" means actinic rays and radiation. The "exposure" in this manual, as long as there is no special stipulation, in addition to exposure using the bright line spectrum of a mercury lamp and extreme ultraviolet, X-ray, and EUV light represented by excimer lasers, it also includes the use of electron beams and Delineation performed by ion beams and other particle beams. In addition, in this specification, "(meth)acrylate" means acrylate and methacrylate. In addition, in this specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. In addition, in this specification, "(meth)acryloyl group" means an acryloyl group and a methacryloyl group. In addition, in this specification, "(meth)acrylamide" means acrylamide and methacrylamide. In addition, in this specification, "monomer" and "monomer" have the same meaning. Monomers are distinguished from oligomers and polymers and refer to compounds with a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound refers to a compound containing a polymerizable group, and it may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

[Curable composition] The curable composition contains a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound. The cured film obtained by curing the curable composition is 1.5μm in the visible light region. The optical density of the film thickness is 4.0 or more. According to the above-mentioned curable composition having such a structure, it is possible to obtain a cured film that maintains excellent light-shielding properties and has an excellent pattern shape (hereinafter, also referred to as "the effect of the present invention"). Although the mechanism by which the effect of the present invention can be obtained by the above-mentioned curable composition is not clear, the inventors of the present invention estimate 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.

The conventionally known curable composition containing a coloring agent such as carbon black and not containing a multifunctional thiol compound can obtain a high light-shielding concentration over a wide wavelength range, and therefore is widely used. 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 high compared to the long-wavelength side. Therefore, for example, when the curable composition layer is pattern-exposed by light in the ultraviolet region such as g-ray, h-ray, and i-ray, some time does not reach the inside of the curable composition layer, and the exposure is insufficient and the pattern shape is deteriorated. Based on the above, using FIGS. 1 to 6 schematically showing the manufacturing process of the cured film for each process, the mechanism of the pattern shape deterioration will be described. First, FIGS. 1 to 3 are cross-sectional views schematically showing the manufacturing process of a cured film using a curable composition that does not contain a polyfunctional thiol for each process. First, as shown in FIG. 1, on the support 101, a curable composition layer 102 is formed using a curable composition. Next, the curable composition layer 102 is exposed through the opening of the mask 103 (in FIG. 1, the arrow indicates the direction of light irradiation, and the A-B line is an extension of one end of the opening of the mask. The same applies below). Next, the curable composition layer 102 after the above-mentioned 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 relatively high, so the light does not easily reach the inside of the curable composition layer 102 during exposure, and the exposure at the lower part of the curable composition layer 102 becomes insufficient. In this way, if image development is performed, the insufficient exposure of the curable composition layer 102 will cause the curable composition to elute (FIG. 2 ). If the cured film 201 is heated and then baked in this state, a defect called "heated sagging" will occur in the part eluted during development. That is, it is estimated that the film thickness of the end portion of the cured film 301 after the obtained post-baking is lower than that of the center portion (FIG. 3 ).

4 to 6 are cross-sectional views schematically showing the manufacturing process of a cured film using the curable composition of the present invention for each process. First, as shown in FIG. 4, on the support 101, a curable composition layer 401 is formed using the curable composition of the present invention. Next, through the opening of the photomask 103, the curable composition layer 401 is exposed. At this time, the curable composition layer 401 contains a polyfunctional thiol compound, and therefore, it is estimated that the curable composition layer 401 is sufficiently cured to the inside of the curable composition layer 401 for the following reasons. Inside the exposed curable 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 curable composition layer 401, and peroxy radicals may be generated. Peroxy radicals do not have the effect of carrying out the polymerization reaction, so the polymerization reaction stops here. On the other hand, when a multifunctional thiol compound is present in the curable composition layer 401, the thiol group in the multifunctional thiol compound supplies hydrogen to the peroxy radical, thereby generating sulfur that is not susceptible to polymerization and deactivation caused by oxygen. Free radicals, the polymerization reaction proceeds. Therefore, it is inferred that the curable composition containing the polyfunctional thiol compound is easily cured to the inside of the curable composition layer 401 sufficiently. In addition, the cured film obtained by curing the curable composition has an optical density of 4.0 or more per 1.5 μm film thickness in the visible light region, and the curable composition layer 401 has high light-shielding properties. Generally, the light irradiated on the curable composition layer 401 through the opening of the mask 103 is diffracted by the opening of the mask 103, and is also irradiated on the light shielding portion 402 of the mask on the outside of the AB line (this is referred to as "Light leakage".). If the light-shielding property of the curable composition layer is low, light leakage will expose the curable composition layer covering the light-shielding portion, resulting in deterioration of the pattern shape. However, the curable composition layer 401 has a high light-shielding property, so light leakage is not absorbed by exposing the light-shielding portion 402 of the mask (FIG. 4 ). Therefore, if the cured film after the above-mentioned exposure is developed, it is sufficiently cured to the inside, and the light diffracted at the opening of the mask is absorbed, so a cured film 501 having an excellent pattern shape can be obtained (FIG. 5 ). It is inferred that the cured film 501 is less likely to cause "heat sag" even after the post-baking process, so the film thickness difference between the center and the end of the cured film 601 after post-baking becomes small, which is excellent The shape of the pattern (Figure 6).

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

Hereinafter, the aspect of each component contained in the said curable composition is explained in full detail.

[Coloring agent] The curable composition described above contains a coloring agent. The colorant is at least one selected from the group consisting of pigments and dyes. With respect to the total solid content of the curable composition, the content of the colorant is preferably 55% by mass or more, more preferably 56% by mass or more, and even more preferably 58% by mass or more. If the content of the coloring agent 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 of the content of the coloring agent is not particularly limited, but it is usually preferably 70% by mass or less with respect to the total solid content of the curable composition. If the content of the colorant is less than or equal to the upper limit, the curable composition has more excellent coatability.

<Pigment> As a pigment, there is no restriction|limiting in particular, A well-known inorganic pigment and/or an organic pigment can be used. Among them, from the viewpoint of obtaining a curable composition having more excellent effects of the present invention, the pigment is preferably an inorganic pigment.

(Inorganic Pigment) There is no particular limitation on the above-mentioned inorganic pigment, and a known inorganic pigment can be used. Examples of inorganic pigments include zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitating barium sulfate and barite powder, lead red, iron oxide red, chrome yellow, zinc yellow (zinc Yellow 1 type, zinc yellow 2 types), ultramarine blue, Prussian blue (potassium ferrocyanide) zircon gray, yellow, chrome titanium yellow, chrome green, peacock, Victoria green, iron blue (not related to Prussian blue ), vanadium zirconium blue, chrome tin red, manganese red, orange red, etc. In addition, as black inorganic pigments, metals containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag can be cited Oxide, metal nitride.

As inorganic pigments, carbon black, titanium black, metallic pigments, etc. (hereinafter, also referred to as "black pigments") can be obtained from the viewpoint of obtaining a curable composition capable of forming a cured film with high optical density even if the content is small. ) Is better. As the metallic pigment, for example, one or more metallic elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag can be cited The 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, metallic pigments containing silver or tin, and metallic pigments 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. In addition, as an 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, but are not limited to these.

In the curable composition described above, in addition to the pigment described as a black pigment, a pigment having infrared absorption properties can also be used. As the infrared-absorbing pigment, tungsten compounds, metal borides, and the like are preferred. Among them, tungsten compounds are preferred from the viewpoint of excellent light-shielding properties in wavelengths in the infrared region. In particular, a tungsten compound is preferred from the viewpoint that the photopolymerization initiator, which is related to the curing efficiency by exposure, has excellent light-transmittance in the light absorption wavelength region and the visible light region.

Two or more of these pigments can be used at the same time, and they can also be used at the same time as the dyes described later. For example, in order to adjust the color tone and improve the light-shielding properties in the desired wavelength region, for example, black or infrared light-shielding pigments are mixed with color pigments such as red, green, yellow, orange, purple, and blue, or dyes described later. Sample. It is preferable to mix a red pigment or dye, or a purple pigment or dye with black or a pigment having infrared light-shielding properties, and it is more preferable to mix a red pigment with black or a pigment having infrared light-shielding properties. Moreover, the near-infrared absorber and infrared absorber mentioned later can also be added.

The black pigment preferably contains titanium black and/or niobium oxynitride. Titanium black is a black particle containing titanium atoms. Lower-order titanium oxide, titanium oxynitride, titanium nitride, etc. are preferable. Titanium black particles can be modified on the surface as needed 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 zirconium oxide, and can also be treated with a water-repellent substance as shown in Japanese Patent Laid-Open No. 2007-302836. Titanium black is typically titanium black particles, and it is preferable that the primary particle size and average primary particle size of each particle are smaller. The same is true for niobium oxynitride. Specifically, the average primary particle diameter is preferably in the range of 10 nm to 45 nm.

In addition, the average primary particle size of the pigment can be measured with a transmission electron microscope (Transmission Electron Microscope, TEM). As a transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used. Measure the maximum length of the particle image obtained with a transmission electron microscope (Dmax: the maximum length of the two points on the outline of the particle image) and the maximum vertical length (DV-max: use 2 straight lines parallel to the maximum length When sandwiching the image, vertically connect the shortest length between two straight lines), and multiply the average value (Dmax×DV-max) ^1/2 as the particle size. The particle diameters of 100 particles are measured by this method, and the arithmetic average is used 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 repellency after surface treatment of titanium black and niobium oxynitride by the water repellent become the specified performance, 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.), etc.

As the coloring agent, titanium oxynitride, titanium nitride or niobium oxynitride is preferably used. In view of the better moisture resistance of the cured film obtained, titanium nitride or niobium oxynitride is more preferable, and niobium oxynitride To be further preferred. This is because these colorants are considered to be hydrophobic.

Furthermore, it is also preferable to contain titanium black as a dispersed body containing titanium black and Si atoms. In this form, titanium black is contained as a dispersion in the curable composition. The content ratio of Si atoms to Ti atoms in the dispersion (Si/Ti) is calculated in terms of mass, and 0.05 or more is preferred. 0.05-0.5 is more preferable, 0.07-0.4 is still more preferable. Here, the above-mentioned dispersed body includes both a titanium black in a state of primary particles and a state of agglomerates (secondary particles). In order to change the Si/Ti of the dispersion (for example, set to 0.05 or more), the following method can be used. First, the dispersion is obtained by dispersing titanium oxide and silicon dioxide particles with a disperser, and the dispersion is reduced at a high temperature (for example, 850 to 1,000°C), thereby obtaining titanium black particles as the main component And it contains Si and Ti to be dispersed. The aforementioned reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia. As titanium oxide, TTO-51N (trade name, manufactured by Ishihara Sangyo Kaisha, Ltd.) etc. are mentioned. Examples of commercially available silicon dioxide particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik Japan Co., Ltd.) and the like. A dispersant can be used to disperse titanium oxide and silicon dioxide particles. Examples of the dispersant include those described in the column of the dispersant described later. The above-mentioned dispersion can also be carried out in a solvent. Examples of the solvent include water and organic solvents. Examples include those described in the column of organic solvents described later. Titanium black whose Si/Ti is adjusted to 0.05 or more, for example, can be produced by the method described in paragraph number [0005] and paragraph numbers [0016] to [0021] of JP 2008-266045, for example.

By adjusting the content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersion containing titanium black and Si atoms to a preferable range (for example, 0.05 or more), a curable composition containing the dispersion is used When the cured film is formed, residues derived from the curable composition outside the area where the cured film is formed are reduced. In addition, the residue contains components derived from curable compositions such as titanium black particles and resin components. Although the reason for the reduction of residues is not clear, the dispersed body as described above has a tendency to decrease in particle size (for example, the particle size is less than 30 nm), and the Si atom-containing component of the dispersed body increases, whereby the entire film The adsorption to the substrate is reduced. It is inferred that this phenomenon contributes to the improvement of the development removability of the uncured curable composition (especially, titanium black) when the cured film is formed. Titanium black has excellent light-shielding properties for light in a wide range of wavelengths from ultraviolet light to infrared light. Therefore, the above-mentioned dispersion containing titanium black and Si atoms (Si/Ti is calculated in terms of mass, 0.05 or more is preferred) ) To form a cured film that exhibits excellent light-shielding properties. In addition, the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersion can be, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP 2013-249417 A Perform the measurement. Regarding the dispersion contained in the cured film obtained by curing the curable composition, when judging whether the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersion is 0.05 or more, the Japanese Patent Application Publication Method (2) described in paragraph 0035 of Bulletin 2013-249417.

Among the dispersions containing titanium black and Si atoms, the above-mentioned titanium black can be used. In order to adjust the dispersibility, colorability, etc. of the dispersion, titanium black can be combined with one or two or more composite oxides including Cu, Fe, Mn, V, and Ni, cobalt oxide, iron oxide, and carbon. Black, aniline black and other black pigments are used. At this time, it is preferable that the dispersed body containing titanium black accounts for 50% by mass or more of all the dispersed bodies. In this dispersion, in order to adjust the light-shielding properties, etc., other colorants (organic pigments and/or dyes, etc.) may be used together with titanium black as needed within a range that does not impair the effects of the present invention. Hereinafter, the materials used when introducing Si atoms into the dispersion are described. When introducing Si atoms into the dispersion, a Si-containing substance such as silicon dioxide may be used. Usable silicas include precipitated silica, fumed silica, colloidal silica, synthetic silica, etc., and these can be appropriately selected and used. Furthermore, if the particle size of the silicon dioxide particles is smaller than the film thickness when the light-shielding film is formed, the light-shielding properties are more excellent, so it is preferable to use fine-particle type silicon dioxide. In addition, as an example of fine particle type silicon dioxide, for example, the silicon dioxide described in paragraph 0039 of JP 2013-249417 A is incorporated, and these contents are incorporated in this specification.

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

Examples of the tungsten compound include tungsten oxide-based compounds, tungsten boride-based compounds, tungsten sulfide-based compounds, and the like. A tungsten oxide-based compound represented by the following general formula (composition formula) (I) is preferred. M _x W _y O _z ... (I) M stands for metal, W stands for tungsten, and O stands for 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.

It is preferable that M is an alkali metal, Rb or Cs is more preferable, and Cs is even more preferable.

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 generation of impurity phases in the tungsten compound. When z/y is 2.2 or more, the chemical stability of the material can be further improved, and when z/y is 3.0 or less, infrared rays can be sufficiently shielded.

As specific examples of the tungsten oxide compound represented by the above general formula (I), Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _3, etc., Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferred, and Cs _0.33 WO ₃ is even more preferred.

The tungsten compound is preferably fine particles. The average primary particle size of the tungsten particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. With the average primary particle size in this range, the tungsten particles are less likely to block visible light due to light scattering, so 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 size is, the better. However, for reasons such as ease of handling during production, the average primary particle size of the tungsten particles is usually 1 nm or more.

Two or more types of tungsten compounds can be used.

The tungsten compound can be obtained as a commercially available product. 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 compound can also be obtained as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd., for example.

Examples of metal borides include lanthanum boride (LaB ₆ ), arsenic boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), 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 of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), etc., and lanthanum boride (LaB ₆ ) is preferred.

The metal boride is preferably fine particles. The average primary particle size of the metal boride particles is preferably 800 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. With the average primary particle size in this range, the metal boride particles are less likely to block visible light due to light scattering, so 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 size is, the better. However, for reasons such as ease of handling during production, the average primary particle size of the metal boride particles is usually 1 nm or more.

Two or more types of metal borides can be used.

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

(Titanium Nitride-Containing Particles) As the inorganic pigment, titanium nitride-containing particles containing Fe atoms can also be used. When manufacturing titanium nitride-containing particles, a gas phase reaction method is generally used, and specifically, an electric furnace method, a thermoplasma method, and the like are mentioned. Among these preparation methods, the thermoplasma method is preferred from the viewpoint of less mixing of impurities, the viewpoint of easy particle size uniformity, and the viewpoint of higher productivity. As a method of generating thermoplasma, DC arc discharge, multiphase arc discharge, high-frequency (RF) plasma, and hybrid plasma, etc. can be cited. High-frequency plasma with less impurities from the electrode is preferred. . As a specific manufacturing method of titanium nitride-containing particles based on the thermoplasma method, for example, high-frequency thermoplasma is used to evaporate the titanium powder, nitrogen is introduced into the device as a carrier gas, and the titanium powder is nitrogenized by a cooling process. To synthesize titanium nitride-containing particles. In addition, the thermoplasma method is not limited to the above.

The manufacturing method of titanium nitride-containing particles is not particularly limited, and the manufacturing method described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to. For example, it can be manufactured as follows, that is, instead of Ag powder of International Publication No. 2010/147098, a Fe-containing component and/or Si-containing component described later is used, and the component is mixed with a titanium powder material (titanium particle) as The raw material is 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 the titanium nitride-containing particles is preferably of high purity. The titanium powder material is not particularly limited. It is better to use titanium with a purity of 99.99% or more, and more preferably to use 99.999% or more.

Titanium powder materials (titanium particles) used in the production of titanium nitride-containing particles sometimes contain atoms other than titanium atoms. Examples of other atoms that the titanium powder material may contain include Fe atoms and Si atoms. When the titanium powder material contains Fe atoms, the content of Fe atoms relative to the total mass of the titanium powder material is preferably more than 0.001% by mass. When the titanium powder material contains Si atoms, the content of Si atoms relative to the total mass of the titanium powder material is preferably more than 0.002% by mass and less than 0.3% by mass, more preferably 0.01-0.15% by mass, and more preferably 0.02-0.1% by 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 considered that the adsorbability of the dispersant when the titanium nitride-containing particles are dispersed to the titanium nitride-containing particles is optimized, the undispersed content of the titanium nitride-containing particles is reduced, and the generation of particles can be suppressed. The moisture in the titanium powder material (titanium particles) used in the production of titanium nitride particles relative to the total mass of the titanium powder material is preferably less than 1% by mass, more preferably less than 0.1% by mass, and does not substantially contain Further better.

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

The method for making the titanium nitride-containing particles contain Fe atoms is not particularly limited. For example, a method of introducing Fe atoms at the stage of obtaining the titanium particles (titanium powder) used as the raw material of the above-mentioned titanium nitride-containing particles can be mentioned. . In more detail, when titanium is produced by the reduction (Kroll) method, etc., it is used as a reaction vessel made of a material containing Fe atoms such as stainless steel (SUS), or used as a material for a punch and a pulverizer when titanium is crushed By containing Fe atoms, Fe atoms can be attached to the surface of titanium particles. When the thermoplasma method is used in the production of titanium nitride-containing particles, in addition to the titanium particles as the raw material, Fe particles, Fe oxides and other components are added, and these are nitrided by the thermoplasma method, thereby enabling the nitrogen-containing The titanium oxide particles contain Fe atoms. In addition, the Fe atoms contained in the titanium nitride-containing particles can be used as ions, metal compounds (including complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, nitrogen oxides, sulfides, and sulfur. Any form such as oxide is included. The Fe atoms contained in the titanium nitride-containing particles may exist as impurities in the inter-lattice positions, or may exist as impurities in an amorphous state at the grain boundaries.

As a result of intensive research, the inventors found that the content of Fe atoms in the titanium nitride-containing particles correlates with pattern formation and the corrosion resistance of the electrode. The Fe atoms contained in the titanium nitride-containing particles have excellent 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 the Fe atoms. It is considered that after the patterning of the cured film such as the development process, Fe atoms remain on the electrode and the substrate, and the titanium nitride is easily removed. Therefore, it is inferred 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 electrode and the substrate increases, which is considered to be a cause of electrode corrosion. Therefore, it is estimated that by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less, the corrosion resistance of the electrode is improved. 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 them, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is still more preferable. When the content of Fe atoms exceeds 0.001% by mass, the pattern formability of the cured film is further improved. With the Fe atom content less than 0.4% by mass, the corrosion resistance of the electrode based on the hardened film is further improved (the hardened film can be prevented from corroding the electrode). That is, when the content of Fe atoms in the titanium nitride-containing particles is within the above range, it is possible to obtain excellent patterning properties of the cured film and corrosion resistance of the electrode. The content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma) emission spectrometry.

The titanium nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the pattern formability of the cured film is further improved. 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 relative to the total mass of the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass, more preferably 0.01-0.15% by mass, more preferably 0.02-0.1% by 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 the polarity of the outermost layer of the titanium nitride-containing particles is more stabilized when the content of Si atoms is less than 0.3% by mass. Thereby, it is considered that the adsorbability of the dispersant when dispersing the titanium nitride-containing particles to the titanium nitride-containing particles is optimized, the undispersed content of the titanium nitride-containing particles is reduced, and the generation of particles can be suppressed. The content of Si atoms in the titanium nitride-containing particles can be measured by the same method as the aforementioned Fe atoms.

The method for making the titanium nitride-containing particles contain Si atoms is not particularly limited. For example, a method of introducing Si atoms at the stage of obtaining the above-mentioned titanium particles (titanium powder) used as the raw material of the titanium nitride-containing particles, etc. . In more detail, when titanium is produced by a reduction method or the like, a reaction vessel made of a material containing Si atoms is used, or a material containing Si atoms is used as a material for a punch and a crusher when titanium is crushed. The 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 the titanium particles as the raw material, Si particles, Si oxides and other components are added, and these are nitrided by the thermoplasma method, thereby enabling the nitrogen-containing The titanium oxide particles contain Si atoms. The Si atoms contained in the titanium nitride particles can be ions, metal compounds (including complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, nitrogen oxides, sulfides, and sulfur oxides. Include in any form. In addition, the Si atoms contained in the titanium nitride-containing particles may be present as impurities in inter-lattice positions, or may be present as impurities in an amorphous state at the grain boundaries.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles relative to the total mass of 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 Further better. 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 relative to the total mass of the titanium nitride-containing particles is preferably 3-60% by mass, more preferably 5-50% by mass, and 10-40% by mass Further better. The content of nitrogen atoms can be analyzed by the inert gas fusion thermal conductivity method. Titanium nitride-containing particles contain titanium nitride (TiN) as the main component, which usually becomes significant when oxygen is mixed during synthesis and when the particle size is small. However, it can also be contained by oxidation of the particle surface. Part of the oxygen atom. The content of oxygen atoms in the titanium nitride-containing particles is preferably from 1 to 40% by mass, more preferably from 1 to 35% by mass, and more preferably from 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 inert gas fusion 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 obtained by the BET (Brunauer, Emmett, Teller) method.

The titanium nitride-containing particles may be composite particles including titanium nitride particles and metal particles. Composite particles refer to particles in which titanium nitride particles and metal particles are compounded or in a highly dispersed state. Among them, "composite" means that the particles are composed of two components, titanium nitride and metal, and "highly dispersed state" means that titanium nitride particles and metal particles exist separately, and the particles of a small amount of components are not aggregated and uniform. , Disperse the same. The metal particles are not particularly limited, and examples include those selected from 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 preferably selected from the group consisting of copper, silver, gold, platinum and tin, and the At least one of these alloys is more preferable. From the viewpoint of being more excellent in moisture resistance, silver is preferred. As the content of the metal fine particles in the titanium nitride-containing particles, relative to the total mass of the titanium nitride-containing particles, 5% by mass or more and 50% by mass or less are preferable, and 10% by mass or more and 30% by mass or less are more preferable.

・Peak diffraction angle 2θ of titanium nitride-containing particles When CuKα rays are used as an X-ray source, it is preferable that the diffraction angle 2θ of the peak derived from the (200) plane of titanium nitride-containing particles exceeds 42.6° and 43.5° or less . The cured film (for example, black matrix, etc.) obtained by using a curable composition containing titanium nitride particles with such characteristics can achieve a higher OD value.

When CuKα rays are used as the X-ray source to measure the X-ray diffraction spectrum of titanium compounds, as the strongest peak, for TiN, the peak derived from the (200) plane appears near 2θ=42.5°, and for TiO, it is derived from ( 200) The peak of the surface appears near 2θ=43.4°. On the other hand, although it is not the strongest peak, for anatase TiO ₂ , a peak derived from the (200) plane is observed near 2θ=48.1°, and for rutile TiO ₂ , it is near 2θ=39.2° A peak originating from the (200) plane is observed. Thereby, the more the crystal state contains a large amount of oxygen atoms, the more the peak position is shifted to the higher angle side with respect to 42.5°.

From the viewpoint of particle stability with time, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.6° and less than 43.5°. Moreover, from the process margin at the time of manufacturing From the viewpoint of excellence, 42.7° or more and less than 43.5° is more preferable, and from the viewpoint of excellent particle performance reproducibility, 42.7° or more and less than 43.4° is more preferable. _{When titanium oxide TiO 2} is contained as an auxiliary component, as the strongest peak, the peak derived from anatase TiO ₂ (101) appears near 2θ=25.3°, and _{the peak derived from rutile TiO 2} (110) appears Now 2θ=27.4°. However, TiO ₂ is white, which is a main cause of reducing the light-shielding property of the black matrix, so it is better to reduce it to the extent that it is not observed as a peak.

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

As the crystallite size, 20 nm or more is preferred, and 20-50 nm is more preferred. By using titanium nitride-containing particles with a crystallite size of 20nm or more to form a black matrix, the transmitted light of the cured film is blue to blue-violet with a peak wavelength of 475nm or less, which can achieve both high light-shielding properties and ultraviolet sensitivity. Black matrix. When the crystallite size is 20 nm or more, the ratio of the surface of the active particle to the particle volume becomes small, and it becomes a good balance, and the titanium nitride-containing particle has more excellent heat resistance and/or durability.

(Metal-containing nitride particles containing atom A) As the inorganic pigment, metal-containing nitride particles can also be used, and a predetermined atom A is contained in the above-mentioned metal-containing nitride 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 a perspective, Nb or V is better. As said atom A, B, Al, Si, Mn, Fe, Ni, Ag, etc. are mentioned, for example. When the metal-containing nitride particle contains the above atom A, the content thereof 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.

There are no particular limitations on the method for producing the metal-containing nitride particles containing the atom A, and a known method can be used. When manufacturing metal-containing nitride particles, a gas phase reaction method is generally used, and specifically, an electric furnace method, a thermoplasma method, and the like are mentioned. Among these preparation methods, the thermoplasma method is preferred from the viewpoint of less mixing of impurities, the viewpoint of easy particle size uniformity, and the viewpoint of higher productivity. As a specific manufacturing method of metal-containing nitride particles by the thermoplasma method, for example, a metal microparticle 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 thermoplasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber with a cooling function, a cyclone that classifies the generated metal particles, and The recycle part is composed of metal particles. In addition, in this specification, metal fine particles refer to particles containing metal elements with a primary particle diameter of 20 nm to 40 μm.

There are no particular limitations on the method of manufacturing metal-containing nitride particles using the metal microparticle manufacturing device, and a known method can be used. Among them, from the viewpoint of improving the yield of metal-containing nitride particles having a predetermined average primary particle size described below, it is preferable that the method for producing metal-containing nitride particles using a metal fine particle production apparatus includes the following processes. Process A: The process of supplying inert gas without nitrogen as the plasma gas into the plasma torch to generate a thermo-plasma flame. Process B: The process of supplying the metal raw material powder containing transition metal to the thermal plasma flame in the plasma torch to evaporate the above-mentioned metal raw material powder, thereby obtaining the gas phase raw material metal. Process C: A process of cooling the above-mentioned gas-phase raw metal to obtain metal particles containing transition metals. Process D: A process of supplying an inert gas containing nitrogen as a plasma gas into the plasma torch to generate a thermoplasma flame. Process E: A process of supplying transition metal-containing metal particles to the thermal plasma flame in the plasma torch to evaporate the above-mentioned metal particles, thereby obtaining the gas phase raw material metal. Process F: A process of cooling the above-mentioned gas-phase raw material metal to obtain metal-containing nitride particles. In addition, after the above-mentioned process C and/or the process F, the manufacturing method of the metal-containing nitride particles may further include the following process G as required. Process G: The process of grading the obtained particles. Moreover, the following process A2 may be included before process A, between process A and process B, between process C and process D, or between process D and process E. Process A2: A process of mixing atoms A into metal raw material powders containing transition metals. Moreover, the following processes A3-1 to A3-3 may be included before the above process A2. Process A3-1: The process of supplying an inert gas without nitrogen as a plasma gas into the plasma torch to generate a thermo-plasma flame. Process A3-2: The process of supplying the raw material powder containing atom A to the thermal plasma flame in the plasma torch to evaporate the above raw material powder, thereby obtaining the gas phase atom A. Process A3-3: The process of cooling the above-mentioned gas-phase atom A to obtain atomized atom A. In addition, process G may be included after process A3-3. In addition, in this specification, atom A to be micronized means a particle containing atom A with a primary particle diameter of 20 nm to 40 μm.

Furthermore, the above-mentioned method for manufacturing the metal-containing nitride particles preferably 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 the metal-containing nitride particles obtained in process F (or process G) are exposed to a mixed atmosphere of water vapor and nitrogen for nitriding treatment. In addition, if necessary, the method for manufacturing the metal-containing nitride particles may also include a process G after the process H. Hereinafter, the preferred state of each manufacturing process will be described in detail.

・Process A Process A is a process in which inert gas without nitrogen is supplied as a plasma gas into the plasma torch to generate a thermal plasma flame. The method of generating thermoplasma flame is not particularly limited. Examples include direct current arc discharge method, multi-phase arc discharge method, high frequency plasma method, and hybrid plasma method. The mixing of impurities from the electrode is relatively low. The frequency plasma method is preferred. The method of generating a thermoplasma flame based on the high-frequency plasma method is not particularly limited. For example, the plasma torch containing a high-frequency oscillation coil and a quartz tube can be supplied with plasma gas, and the above-mentioned high-frequency A method of applying a high-frequency current to an oscillation coil to obtain a thermoplasma flame. As the plasma gas in the process A, an inert gas that does not contain nitrogen can be cited. Examples of the inert gas that does not contain nitrogen include argon, hydrogen, and the like. The inert gas that does not contain nitrogen can be used singly, or two or more of them can be used at the same time.

・Process A2 Process A2 is a process in which atoms A are mixed with metal raw material powders containing transition metals. The mixing method of the raw metal powder and atom A is not particularly limited, and a known method can be used. For example, the aforementioned material supply device for supplying metal raw material powder into the plasma torch may include mixing and dispersing functions. 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 in this specification. The manufacturing method of metal-containing nitride particles may also include the following processes A3-1 to A3-3 before process A2.

・Process B Process B is a process of supplying the metal raw material powder containing transition metal to the thermal plasma flame in the plasma torch to evaporate the above-mentioned metal raw material powder, thereby obtaining the raw material metal in the gas phase. The method of supplying the metal raw material powder to the thermoplasma flame in the plasma torch is not particularly limited. From the viewpoint that the obtained gas phase raw material metal becomes a more uniform state, it is preferable to spray with a carrier gas. As the carrier gas, an inert gas that does not contain nitrogen is preferably used. The state of the inert gas that does not contain nitrogen is as described above. When the method for producing metal-containing nitride particles includes the above-mentioned process A2, it is preferable that the metal raw material powder maintains a uniform dispersion 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 material metal in the gas phase obtained in the process B is introduced into the chamber containing the above-mentioned cooling function, and is rapidly cooled in the chamber, whereby metal fine particles of the following desired particle size can be produced. The generated metal particles are recovered, for example, by the recovery section. As the atmosphere in the chamber, an inert gas that does not contain nitrogen is preferred. The state of the inert gas that does not contain nitrogen is as described above. In addition, by going through the above-mentioned processes A to C, metal particles containing transition metals can be obtained. Metal particles containing transition metals are easy to evaporate in process E. When the metal raw material powder contains impurities, the above-mentioned impurities can also be removed by going through the above-mentioned process A to C.

・Process D Process D is a process in which an inert gas containing nitrogen is supplied as a plasma gas into the plasma torch to generate a thermal plasma flame. Examples of the inert gas containing nitrogen include nitrogen and nitrogen containing inert gas. As the inert gas, argon gas, hydrogen gas, and the like can be cited. The nitrogen containing 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 aspects are the same as process A.

・Process E Process E is a process of supplying transition metal-containing metal particles to the thermal plasma flame in the plasma torch to evaporate the above-mentioned metal particles, thereby obtaining the raw material metal in the gas phase. As a method of supplying metal particles to the thermoplasma flame in the plasma torch, as described above, as the carrier gas, an inert gas containing nitrogen is preferable. The state of the inert gas containing nitrogen is as described above. In the process E, the raw material metal that becomes the metal particles through the process A to the process C is supplied to the thermoplasma flame, so the gas phase raw material metal is easily obtained, and the state of the gas phase raw material metal becomes more uniform.

・Process F Process F is a process for cooling the raw material 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. The preferred aspect of the inert gas containing nitrogen is as described above.

・Process G Process G is a process of classifying the obtained metal particles and/or metal-containing nitride particles. The classification method is not particularly limited. For example, a cyclone separator 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 carried out in an atmosphere of inert gas. The state of the inert gas is as described above.

・Process H Process H is a process in which metal-containing nitride particles are exposed to a mixed atmosphere of water vapor and nitrogen for nitriding treatment. Through this process, the content of metal nitride in the metal nitride-containing particles can be increased. The method of exposing the metal-containing nitride particles to the mixed atmosphere of water vapor and nitrogen is not particularly limited. For example, the metal-containing nitride particles can be introduced into a constant temperature bath filled with a gas mixed with water vapor and nitrogen. , The method of standing or stirring for a predetermined time, from the perspective of more stabilization of the surface and grain boundaries of the metal-containing nitride particles, standing still is better. As the mixing ratio of water vapor and nitrogen, if it is in the air, it is preferable that the relative humidity is 25 to 95%. 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.

・Processes A3-1～A3-3 Processes A3-1～A3-3 are processes in which inert gas without nitrogen is supplied into the plasma torch as a plasma gas to generate a thermoplasma flame (A3-1), The thermal plasma flame in the slurry torch supplies the raw material powder containing atom A to evaporate the raw material powder to obtain atom A in the gas phase (A3-2), and cool the gas phase atom A to obtain particles containing atom A The manufacturing process (A3-3). The state of each process is as in the above process A, process B (instead of the metal raw material powder containing transition metal, use the raw material powder containing atom A), and process C (instead of the metal particles containing transition metal to obtain atomized atoms A.) The content has been explained in. Through the above process, the atom A is atomized, and the atom A becomes easy to evaporate in the process E. In addition, by going through the above process, impurities (metal components other than atom A, etc.) contained in the raw material powder containing atom A can be removed.

・Preferable aspect of the method for producing metal-containing nitride particles containing atom A As a preferable aspect of the method for producing metal-containing nitride particles containing atom A, a method having the following processes in order can be mentioned.・Process A: A process in which inert gas without nitrogen is supplied as a plasma gas into the plasma torch to generate a plasma flame.・Process B: The process of supplying the metal raw material powder containing transition metal to the thermal plasma flame in the plasma torch to evaporate the above raw metal powder to obtain the raw material metal in the gas phase.・Process C: The process of cooling the above-mentioned raw material metals in the gas phase to obtain metal particles containing transition metals.・Process G: The process of classifying the obtained particles.・Process A3-1: A process in which inert gas without nitrogen is supplied as a plasma gas into the plasma torch to generate a thermoplasma flame ・Process A3-2: Atom A is supplied to the thermoplasma flame in the plasma torch The raw material powder to evaporate the raw material powder to obtain the atom A in the gas phase. Process A3-3: The process of cooling the atom A in the gas phase to obtain atom A that is atomized. Process G: For the obtained atom A The process of particle classification.・Process A2: A process in which atom A (atom A to be atomized) is mixed with transition metal-containing metal raw material powder (in this case, metal particles).・Process D: A process in which inert gas containing nitrogen is supplied as a plasma gas into the plasma torch to generate a thermo-plasma flame.・Process E: The process of supplying transition metal-containing metal particles to the thermal plasma flame in the plasma torch to evaporate the above-mentioned metal particles to obtain the raw material metal in the gas phase.・Process F: The process of cooling the above-mentioned gaseous raw material metal to obtain metal-containing nitride particles.・Process G: The process of classifying the obtained particles.・Process H: A process in which the metal-containing nitride particles obtained in Process G are exposed to a mixed atmosphere of water vapor and nitrogen for nitriding treatment. In the above series of manufacturing processes, the order of the processes A to C and the processes A3-1 to A3-3 can be replaced. That is, the processes A to C may be implemented after the processes A3-1 to A3-3.

According to the 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-containing nitride particles having a desired average primary particle size can be produced . As the reason for this, it is presumed that the transition metal and/or atom A are ionized by plasma treatment, and when the ions are cooled, the transition metal, atom A, and impurities reflect the melting point to be atomized. At this time, the atomization of the atom with the lower melting point is faster, and the atomization of the atom with the higher melting point is slower. Therefore, as described above, it is inferred that the particles (processes B and C, and processes A3-2 and A3-3) that have undergone a plasma treatment are those that easily become a single component (single crystal). If the single-component particles obtained as described above are classified, the impurity particles can be removed by the difference in the density and/or particle size of the transition metal particles and/or the atom A particles and the impurity particles. The above-mentioned classification can be performed, for example, by using a cyclone separator and the like and appropriately setting classification conditions.

・Purification of metal raw material powder and raw material powder as a transition metal-containing metal raw material powder (hereinafter, simply referred to as "metal raw material powder".) and raw material powder containing atom A (hereinafter, simply referred to as It is referred to 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, but 99.99% or more is preferable, and 99.999% or more is more preferable. The content of atom A in the raw material powder is also the same.

The metal raw material powder and/or raw material powder may contain the 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. In addition, as the impurities contained in the raw material powder, metal elements and the like can be mentioned.

The manufacturing method of the metal-containing nitride particles may also include the following process A0 before the process B (when the process A2 is included, it is 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 of removing impurities from the raw metal powder and/or raw material powder (separation and purification method) is not particularly limited. For example, for niobium, paragraph 0013 of JP 2012-211048 A can be used The method described in ～0030, for other raw metal powder and/or raw material powder, can also use the method based on the content.

・Coated metal-nitride-containing particles may be metal-nitride-containing particles coated with an inorganic compound. That is, it may be a coated metal-containing nitride particle having a metal-containing nitride particle and a coating layer formed of an inorganic compound that coats the metal-containing nitride particle. The curable composition containing metal-containing nitride particles coated with an inorganic compound has more excellent dispersion stability. The inorganic compound is not particularly limited, and includes _{oxides such as SiO 2} , ZrO ₂ , TiO ₂ , GeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ and P ₂ O ₅ , as well as aluminum hydroxide and zirconium hydroxide Waiting for hydroxide. Among them, aluminum hydroxide is preferred from the viewpoint of easy formation of a thinner film and easy formation of a film with a higher coverage rate. When it is intended to control the refractive index of the metal-containing nitride particles, silicon oxide is preferable as the low refractive index film, and zirconium hydroxide is preferable as the high refractive index film. The method for coating metal-containing nitride particles with inorganic compounds is not particularly limited, and it is preferable that the method for producing metal-containing nitride particles 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 oxides and/or hydroxides. There is no restriction|limiting in particular as a coating method, For example, the following wet coating method etc. are mentioned.

As the first wet coating method, first, the metal-containing nitride particles and water are mixed to prepare a slurry. Then, the above 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, by decantation and / Or ion exchange resin, etc. to remove excess alkali ions. After that, the slurry is dried to obtain oxide-coated metal-containing nitride particles.

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

As a third wet coating method, urea and aluminum chloride are used in the presence of metal-containing nitride particles to prepare a slurry containing an ionic liquid. The metal-containing nitride particles are taken out from the slurry and dried, and then the above-mentioned metal-containing nitride particles are fired to obtain metal-containing nitride particles coated with a hydroxide containing aluminum hydroxide.

(Organic pigments) Examples of organic pigments include the following: Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 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 etc. In addition, a pigment may be used individually by 1 type, and may use 2 or more types together.

<Dyes> As dyes, for example, Japanese Patent Application Publication No. 64-90403, Japanese Patent Application Publication No. 64-91102, Japanese Patent Application Publication No. 1-94301, Japanese Patent Application Publication No. 6-11614, Japanese Patent Publication No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5,677,920, U.S. Patent No. 505,950, Japanese Patent Application Publication No. 5-333207, Japanese Patent Application Publication No. 6-35183, Japanese Patent Application Publication No. 6-51115 , The pigment disclosed in Japanese Patent Laid-Open No. 6-194828, etc. If distinguished by chemical structure, pyrazole azo compounds, pyrromethene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxacyanine compounds, pyrazolo three compounds can be used. Azoleazo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazol azomethine compounds, and the like. As dyes, pigment multimers can also be used. Examples of the dye multimer include compounds described in Japanese Patent Application Publication No. 2011-213925 and Japanese Patent Application Publication No. 2013-041097. A polymerizable dye having polymerizability in the molecule can be used, and as a commercially available product, for example, the RDW series manufactured by Wako Pure Chemical Industries, Ltd. can be cited.

<Infrared absorber> The colorant may further contain an infrared absorber. Infrared absorber means a compound that has absorption in the wavelength region of the infrared region (wavelength 650-1,300 nm is preferable). The infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm. Examples of coloring agents having such spectroscopic properties include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, Squaraine compounds, naphthalocyanine compounds, quartacene compounds, dithiol metal complex compounds, croconium compounds, and the like. As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squaraine compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Application Laid-Open No. 2010-111750 can be used, and this content is incorporated herein. In the manual. For the cyanine compound, refer to "Functional Dye, Nobuhiro Ogawara/Ken Matsoka/Teijiro Kitao/Hirashima Tsunehiro Edited, Kodansha Scientific Ltd.", and this content is incorporated in this specification.

As a coloring agent having the aforementioned spectroscopic properties, the compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Laid-Open No. 07-164729 and/or the compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Laid-Open No. 2002-146254 can also be used. Paragraphs 0034 to 0067 of JP 2011-164583 A disclose near-infrared absorbing particles containing Cu and/or P oxide-containing crystallites and having a number average aggregate particle size of 5 to 200 nm.

As a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm, at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squaraine compounds, phthalocyanine compounds, and naphthalocyanine compounds good. The infrared absorber preferably dissolves 1% by mass or more of the compound in 25°C water, and more preferably dissolves 10% by mass or more of the compound in 25°C water. By using this compound, solvent resistance is optimized. For the pyrrolopyrrole compound, refer to paragraph numbers 0049 to 0062 of JP 2010-222557 A, and the contents are incorporated in this specification. For cyanine compounds and squaraine 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 No. 0028 of Japanese Patent Application Publication No. 2014-59550. ～0074, International Publication No. 2012/169447, Paragraph Nos. 0013 to 0091, JP 2015-176046, Paragraph Nos. 0019 to 0033, JP 2014-63144, Paragraph Nos. 0053 to 0099, JP Patent Paragraph numbers 0085 to 0150 of 2014-52431, Paragraph numbers 0076 to 0124 of JP 2014-44301, Paragraph numbers 0045 to 0078 of JP 2012-8532, and JP 2015-172102 Paragraph Nos. 0027～0067, Paragraph Nos. 0029～0067 of JP 2015-172004, Paragraph Nos. 0029～0085 of JP 2015-40895, Paragraph Nos. 0022～ of JP 2014-126642 0036, Japanese Patent Application Publication No. 2014-148567, paragraph numbers 0011 to 0017, Japanese Patent Application Publication No. 2015-157893, paragraph numbers 0010 to 0025, Japanese Patent Application Publication No. 2014-095007, paragraph numbers 0013 to 0026, Japanese Patent Application Publication Paragraph numbers 0013 to 0047 of 2014-80487 and paragraph numbers 0007 to 0028 of JP 2013-227403 A are incorporated into this specification.

通式1中，A¹ 及A² 分別獨立地表示芳基、雜芳基或以下述通式1-A表示之基團。 通式1-A 【化學式2】

通式1-A中，Z^1A 表示形成含氮雜環之非金屬原子團，R^2A 表示烷基、烯基或芳烷基，d表示0或1，波浪線表示連結鍵。 通式2 【化學式3】

通式2中，R^1a 及R^1b 分別獨立地表示烷基、芳基或雜芳基， R² ～R⁵ 分別獨立地表示氫原子或取代基，R² 與R³ 、R⁴ 與R⁵ 可分別鍵結而形成環， R⁶ 及R⁷ 分別獨立地表示氫原子、烷基、芳基、雜芳基、-BR^A R^B 或金屬原子，R^A 及R^B 分別獨立地表示氫原子或取代基， R⁶ 可與R^1a 或R³ 共價鍵結或配位鍵結， R⁷ 可與R^1b 或R⁵ 共價鍵結或配位鍵結。 通式3 【化學式4】

通式3中，Z¹ 及Z² 分別獨立地為形成可以縮環之5員或6員的含氮雜環之非金屬原子團， R¹⁰¹ 及R¹⁰² 分別獨立地表示烷基、烯基、炔基、芳烷基或芳基， L¹ 表示包含奇數個次甲基之次甲基鏈， a及b分別獨立地為0或1， a為0時，碳原子與氮原子以雙鍵鍵結，b為0時，碳原子與氮原子以單鍵鍵結， 式中以Cy表示之部位為陽離子部時，X¹ 表示陰離子，c表示為了維持電荷的平衡而所需之數，式中以Cy表示之部位為陰離子部時，X¹ 表示陽離子，c表示為了維持電荷的平衡而所需之數，式中以Cy表示之部位的電荷在分子內被中和時，c為0。The infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following general formulas 1 to 3. General formula 1 [Chemical formula 1]

In the general formula 1, A ¹ and A ² each independently represent an aryl group, a heteroaryl group, or a group represented by the following general formula 1-A. General formula 1-A [Chemical formula 2]

In the general 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 connecting bond. General formula 2 [Chemical formula 3]

In the general 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, R ² and R ³ , R ⁴ and R ⁵ They can be bonded separately 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 coordinately bonded ^{to R 1a} or R ^{3 , and R 7} may be ^{covalently bonded or coordinately bonded to R 1b} or R ⁵ . General formula 3 [Chemical formula 4]

In the general formula 3, Z ¹ and Z ² are each independently a non-metal atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be condensed, 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 each independently 0 or 1, when a is 0, the carbon atom and the nitrogen atom are bonded by a double bond , When b is 0, the carbon atom and the nitrogen atom are bonded by a single bond, and when the part represented by Cy in the formula is the cationic part, X ¹ represents an anion, and c represents the number required to maintain the balance of charges, where When the part represented by Cy is an anion part, X ¹ represents a cation, and c represents the number required to maintain the balance of charges. When the charge at the part represented by Cy in the formula 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 substituted by an acidic group, a basic group or a phthalic iminomethyl group. As the pigment derivative, from the viewpoint of the dispersibility and dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferable. It is particularly preferred that the pigment derivative has a basic group. The combination of the above-mentioned resin (dispersant) and the pigment derivative is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

Examples of organic pigments used to form pigment derivatives include dioxopyrrolopyrrole-based pigments, azo-based pigments, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, and dioxazine-based pigments. , Perylene pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, Shilin pigments, metal complex pigments, etc. As the acidic group possessed by the pigment derivative, a sulfonic acid group, a carboxylic acid group and a salt thereof are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is even more preferable. As the basic group possessed by the pigment derivative, an amine group is preferred, and a tertiary amine group is more preferred.

When the curable composition contains a pigment derivative, the content of the pigment derivative relative to the mass of the pigment is preferably 1-30% by mass, and more preferably 3-20% by mass. Only one type of pigment derivative may be used, or two or more types may be used at the same time.

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

As the content of the photopolymerization initiator, relative to the total solid content of the curable composition, 0.1% by mass or more is preferable, 0.5% by mass or more is more preferable, 1% by mass or more is more preferable, and more than 1% by mass is more preferable Particularly preferred, 30% by mass or less is preferred, 20% by mass or less is more preferred, 10% by mass or less is more preferred, and less than 10% by mass is particularly preferred. If 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. A photopolymerization initiator may be used individually by 1 type, and may use 2 or more types together. When two or more photopolymerization initiators are used at the same time, the total amount thereof is preferably within the above-mentioned range.

As the photopolymerization initiator, for example, halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as phosphine oxide, hexaarylbisimidazole, Oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and p-hydroxyacetophenone, etc. Examples of halogenated hydrocarbon compounds containing the above triazine skeleton include compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in the specification of British Patent No. 1388492, and Japanese The compound described in Japanese Patent Laid-Open No. 53-133428, the compound described in German Patent No. 3337024, the compound described in J. Org. Chem. based on FC Schaefer et al.; 29, 1527 (1964), and the compound described in Japanese Patent Laid-Open No. The compound described in 62-58241, the compound described in JP 5-281728, the compound described in JP 5-34920, the compound described in the specification of U.S. Patent No. 4212976, and the like.

From the viewpoint of exposure sensitivity, it is selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, phosphine compounds, and phosphine oxides. Compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron compound Compounds and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

Among them, trihalomethyl triazine compound, α-amino ketone compound, phosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound or acetophenone The compound is more preferred, and at least one compound selected from the group consisting of trihalomethyl triazine compound, α-amino ketone compound, oxime compound, triallylimidazole dimer and benzophenone compound is further Better.

In particular, when a curable composition is used in the production of a light-shielding film, since it is necessary to form a fine pattern into a clear shape, not only the curability but also development without leaving residue in the unexposed part is important. From this viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when forming a fine pattern, a stepper is used for exposure for curing. However, the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to a low level. In consideration of these points, when forming a fine pattern, it is particularly preferable to use an oxime compound as a photopolymerization initiator. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP 2013-29760 A can be referred to, and this content is incorporated in this specification.

As a photopolymerization initiator, a p-hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the phosphine-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 (brand names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone compound, IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (brand names, all manufactured by BASF Corporation), which are commercially available products, can be used. As the aminoacetophenone compound, it is also possible to use 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. As the phosphine compound, commercially available IRGACURE-819 or DAROCUR-TPO (brand name, both manufactured by BASF Corporation) can be used.

<Oxime compound> As the photopolymerization initiator, an oxime compound (oxime-based initiator) can be more preferably used. In particular, the oxime compound has high sensitivity and high polymerization efficiency, can harden the curable composition layer regardless of the concentration of the coloring agent, and it is easy to design the concentration of the coloring agent to be high, which is preferable. As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-80068 A, or the compound described in JP 2006-342166 A can be used. As the oxime compound, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionoxyimine Butan-2-one, 2-acetoxyiminopentane-3-one, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4- Tosyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In addition, JCSPerkinII (1979) pp.1653-1660, JCSPerkinII (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japanese Patent Application Publication 2000- Compounds described in 66385, JP 2000-80068, JP 2004-534797, and JP 2006-342166, compounds, etc. Commercially available products can also suitably use IRGACURE-OXE01 (manufactured by BASF Corporation), IRGACURE-OXE02 (manufactured by BASF Corporation), IRGACURE-OXE03 (manufactured by BASF Corporation), or IRGACURE-OXE04 (manufactured by BASF Corporation). In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) or N-1919 (containing carbazole oxime ester skeleton Starter (manufactured by ADEKA CORPORATION)).

As oxime compounds other than those described above, the compounds described in Japanese Patent Publication No. 2009-519904 with an oxime linked to the N-position of the carbazole can also be used; US Patent No. 7626957 with heterosubstituents introduced at the benzophenone site The compound described in the publication; the compound described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into the pigment site; the ketoxime compound described in the International Publication No. 2009-131189; A compound described in U.S. 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 with maximum absorption at 405 nm and good sensitivity to g-ray light sources Wait. Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, and this content is incorporated in this specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. In addition, it may be an oxime compound in which the N-O bond of the oxime compound is (E) body, it may be an oxime compound in (Z) body, or a mixture of (E) body and (Z) body.

【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 non-metal atomic group is preferred. As a monovalent non-metal atomic group, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group, etc. are mentioned. These groups may have one or more substituents. In addition, the aforementioned substituents may be further substituted with other substituents. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group. In the formula (OX-1), 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 more than one substituent. Examples of the substituent include the aforementioned substituents. In the formula (OX-1), as the divalent organic group represented by A, an alkylene group, cycloalkylene group or alkynylene 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, an oxime compound containing a fluorine atom can also be used. Specific examples of the oxime compound containing a fluorine atom include compounds described in JP 2010-262028 A; compounds 24, 36 to 40 described in JP 2014-500852 A; JP 2013-164471 The compound (C-3) described in the bulletin; etc. This content is incorporated into this manual.

As the photopolymerization initiator, compounds represented by the following general formulas (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 carbons, an alicyclic hydrocarbon group having 4 to 20 carbons, an aryl group having 6 to 30 carbons, or a carbon number of 7-30 In the aralkyl group, when R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a stilbene group, and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons, and a carbon number of 6 to The aryl group of 30, the aralkyl group of 7 to 30 carbons, or the heterocyclic group of 4 to 20 carbons, 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 Hydroxy, R ⁶ represents an alkyl group with 1 to 20 carbons, an aryl group with 6 to 30 carbons, an aralkyl group with 7 to 30 carbons, or a heterocyclic group with 4 to 20 carbons, and X represents a direct bond or a carbonyl group , A represents an integer of 0-4.

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

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

In the above formula (1) and formula (2), it ^{is preferred that R 1} and R ² are independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. Preferably, R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. In the above formulas (3) and (4), it ^{is preferred that R 1 is} each independently a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclohexyl group or a phenyl group. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. Preferably, R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. As specific examples of the compounds represented by formula (1) and formula (2), for example, the compounds described in paragraphs 0076 to 0079 of JP 2014-137466 A can be cited. This content is incorporated into this manual.

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

【Chemical formula 8】

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

[Polymerizable compound] The curable composition contains a polymerizable compound. The content of the polymerizable compound is preferably 0.1 to 40% by mass relative to 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. For example, the upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably less than 20% by mass. If 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, the pattern shape of the cured film obtained by curing the curable composition is more excellent. A polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When two or more types of polymerizable compounds are used at the same time, the total amount thereof is preferably within the above-mentioned range.

The polymerizable compound is preferably a compound containing more than one ethylenically unsaturated bond-containing group, more preferably a compound containing two or more, more preferably containing three or more, and particularly preferably containing five or more groups . 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)acryloyl group.

The polymerizable compound may be any of chemical forms such as monomers, prepolymers, oligomers, mixtures of these, and multimers of these, and monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 3,000, 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 amides And their multimers are preferably esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and their multimers. In addition, it is also suitable to use unsaturated carboxylic acid esters or amides containing nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups, addition reactants with monofunctional or polyfunctional isocyanates or epoxy groups, and the above-mentioned unsaturated groups. Dehydration condensation reaction products of carboxylic acid esters or amides and monofunctional or polyfunctional carboxylic acids, etc. In addition, reactants of unsaturated carboxylic acid esters or amides containing electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, containing halogenated groups or A reaction product of unsaturated carboxylic acid esters or amides with detachable substituents such as toluene sulfonyloxy group and monofunctional or polyfunctional alcohols, amines, or thiols is also suitable. In addition, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with vinyl benzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, and the like can also be used. As their specific compounds, the compounds described in paragraphs 0095 to 0108 of JP 2009-288705 A can also be suitably used in the present invention.

It is also preferable that the polymerizable compound contains one or more groups containing ethylenically unsaturated bonds and has a boiling point of 100°C or higher under normal pressure. For example, the compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, and the content is incorporated in this specification.

The polymerizable compound is dipentaerythritol triacrylate (as a commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product is KAYARAD D-320; Nippon Kayaku Co. , Ltd.) dipentaerythritol penta(meth)acrylate (as a commercial product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structure of these (meth)acrylic groups via diethanol residues or propylene glycol residues (For example, SR454 and SR499 commercially available from Sartomer Company) are preferred. It is also possible to use their oligomer types. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), etc. can also be used. The aspect of the 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 a polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred. The unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to polymerize having an acid group The sex compound is more preferable, and the aliphatic polyhydroxy compound in the ester is pentaerythritol and/or dipentaerythritol is more preferable. 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 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development dissolution characteristic is good, and if it is 40 mgKOH/g or less, it is advantageous for production and/or handling. Moreover, by being within the above-mentioned range, the photopolymerization performance is good, and the curability is excellent.

The compound containing the 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. Polyols such as methylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine are esterified with (meth)acrylic acid and ε-caprolactone. The obtained ε-caprolactone is modified to multifunctional (meth)acrylate. Among them, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

【Chemical formula 9】

In formula (Z-1), all 6 Rs are groups represented by the following formula (Z-2), or 1 to 5 of the 6 Rs are groups represented by the following formula (Z-2), and the remainder It 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 the number of 1 or 2, and * represents a bonding bond.

【Chemical formula 11】

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

Polymerizable compounds containing a caprolactone structure, for example, are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series. Examples include DPCA-20 (formula (Z-1) to (Z-3) where m is 1, The number of groups represented by formula (Z-2) is 2, and R ¹ is a compound with hydrogen atoms), DPCA-30 (in this formula, m is 1, the number of groups represented by formula (Z-2) The compound whose number is 3 and R ¹ is a hydrogen atom) ､DPCA-60 (In the formula, m is 1, the number of the group represented by formula (Z-2) is 6, and R ¹ is a compound that is hydrogen atom ), DPCA-120 (in the formula, m is 2, the formula (Z-2) represented by 6, R ¹ are hydrogen atoms) to the number of groups 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 independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y respectively Each independently represents an integer of 0-10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group. In formula (Z-4), the total of (meth)acrylic groups is 3 or 4, m each independently represents an integer of 0-10, and the total of each m is an integer of 0-40. In formula (Z-5), the total of (meth)acrylic groups is 5 or 6, n each independently represents an integer of 0-10, and the total of each n is an integer of 0-60.

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

The compound represented by the formula (Z-4) or the formula (Z-5) may be used singly, or two or more of them may be used at the same time. In particular, in formula (Z-5), 6 Xs are all acryloyl groups, in formula (Z-5), 6 Xs are all acryloyl groups, and compounds in which at least one of the 6 Xs is a hydrogen atom The form of the mixture is better. With this structure, the developability can be further improved.

The total content in 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 formula (Z-4) or 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 The process of forming a reaction to bond the ring-opening skeleton; and for example, the process of reacting the terminal hydroxyl group of the ring-opening skeleton with (meth)acrylic acid chloride to introduce (meth)acrylic acid groups. Each process is a well-known process, and those skilled in the art can easily synthesize the compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred. Specifically, the compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to (f)") can be given, among which, the exemplified compounds (a) and (b) , (E), (f) are better.

【Chemical formula 13】

【Chemical formula 14】

As a commercially available product of the polymerizable compound represented by the formula (Z-4) and (Z-5), for example, SR-494, a 4-functional acrylate containing 4 ethoxy chains manufactured by Sartomer Company , Nippon Kayaku Co., Ltd. is a 6-functional acrylate containing 6 pentoxy chains, namely DPCA-60, and a 3-functional acrylate containing 3 isobutoxy chains, namely TPA-330, etc.

As a polymerizable compound, polyurethanes described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765 Acrylics; those containing ethylene oxide-based skeletons described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Urethane compounds are also preferred. In addition, by using the addition of the amine structure and/or the thioether structure described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238, the molecule contains an amine structure and/or a sulfide structure. As a polymerizable compound, it is possible to obtain a curable composition with a very excellent photosensitive speed. Commercial products include urethane oligomer 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.), etc.

The SP (Solubility Parameter) value of the polymerizable compound is preferably 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more. In this specification, the SP value is calculated by the Hoy method (HLHoy Journal of Painting, 1970, Vol. 42, 76-118) unless otherwise specified. Regarding the SP value, the unit is omitted and 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 a polymerizable compound containing a cardo skeleton, a polymerizable compound having a 9,9-diaryl fluoride skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

Formula (Q3) 【Chemical formula 15】

In the above 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 substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted by a heteroatom. 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 greater than or equal to 0, and the upper limits of e, f, g, and h are each that can be contained ^{from Ar 11} to Ar ¹⁴ The number of substituents minus the value of a, b, c or d. Wherein, 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 each independently be substituted with The benzene ring enclosed by the dotted line may be substituted with a ring other than the benzene ring enclosed by the dotted line.

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

In the formula (Q3), X ¹ to X ⁴ each independently represent a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a heteroatom. The ^{polymerizable group-containing substituent represented by X 1} to X ⁴ is not particularly limited, but an aliphatic group containing a polymerizable group is preferred. The aliphatic group containing a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but an alkylene group having 1 to 12 carbon atoms other than the polymerizable group is preferred, and the number of carbon atoms is 2 to 10 The alkylene group is more preferable, and the alkylene group having 2 to 5 carbon atoms is more preferable. Among the aliphatic groups containing polymerizable groups represented by X ¹ to X ⁴ , when the aliphatic group is substituted by a hetero atom, it is preferably substituted by -NR- (R is a substituent), an oxygen atom, or a sulfur atom. It is more preferable that the non-adjacent -CH ₂ -in the aliphatic group is substituted by an oxygen atom or a sulfur atom, and the non-adjacent -CH ₂ -in the aliphatic group is further preferably substituted by an oxygen atom. It ^{is preferable that one or two places of the aliphatic group containing polymerizable groups represented by X 1} to X ⁴ are substituted by heteroatoms, and one place is more preferable to be substituted by heteroatoms, and it is contained ^{with Ar 11} ～Ar ¹⁴ It is more preferable that one adjacent aryl group of the benzene ring surrounded by a dotted line is substituted with a heteroatom. As the ^{polymerizable groups contained in the aliphatic groups containing polymerizable groups represented by X 1} to X ⁴ , polymerizable groups capable of undergoing radical polymerization or cationic polymerization (hereinafter, also referred to as radical polymerizable groups, respectively) Group and cationically polymerizable group) are preferred. As the radical polymerizable group, a generally known radical polymerizable group can be used. Preferably, a polymerizable group containing an ethylenically unsaturated bond capable of radical polymerization can be used. Specifically, Examples include vinyl groups, (meth)acryloxy groups, and the like. Among them, (meth)acryloxy is preferred, and acryloxy is more preferred. As the cationically polymerizable group, generally known cationically polymerizable groups can be used. Specifically, alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, and spiro Cycloorthoester group, vinyloxy group, etc. Among them, alicyclic ether groups and vinyloxy groups are preferred, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferred. The above-mentioned polymerizable groups contained in the substituents contained in Ar ¹¹ to Ar ^{14 are preferably radical polymerizable groups.} Ar ¹¹ ~ Ar ¹⁴ above in 2 comprises a polymerizable group-containing substituents of group, Ar ¹¹ ~ Ar ¹⁴ in 2 to 4 comprising a polymerizable group-containing substituent is a group of preferred, Ar ¹¹ ~ Ar ¹⁴ in It is more preferable that two or three of it contain a substituent containing a polymerizable group, and it is more preferable that two of Ar ¹¹ to Ar ¹⁴ contain a substituent containing a polymerizable group. 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 each independently be substituted with a benzene ring surrounded by a dotted line, or Substitution is a ring other than the benzene ring surrounded by a dotted line.

In formula (Q3), a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably both a and b are 1. In formula (Q3), c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and more preferably both c and d are 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. Examples include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, and aryl groups. , Heteroaryl and alicyclic groups, etc. The substituent represented by R ¹ to R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group are more preferable. A group, a methoxy group or a phenyl group 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 substituted with a ring other than the benzene ring surrounded by a dotted line.

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

As the compound represented by the formula (Q3), for example, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]sulfonate and the like can be cited. As the polymerizable compound containing a 9,9-diaryl sulfide skeleton, the compounds described in JP 2010-254732 A can also be preferably used.

The polymerizable compound containing the 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.).

[Multifunctional thiol compound] The curable composition contains a multifunctional thiol compound. In this specification, a multifunctional thiol compound means a compound containing two or more thiol groups (that is, groups represented by -SH) in the same molecule. The content of the polyfunctional thiol compound is not particularly limited, but it is usually 1 to 10% by mass with respect to the content of the above-mentioned coloring agent in many cases. Among them, from the viewpoint that the curable composition has a more excellent effect of the present invention, 1 to 5.5% by mass is preferable, and 1.5 to 3.5% by mass is more preferable. The content of the polyfunctional thiol compound relative to the total solid content of the curable composition is preferably 0.55 to 3.5% by mass, and more preferably 0.8 to 2.0% by mass. A polyfunctional thiol compound may be used individually by 1 type, and may use 2 or more types together. When two or more types are used at the same time, the total of them is preferably within the above-mentioned 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 150 to 1,000 is more preferable. The multifunctional thiol compound contains 2 or more thiol groups in the molecule, preferably 3 or more, more preferably 10 or less, more preferably 6 or less, and more preferably 4 or less. good. Among them, the polyfunctional thiol compound is preferably trifunctional or higher, and more preferably trifunctional or tetrafunctional. If 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 a polyfunctional thiol compound, a compound containing 2-6 groups represented by formula (1) in each molecule is preferred, a compound containing 2 to 4 is more preferred, a compound containing 3 or 4 To be further preferred. ^{Examples of the divalent linking group in L 2} in formula (1) include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene , Substituted alkynylene groups), divalent aromatic groups (for example, arylalkylene groups, substituted arylalkylene groups), divalent heterocyclic groups, oxygen atoms (-O-), imino groups (-NH-), A substituted imino group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl group (-CO-), a combination of these, and the like. When the divalent linking group is an alkylene group, the number of carbon atoms in 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 preferable.

【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 2-6. In addition, a plurality of L ¹ and L ² may be the same or different.

The states of L ¹ and L ² in formula (2) are the same as those of formula (1). In formula (2), n is preferably 2 to 4, more preferably 3 or 4. As the n-valent linking group in formula (2), that is, X, for example: -(CH ₂ ) _m- (m represents an integer of 2 to 6) and other divalent linking groups; having 3 trihydroxy groups Trivalent linking group such as methyl propane residue and -(CH ₂ ) _p- (p represents an integer of 2-6.) isocyanurea ring; tetravalent linking group such as pentaerythritol residue; or 5 valent linking group Group; 6-valent linking group such as dipentaerythritol residues.

As specific examples of polyfunctional thiol compounds, for example, 1,4-butanediol bis(thioglycolate), pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tris(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-mercaptobutanoyloxy)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, the polyfunctional thiol compound is selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and trimethylolpropane tris (3-mercaptopropionic acid) from the viewpoint that the curable composition has more excellent effects of the present invention. At least one of the group consisting of ester) is more preferable.

[Optional components] <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 even when the curable composition is prepared and stored for a predetermined period of time, a cured film having an excellent pattern shape can be obtained. The polymerization inhibitor has the effect of suppressing the reaction between the polyfunctional thiol compound and the polymerizable compound in the curable composition in 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. If 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% by mass relative to the total solid content of the curable composition, and more preferably 0.0015 to 0.01% by mass.

The polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used. Examples of compounds used as polymerization inhibitors include phenol-based compounds, quinone-based compounds, hindered amine-based compounds, phenothiazine-based compounds, and nitrobenzene-based compounds. The above-mentioned compounds may be used singly, or two or more of them may be used at the same time.

Examples of phenolic compounds include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butylcatechol, 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-tert-butylphenol, pentaerythritol tetrakis (3,5-di-tert-butyl 4-hydroxyphenyl ethyl propionate), 4-methoxy-1-naphthol and 1,4-dihydroxynaphthalene Wait.

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

【Chemical formula 18】

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

_{As R 1} to R ₅ in the formula (IH-1), a hydrogen atom, an alkyl group having 1 to 5 carbons (for example, methyl and ethyl, etc.), an alkoxy group having 1 to 5 carbons (for example, methyl An oxy group, an ethoxy group, etc.), an alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group, etc.), or a phenyl group are preferred. Among them, it _{is more preferable that R 1} and R ₅ are independently a hydrogen atom or a tertiary butyl group, it is more preferable that R ₂ and R ₄ are a hydrogen atom, and R ₃ is a hydrogen atom, an alkyl group having 1 to 5 carbons or a carbon. An alkoxy group having a number of 1 to 5 is more preferable.

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

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

【Chemical formula 19】

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

As the polymerization inhibitor, each of the above-mentioned compounds may be used singly, two kinds may be used simultaneously, or three or more kinds may be used simultaneously. The polymerization inhibitor preferably contains a phenolic compound. Among them, it is more preferable that the polymerization inhibitor 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 phenolic compound and a hindered amine compound. The curable composition containing a phenolic compound and a hindered amine 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 10-40% by mass. If the solid content of the curable composition is equal to or greater than the lower limit, the viscosity will be low and the coating properties will be optimized. Moreover, by reducing the concentration of the more reactive compound, the stability over time is optimized. If the solid content of the curable composition is equal to or less than the upper limit, the viscosity will be kept low and the coatability will be optimized. Moreover, colorants with heavier specific gravity are not easy to settle, and their 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 relative to the total mass of the curable composition. Moreover, an organic solvent may be used individually by 1 type, and may use 2 or more types together. When two or more organic solvents are used at the same time, it is preferable that the total amount thereof falls within the above-mentioned range.

The organic solvent is not particularly limited, and examples 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, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfide , 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 and Ethyl Lactate, etc.

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

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

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

When the curable composition contains a dispersant, the content of the dispersant relative to the total solid content of the curable composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 5% by mass or more. The mass% or more is particularly good, and 17 mass% or more is the best. Regarding the upper limit of the content of the dispersant, relative to the total solid content of the curable composition, 50% by mass or less is preferable, 30% by mass or less is more preferable, and 22% by mass or less is more preferable. 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. One type of dispersant may be used alone, or two or more types may be used at the same time. When two or more dispersants are used at the same time, 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, polymer compounds are preferred. Examples of dispersants include polymer dispersants [for example, polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, Modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine and pigment derivatives, etc. Polymer compounds can be further classified into linear polymers, end-modified polymers, grafted polymers, and block polymers according to their structures.

(Polymer compound) The polymer compound is adsorbed on the surface of the dispersed body such as colorant (for example, inorganic pigment), and plays a role of preventing the re-aggregation of the dispersed body. Therefore, terminal-modified polymers, graft-type polymers, and block-type polymers containing fixed sites on the surface of the pigment are preferred.

The polymer compound preferably contains a structural unit including a graft chain. In this manual, "structural unit" has the same meaning as "repeating unit". This kind of polymer compound containing structural units containing graft chains has affinity with solvents through the graft chains, so it is the dispersibility of black pigments and other colorants and the dispersion stability over time (stability over time) Outstanding ones. The polymer compound containing the structural unit including the graft chain has affinity with the polymerizable compound or other resins that can be used at the same time due to the existence of the graft chain. As a result, residues are less likely to be generated in alkaline development. If the graft chain becomes longer, the steric repulsion effect is improved and the dispersibility of black pigments and the like is improved. On the other hand, if the graft chain is too long, the adsorption power to color pigments such as black pigments will decrease, and the dispersibility of black pigments and the like will tend to decrease. Therefore, the graft chain is preferably 40 to 10,000 atoms other than hydrogen atoms, more preferably 50 to 2,000 atoms other than hydrogen atoms, and more preferably 60 to 500 atoms other than hydrogen atoms. good. Wherein, the graft chain means the root of the main chain of the copolymer (atoms bonded to the main chain from the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure. Examples of the polymer structure include a poly(meth)acrylate structure (for example, a poly(meth)acrylic acid structure), a polyester structure, and a polyurethane structure. Acid ester structure, polyurea structure, polyamide structure and polyether structure. In order to improve the interaction between the graft chain and the solvent, and thereby improve the dispersibility of black pigments, etc., the graft chain contains a group selected from the group consisting of polyester structure, polyether structure and poly(meth)acrylate structure. A graft chain of at least one of the group is preferable, and a graft chain containing at least either a polyester structure or a polyether structure is more preferable.

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

Corresponding to the structural unit containing the graft chain contained in the polymer compound, commercially available macromonomers suitable for synthesizing polymer compounds 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, Toagosei Company, Limited.), AA-714 (trade name, Toagosei Company, Limited.), AY-707 (trade name, Toagosei Company, Limited.) Manufacturing), 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.), Blemmer PP-1000 (trade name, manufactured by NOF CORPORATION.), Blemmer 55-PET-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-400 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-1300 (trade name, manufactured by NOF CORPORATION.), Blemmer 43PAPE-600B (trade name, manufactured by NOF CORPORATION.), and the like. Among them, AA-6 (trade name, manufactured by Toagosei Company, Limited.), AA-10 (trade name, Toagosei Company, Limited.), AB-6 (trade name, manufactured by Toagosei Company, Limited.), AS- 6 (trade name, Toagosei Company, Limited.), AN-6 (trade name, manufactured by Toagosei Company, Limited.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.), etc. are preferred.

The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. It is more preferable that the dispersant 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 contain the above-mentioned structure in one dispersant alone, or may contain a plurality of such structures in one dispersant. Here, the polycaprolactone structure refers to a structure containing a ring-opening structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opening structure for δ-valerolactone as a repeating unit. As a specific example of the dispersant containing a polycaprolactone structure, j and k in the following formula (1) and following formula (2) are mentioned. In addition, as a specific example of the dispersant containing a polyvalerolactone structure, those in which j and k are 4 in the following formula (1) and the following formula (2) can be given. As a specific example of the dispersant containing a polymethyl acrylate structure, in the following formula (4), X ⁵ is a hydrogen atom and R ⁴ is a methyl group. In addition, as a specific example of the dispersant containing a polymethyl methacrylate structure, in the following formula (4), X ⁵ is a methyl group and R ⁴ is a methyl group.

・As the structural unit containing the graft chain, the polymer compound containing the structural unit of the graft chain preferably contains a structural unit represented by any one of the following formulas (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 formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. Preferably, W ¹ , W ² , W ³ and W ⁴ are oxygen atoms. In formula (1) to formula (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 atoms) from the viewpoint of synthesis restriction, and each independently It is more preferable to be a hydrogen atom or a methyl group, and a methyl group is still more preferable.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and there is no particular restriction on the structure of the linking group. As the ^{bivalent linking group represented by Y 1} , Y ² , Y ³ and Y ⁴ , specifically, the following linking groups (Y-1) to (Y-21) and the like can be given as examples. In the structure shown below, A and B respectively represent bonding sites. Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease 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. Specifically, it includes an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an arylene sulfide group, and a heteroarylene sulfide group. And amine groups and so on. Among these, as ^{the organic groups represented by Z 1} , Z ² , Z ³ and Z ⁴ , especially from the viewpoint of improving dispersibility, those containing stereorepulsive effects are preferred, and each independently has a carbon number of 5 to 24 The alkyl or alkoxy group is more preferably, wherein each independently a branched alkyl group having 5 to 24 carbons, a cyclic alkyl group having 5 to 24 carbons, or an alkoxy group having 5 to 24 carbons is further good. In addition, the alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic.

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

In the formula (3), R ³ represents a branched or straight chain alkylene group, and 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, the presence of a plurality of R ³ may be the same or different from each other. In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in 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 carbons, a branched alkyl group having 3 to 20 carbons, or a cyclic alkyl group having 5 to 20 carbons are preferred, and those having 1 to 20 carbons are preferred. The linear alkyl group is more preferable, and the linear alkyl group having 1 to 6 carbon atoms is more preferable. In the formula (4), when q is 2 to 500, multiple X ⁵ and R ^{4 in the} graft copolymer may be the same or different from each other.

The polymer compound may contain two or more different structures and the structural unit of the graft chain. That is, the molecules of the polymer compound may contain structural units represented by formulas (1) to (4) that are different in structure. In formulas (1) to (4), n, m, p, and q are respectively When it represents an integer of 2 or more, in formulas (1) and (2), structures with different j and k can be included in the side chain. In formulas (3) and (4), there are multiple R ³ , R ⁴ and X ⁵ may be the same or different from each other.

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

【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), from the viewpoint of the temporal stability and developability of the curable composition, the structural unit represented by the following formula (3A) or formula (3B) is more preferable.

【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 the structural unit containing the graft chain, the polymer compound preferably contains the 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 calculated by mass, and relative to the total mass of the polymer compound, 2 to 90% It is preferable to include in the range, and it is more preferable to include in the range of 5 to 30%. If the structural unit containing the graft chain is included in this range, the dispersibility of the black pigment will be high, and the developability at the time of forming a cured film will be good.

・Hydrophobic structural unit It is preferable that the polymer compound contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (that is, it is not equivalent to the structural unit containing the graft chain). However, 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 phosphoric acid group, a phenolic hydroxyl group, etc.).

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

The ClogP value is calculated by the program "CLOGP" that can be obtained from Daylight Chemical Information System, Inc. This program provides the value of "calculated logP" calculated by Hansch, Leo's fragment approach (refer to the following documents). Fragmentapproach divides the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and sums up the logP contribution allocated to the fragments to calculate the logP value of the compound. The details are described in the following documents. In this manual, the 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), which is a quantitative value that represents the physical property value of how an organic compound is distributed in the two-phase equilibrium of oil (usually 1-octanol) and water, as follows式 expression. logP=log(Coil/Cwater) In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase. If the value of logP sandwiches 0 and increases in the positive direction (plus), it means that the oil solubility increases. If the absolute value (minus) increases in the negative direction, it means that the water solubility increases, which is negatively correlated with the water solubility of organic compounds. It is widely used to estimate the hydrophilic and hydrophobic parameters of organic compounds.

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

【Chemical formula 24】

In formulas (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or 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, more preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably hydrogen atoms. X represents an oxygen atom (-O-) or an imino 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 divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), divalent Aromatic groups (for example, aryl group, substituted aryl group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted arylene group An amino group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl group (-CO-), a combination of these, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, and a saturated aliphatic group is preferred. In addition, 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 6-20, more preferably 6-15, and still more preferably 6-10. The aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups.

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 substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), substituted imino groups (=NR ³² , where 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 oxyethylene structure or an oxypropylene structure. L may include a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As the polyoxyethylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by -(OCH ₂ CH ₂ )n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2-10.

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

The aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group also includes a ring assembly hydrocarbyl group and a cross-linked cyclic hydrocarbyl group. Examples of the ring assembly hydrocarbyl group include bicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. As the crosslinked cyclic hydrocarbon ring, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2] 2-cyclic hydrocarbon rings such as octane ring and bicyclic [3.2.1] octane ring, etc.), homobrylene (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-cyclic hydrocarbon rings such as methylene naphthalene ring, etc. The cross-linked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydropyrene, perhydroindene, and perhydrogen ring Condensation has a plurality of 5 to 8-membered cycloalkane ring condensed ring. Compared with an unsaturated aliphatic group, the aliphatic group is preferably a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

The carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. Among them, 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 substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR ³² , where R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Among them, the heterocyclic group does not have an acid group as a substituent.

In the formula (iii), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl Group, ethyl, propyl, etc.), Z or -LZ. However, the meanings of L and Z are the same as those of L and Z in the 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 a monomer represented by the above general formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, and L is a single bond or an alkylene group, or a divalent compound containing an oxyalkylene structure Compounds in which X is an oxygen atom or imino group, and Z is an aliphatic group, heterocyclic group or 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), compounds 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 are preferred.

Examples of representative compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, and styrenes. As examples of representative compounds represented by formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of JP 2013-249417 A, and these contents are incorporated in this specification.

In the polymer compound, the hydrophobic structural unit is calculated in terms of mass, and it is preferably contained in the range of 10 to 90%, and more preferably contained in the range of 20 to 80% relative to the total mass of the polymer compound. When the content is within the above range, more satisfactory 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 further includes a structural unit containing a functional group that can interact with colorants such as black pigments. Examples of functional groups that can interact with colorants such as black pigments include acid groups, basic groups, coordinating groups, and reactive functional groups. When the polymer compound contains an acid group, a basic group, a coordination 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. Or it is preferable to contain reactive structural units. In particular, the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, whereby the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of colorants such as black pigments in the curable composition has alkali solubility. The curable composition containing this type of polymer compound is excellent in the light-shielding property of the exposed part, and the alkali developability of the unexposed part is improved. Since the polymer compound has a structural unit containing an acid group, the polymer compound becomes easy to integrate with the solvent and the coating properties are also improved. It is presumed that this is because the acid group in the structural unit containing the acid group easily interacts with the colorant such as black pigment, and the polymer compound makes the colorant such as black pigment stably disperse, and the polymer compound disperse the colorant such as black pigment The viscosity becomes lower, and the polymer compound itself is easily dispersed stably.

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

As a functional group that can interact with black pigments and other colorants, that is, an acid group, for example, there are carboxylic acid group, sulfonic acid group, phosphoric acid group or phenolic hydroxyl group. Among them, carboxylic acid group, sulfonic acid group and phosphoric acid group At least one is preferable, and the carboxylic acid group is more preferable from the viewpoint of good adsorption force for colorants such as black pigments and high dispersibility of the colorants. That is, it is preferable that the polymer compound further 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 more structural units containing acid groups. The polymer compound may contain structural units with acid groups or not. When it is contained, the content of structural units with acid groups is calculated by mass. Relative to the total mass of the polymer compound, 5 to 80% is preferred. From the viewpoint of damage to the image intensity of alkali development, 10-60% is more preferable.

As functional groups that can interact with black pigments and other colorants, that is, basic groups, for example, there are primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, and amide groups. In view of the good adsorption power of colorants such as black pigments and the higher dispersibility of the pigments, the tertiary amino group is preferred. The polymer compound can contain one kind or two or more kinds of these basic groups. The polymer compound may or may not contain a structural unit with a basic group. When it is contained, the content of a structural unit with a basic group is calculated by mass. Relative to the total mass of the polymer compound, 0.01% or more and 50% or less is Preferably, from the viewpoint of suppressing the hindrance of developability, 0.01% or more and 30% or less are more preferable.

As a functional group that can interact with colorants such as black pigments, that is, a coordinating group and a reactive functional group, for example, acetylacetoxy, trialkoxysilyl, Isocyanate group, acid anhydride and chlorinate etc. From the viewpoints of good adsorption force for colorants such as black pigments and high dispersibility of the pigments, acetylacetoxy is preferred. The polymer compound may have one kind or two or more kinds of these groups. The polymer compound may contain a structural unit with a coordinating group or a reactive functional group, or not. When it is contained, the content of the structural unit is calculated by mass, relative to the total mass of the polymer compound, 10% The above and 80% or less are preferable, and from the viewpoint of suppressing the hindrance of developability, 20% or more and 60% or less are more preferable.

When the polymer compound contains, in addition to the graft chain, a functional group that can interact with colorants such as black pigments, it may contain the above-mentioned functional group that can interact with colorants such as various black pigments, and is not particularly limited. 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 formulas (iv) to (vi).

【Chemical formula 25】

In formulas (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 Group (for example, methyl, ethyl, propyl, etc.). In formulas (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbons, and each independently is a hydrogen atom or a methyl group. good. In the general formula (iv), it ^{is more preferable that R 12} and R ¹³ are each a hydrogen atom.

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

_{L 1 in} formula (iv) to formula (v) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), 2 Valence aromatic groups (for example, aryl and substituted aryl groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imine bond (-NR ³¹ '-, wherein, R ^31' is an aliphatic group, an aromatic group or a heterocyclic group), carbonyl bond (-CO-), and the plurality of combinations and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. Compared with an unsaturated aliphatic group, the aliphatic group is preferably a saturated 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 6-20, 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, 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. One or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed in the heterocyclic ring. The heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR ³² , where R 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 oxyethylene structure or an oxypropylene structure. L ₁ may contain a polyoxyalkylene structure including two or more oxyalkylene structures repeatedly. As the polyoxyethylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by -(OCH ₂ CH ₂ ) _n -, and n is preferably an integer of 2 or more, and more preferably an integer of 2-10.

In formulas (iv) to (vi), Z ₁ represents a functional group other than the graft chain that can interact with colorants such as black pigments. Carboxylic acid groups and tertiary amine groups are preferred, and carboxylic acid groups are more preferred. good.

In 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.), an alkyl group having 1 to 6 carbon atoms (for example, a , 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. As R ¹⁴ , R ¹⁵ and R ¹⁶ , each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom is more preferred.

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, X _{A compound in which 1} is an oxygen atom or an imino 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 preferred. Furthermore, as a 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.

Hereinafter, representative examples of monomers (compounds) represented by formula (iv) to formula (vi) are shown. Examples of monomers include the reaction of methacrylic acid, crotonic acid, isocrotonic acid, compounds containing addition polymerizable double bonds and hydroxyl groups in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride The reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and phthalic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride, A reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group and trimellitic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group and a pyromellitic anhydride in the molecule, acrylic acid, acrylic acid dimer, acrylic acid Oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol and 4-hydroxybenzyl acrylamide, etc.

From the viewpoints of interaction with colorants such as black pigments, dispersion stability, and permeability to developing solutions, the content of structural units containing functional groups that can interact with colorants such as black pigments is relative to that of polymer compounds. For the total mass of, 0.05% by mass to 90% by mass is preferable, 1.0% by mass to 80% by mass is more preferable, and 10% by mass to 70% by mass is still more preferable.

・Other structural units In addition, in order to improve various properties such as image strength, the polymer compound can further contain structural units containing graft chains, hydrophobic structural units, and contain black pigments without compromising the effects of the present invention. Other structural units with various functions (for example, structural units with functional groups that have affinity with the dispersion medium used for the dispersion) are different from the structural units of the functional groups that interact with other colorants. Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles. The polymer compound can use one or more of these other structural units, and the content is calculated by mass. Relative to the total mass of the polymer compound, 0% or more and 80% or less is preferred, 10% or more and 60% The following is better. The content can maintain sufficient pattern formability within the above-mentioned range.

・Physical properties of the polymer compound The acid value of the polymer compound is preferably in the range of 0 mgKOH/g or more and 250 mgKOH/g, more preferably in the range of 10 mgKOH/g or more and 200 mgKOH/g, and 20 mgKOH/g or more and 120 mgKOH/g. The range of g or less is more preferable. If the acid value of the polymer compound is 160 mgKOH/g or less, it is more effective to suppress pattern peeling during development when the cured film is formed. If the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability is more favorable. In addition, when the acid value of the polymer compound is 20 mgKOH/g or more, the sedimentation of colorants such as black pigments can be more suppressed, the number of coarse particles can be reduced, and the temporal stability of the curable composition can be further improved.

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

When forming a light-shielding film, from the viewpoint of suppression of pattern peeling during development and developability, the weight average molecular weight of the polymer compound in the present invention is used as the polymerization method by GPC (Gel Permeation Chromatography) method. The styrene conversion value is preferably 4,000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, more preferably 6,000 or more and 100,000 or less, and particularly preferably 10,000 or more and 50,000 or less. The GPC method is based on the following method, that is, using HLC-8020GPC (manufactured by TOSOH CORPORATION), using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID×15cm) as a column, and used as an eluent THF (tetrahydrofuran).

The polymer compound can be synthesized according to a known method. As a solvent used in the synthesis of polymer compound, for example, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethyl Methyl methamide, N,N-dimethyl acetamide, dimethyl sulfide, toluene, ethyl acetate, methyl lactate and ethyl lactate, etc. These solvents may be used alone or in mixture of two or more kinds.

Specific examples of polymer compounds include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., "Disperbyk-101 (polyamide phosphate), 107 (carboxylate), 110 (containing Acid-based copolymer), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050-4010-4165 (urethane series), EFKA 4330-4340 (block copolymer), 4400-4402 (modified poly 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)", manufactured by Kusumoto Chemicals, Ltd. "disparon KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50 , DA-705, DA-725", Kao Corporation "DEMOL RN, N (formalin naphthalenesulfonate condensation polymer), MS, C, SN-B (aromatic sulfonate formalin condensation polymer)", "HOMOGENOL L -18 (polymer polycarboxylic acid)", "EMULGEN920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)", "ACETAMIN86 (stearyl amine acetate)", Lubrizol Japan Limited "Solsperse 5000 ( Phthalocyanine derivatives), 22000 (azo pigment derivatives), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymers with functional parts at the end), 24000, 28000, 32000, 38500 (Graft copolymer)", "NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene stearate)" manufactured by Nikko Chemicals Co., Ltd., Kawaken Fine Che "HINOACT T-8000E" manufactured by micals Co., Ltd., "organosiloxane polymer KP341" manufactured by Shin-Etsu Chemical Co., Ltd., "W001: cationic surfactant" manufactured by Yusho Co., Ltd. ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol laurate, polyoxyethylene Nonionic surfactants such as ethylene glycol distearate and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, and 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 ”And other polymer dispersants, manufactured by ADEKA CORPORATION “ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ", and "Ionet (trade name) S-20" manufactured by Sanyo Chemical Industries, Ltd., etc. In addition, Acrylic base FFS-6752, Acrylic base FFS-187, Akurikyua-RD-F8, and Cyclomer P can also be used. As commercial products of amphoteric resins, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, manufactured by BYK Chemie GmbH DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822 and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. etc. These polymer compounds may be used singly, or two or more of them may be used at the same time.

As a specific example of the polymer compound, the polymer compound described in paragraphs 0127 to 0129 of JP 2013-249417 A can be referred to, and these contents are incorporated in this specification.

As the dispersant, in addition to the above-mentioned polymer compounds, the graft copolymers of paragraphs 0037 to 0115 (corresponding to the paragraphs 0075 to 0133 of US2011/0124824) of JP 2010-106268 A can also be used. The content can be used and incorporated into this manual. In addition to the above, paragraphs 0028 to 084 of Japanese Patent Application Publication No. 2011-153283 (corresponding to the columns of paragraphs 0075 to 0133 of US2011/0279759) containing side chain structures containing acidic groups bonded via linking groups can also be used. For the high molecular compound of the constituent components, these contents can be cited and incorporated into this specification.

<Binder Resin> The curable composition preferably contains a binder resin. The content of the binder resin relative to the total solid content of the curable composition 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, 30% by mass % Or less is preferable, 25 mass% or less is more preferable, 18 mass% or less is more preferable, and 10 mass% or less is particularly preferable. If 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 binding resin can be used singly, or two or more of them can be used at the same time. When two or more binder resins are used at the same time, the total amount is preferably within the above-mentioned range.

As the binder resin, it is preferable to use a linear organic polymer. As such linear organic polymers, known ones can be used arbitrarily. In order to realize water development or weak alkaline water development, it is better to select linear organic polymers that are soluble or swellable to water or weak alkaline water. Among them, as the binder resin, alkali-soluble resin (resin containing a group that promotes alkali solubility) is particularly preferred. As a binding resin, it can contain at least one group that promotes alkali solubility from a linear organic polymer and a molecule (preferably a molecule with a (meth)acrylic copolymer or a styrene copolymer as the main chain) The alkali-soluble resin is appropriately selected. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic acid/(meth)acrylic acid resins Amine copolymer resins, epoxy resins, and polyimide resins are preferred. From the viewpoint of developability control, (meth)acrylic resin, (meth)acrylamide resin, (meth)acrylic acid /(Meth)acrylamide copolymer resin and polyimide resin are more preferable. Examples of groups that promote alkali solubility (hereinafter, also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. Among them, those that are soluble in organic solvents and can be developed by weakly alkaline aqueous solutions are preferred, and more preferred include alkali-soluble resins containing structural units derived from (meth)acrylic acid. There may be only one type of these acid groups, or two or more types.

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

Among these, [benzyl (meth)acrylate/(meth)acrylic acid/other addition polymerizable vinyl monomers as required] copolymer and [(meth)acrylate/(meth)acrylic acid /Other addition polymerizable vinyl monomers as needed] The copolymer has excellent film strength, sensitivity, and developability, and is preferable. As commercially available products, for example, Acrylic base FF-187, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.), Akurikiyua-RD-F8 (NIPPON SHOKUBAI CO., LTD.), and DAICEL-ALLNEX LTD. Manufacturing 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 the polymerization conditions such as the temperature, pressure, the type and amount of the radical initiator, and the type of solvent when the binder 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 above-mentioned dispersant, and the preferred range is also the same. The acid group includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. At least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable.

(Structural unit containing an acid group) As a structural unit containing an acid group, it is preferable to contain 1 or more types of structural units selected from the structural unit derived from the monomer represented by following formula (vii)-formula (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 The alkyl group (for example, methyl, ethyl, propyl, etc.). In formulas (vii) to (ix), R ²¹ , R ²² and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently is a hydrogen atom or a methyl group. good. In the formula (vii), it ^{is particularly preferable that R 21} and R ²³ are each a hydrogen atom.

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

_{L 2 in} formula (vii) to formula (ix) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), 2 Valence aromatic groups (for example, aryl and substituted aryl groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imine bond (-NR ⁴¹ '-, wherein, R ^41' is an aliphatic group, an aromatic group or a heterocyclic group), carbonyl bond (-CO-), and the plurality of combinations.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. Compared with an unsaturated aliphatic group, the aliphatic group is preferably a saturated 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 6-20, 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, 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. One or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed in the heterocyclic ring. The heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR ⁴² , where R 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, alkylene or oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₂ may include a polyoxyalkylene structure including two or more oxyalkylene structures repeatedly. As the polyoxyethylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by -(OCH ₂ CH ₂ )n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2-10.

In formulas (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.), an alkyl group having 1 to 6 carbon atoms (for example, methyl, 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. As R ²⁴ , R ²⁵ and R ²⁶ , each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom is more preferred.

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 oxyalkylene structure, and X _{A compound in which 2} is an oxygen atom or an imino 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 preferred. Furthermore, 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 binding resin can be synthesized by the same method as the dispersant containing the above-mentioned structural unit containing the graft chain, and its preferred acid value and weight average molecular weight are also the same.

The binding resin may have one or more structural units containing acid groups. The content of the acid group-containing structural unit is calculated by mass. Relative to the total mass of the binder resin, 5-95% is preferred. From the viewpoint of suppressing damage to the image strength caused by alkali development, 10~90% is more preferred. .

<Surfactant> The curable composition preferably contains a surfactant. The surfactant contributes to improving the coatability of the curable composition.

When the curable composition contains a surfactant, the content of the surfactant relative to the total mass of the curable composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. Surfactants may be used singly, or two or more of them may be used at the same time. When two or more surfactants are used at the same time, the total amount is preferably within the above range.

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

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

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

Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F475, F482, Megafac F554, Megafac F780 (above, manufactured by DIC), 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 JP 2011-89090 A can be cited. As the fluorine-based surfactant, a compound (F-1) represented by the following formula can also be mentioned. In 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 relationship of a+c=14 and b=17, respectively. In addition, the weight average molecular weight of the following compound is 15,311, for example.

【Chemical formula 27】

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin Ethoxylates, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901 manufactured by BASF , 904, 150R1), Solsperse20000 (manufactured by Japan Lubrizol Corporation), etc. In addition, Pionin D-6112-W manufactured by TAKEMOTO OIL & FAT CO., LTD, and NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of cationic surfactants include phthalocyanine derivatives (trade name, EFKA-745, manufactured by MORISHITA & CO., LTD.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) .Manufacturing), (meth)acrylic (co)polymer polyflow No.75, No.90, No.95 (manufactured by KYOEISHA CHEMICAL CO., LTD.), W001 (Yusho Co., Ltd.), etc.

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

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

<Silane coupling agent> The silane coupling agent refers to a compound containing a hydrolyzable group and other functional groups in the molecule. In addition, 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 by a hydrolysis reaction and/or condensation reaction. As the hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group can be given. When the hydrolyzable group contains carbon atoms, the carbon number is preferably 6 or less, and more preferably 4 or less. Alkoxy groups having 4 or less carbon atoms or alkenyloxy groups having 4 or less carbon atoms are 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 the silicon atoms bonded by the hydrolyzable group). Does not contain fluorine atoms, silicon atoms (excluding silicon atoms bonded to hydrolyzable groups), alkylene substituted by silicon atoms, straight chain alkyl groups with 8 or more carbons, and branched chain alkanes with 3 or more carbons The base is better.

The silane coupling agent preferably contains a group represented by the following formula (Z). * Indicates the position of the bond. 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 curable functional groups selected from the group consisting of (meth)acryloxy groups, epoxy groups, and oxetanyl groups. The hardenable functional group can be directly bonded to the silicon atom, or can be bonded to the silicon atom via a linking group. Moreover, as a preferable aspect of the hardenable functional group contained in the said silane coupling agent, a radical polymerizable group can also be mentioned.

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

As one of the preferred aspects of the silane coupling agent, a silane coupling agent X represented by the formula (W) can be cited. 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 curable functional group, which is defined as described above, and the preferred range is also the same as described above. Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include an alkylene group substituted with a halogen atom, an aryl group substituted with a halogen atom, -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 substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group substituted with a halogen atom having 6 to 12 carbon atoms, or containing these groups and selected Free -NR ¹² -, -CONR ¹² -, _{-CO-, -CO 2} -, SO ₂ NR ¹² -, -O-, -S- and SO ₂ -consisting of a combination of at least one group Groups are preferred. Groups containing alkylene substituted by a halogen atom with 2 to 10 carbon atoms, -CO ₂ -, -O- ^{, -CO-, -CONR 12} -or a combination of these groups are Better. However, the above-mentioned R ¹² represents a hydrogen atom or a methyl group.

As the silane coupling agent X, 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 -Etsu Chemical Co., Ltd., trade name KBM-503) and glycidoxy octyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-4803), etc.

As another preferred aspect of the silane coupling agent, a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a hardenable functional group in the molecule, and containing a hydrolyzable group bonded to the silicon atom . The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can bond with the following atoms and substituents. These may be the same atom, substituent, or different. Examples of bondable atoms and substituents include hydrogen atoms, halogen atoms, hydroxyl groups, alkyl groups having 1 to 20 carbon atoms, alkenyl groups, alkynyl groups, aryl groups, amine groups that can be substituted with alkyl groups and/or aryl groups, Silyl group, alkoxy group having 1 to 20 carbon atoms, aryloxy group, etc. These substituents may be further substituted by silyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, amine groups that can be substituted with alkyl and/or aryl groups, halogen atoms, Sulfonamide group, alkoxycarbonyl group, amide group, urea group, ammonium group, alkylammonium group, carboxylic acid group or its salt, sulfo group or its salt, etc. are substituted. 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 formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule. 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 Group is better. In addition, the structure of the amino 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 amino 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 of these. These may further have substituents. Examples of the substituents that can be introduced include silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, amino groups, and halogen atoms. , Sulfonamide group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkoxy ammonium group, alkyl ammonium group, carboxylic acid group or its salt, sulfo group, etc. The nitrogen atom is preferably bonded to the curable functional group via any organic linking group. As a preferable organic linking group, the substituent which can be introduced into the above-mentioned nitrogen atom and the organic group bonded to it can be mentioned.

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

The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, and can be in the above-mentioned range (270 or more is preferable).

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

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

<Ultraviolet absorber> The curable composition may contain an ultraviolet absorber. Thereby, the pattern shape of the cured film can be made more excellent (fine). As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples of these, the compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012/0068292) of JP 2012-068418 A can be used, and these contents can be incorporated into this specification. . In addition, diethylamino-phenylsulfonyl-based ultraviolet absorbers (manufactured by DAITO CHEMICAL CO., LTD., trade name: UV-503) and the like can also be preferably used. Examples of the ultraviolet absorber include the compounds exemplified in paragraphs 0134 to 0148 of JP 2012-32556 A. The content of the ultraviolet absorber is preferably 0.001 to 15% by mass relative to the total solid content of the curable composition, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass.

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

[Mixing and Dispersing Process] The mixing and dispersion process is a process in which the above-mentioned components are mixed by a known mixing method (for example, agitator, homogenizer, high-pressure emulsification device, wet grinder, and wet disperser) to obtain a curable composition . In the mixing and dispersing process, each component constituting the curable composition can be mixed at once, or it can be mixed sequentially after dissolving or dispersing each component in an organic solvent. The order of input and working conditions during cooperation are not particularly limited. The mixing and dispersing process may include the process of making a dispersion.

(Process for making dispersion) The process for making dispersion is to mix colorant, dispersant and solvent, and disperse the colorant by the above method to make the dispersion. Other components can be mixed with the prepared dispersion to produce a curable composition. In the manufacturing process of the dispersion, as the mechanical force used for the dispersion of the pigment, compression, squeezing, impact, cutting or pitting can be mentioned. Specific examples of these processes include bead milling, sand mixing, roll milling, high-speed impeller, sanding, jet mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, it is possible to appropriately use the "Dispersion Technology Encyclopedia, issued by the Information Agency Co., Ltd., July 15, 2005" and "suspension (solid/liquid dispersion system)-centered dispersion technology and actual comprehensive data on industrial applications." Collected, issued by the Publishing Department of the Management Development Center, October 10, 1978, "the craft and dispersing machine recorded in". In the process of making the dispersion liquid, the miniaturization of the pigment based on the salt milling process can be carried out. The raw materials, equipment, and processing conditions used in the salt milling process can be those described in Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629, for example. The production method of the curable composition preferably includes a process for obtaining the above-mentioned coloring agent by the thermoplasma method. The process of obtaining the colorant is carried out before mixing the above-mentioned components. The specific manufacturing process of the coloring agent based on the thermoplasma method is as described above.

<Standing process> The colorant can go through the following standing process before being supplied to the mixing and dispersion process or the process of making a dispersion. The static process is that the colorant obtained by the thermoplasma method is not exposed to the atmosphere after its manufacture, but is placed in a sealed container with controlled oxygen concentration for a predetermined time (12-72 hours is preferred, 12 ~48 hours is more preferable, and 12-24 hours is more preferable). At this time, it is better to control the moisture content 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 moisture content in the sealed container can be adjusted by adjusting the oxygen concentration and moisture content in the inert gas supplied into the sealed container. As the inert gas, nitrogen and argon are preferred, and among them, nitrogen is more preferred. After the above-mentioned standing process, the surface of the colorant and the grain boundary become stable. This can 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 colorant manufacturing method. From the viewpoint that the curable composition has more excellent effects of the present invention, it is better to replace the process H by the process H.

<Filtration process> The filtration process is a process in which the hardenable composition manufactured by the above mixing and dispersion process is filtered by a filter. In the filtration process, foreign matter can be removed from the hardenable composition and/or defects can be reduced. As the filter, as long as it has been used for filtering purposes, etc., it can be used without particular limitation. For example, fluororesins such as PTFE (polytetrafluoroethylene: polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP), etc. can be mentioned. 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, the filter clogging of the pigment can be suppressed, and fine foreign matter such as impurities and agglomerates contained in the pigment can be reliably removed. When using filters, different filters can also be combined. At this time, the filtration by the first filter may be performed only once, or may be performed two or more times. When combining different filters for more than two filtrations, the pore size after the second filtration is the same as the pore size of the first filtration or larger than the pore size of the first filtration. It is also possible to combine the first filters with different pore diameters within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., ADVANTEC TOYO KAISHA, LTD., Nihon Entegris K.K. (formerly Mykrolis Corpration), or KITZ MICRO FILTER CORPORATION. The second filter can be formed of the same material as the above-mentioned first filter. The appropriate pore size of the second filter is about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

[Cured 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, specifically, it is suitable for light-shielding the peripheral part of the light-receiving part of an image sensor. Hereinafter, as an example, a case where the cured film is used as a light-shielding film in the peripheral portion of the light-receiving portion of an image sensor will be described.

The film thickness of the light-shielding film is not particularly limited. From the viewpoint that the light-shielding film has more excellent effects of the present invention, in terms of the film thickness after drying, 0.2 μm or more and 50 μm or less is preferred, 0.3 μm or more and 10 μm The following are more preferable, and 0.3 μm or more and 5 μm or less are more preferable. The above-mentioned curable composition has a high optical density per unit volume (high light-shielding properties), and therefore, it is possible to further reduce the film thickness compared to the conventional curable composition using black pigments. As for the size of the light-shielding film (the length of one side of the light-shielding film provided on the periphery of the light-receiving part of the sensor), from the viewpoint that the light-shielding film has more excellent effects of the present invention, 0.001mm or more and 10mm or less is preferable, 0.05mm Above and 7 mm or less is more preferable, and 0.1 mm or more and 3.5 mm or less is still more preferable.

[Method of Manufacturing Cured Film] Next, a method of manufacturing 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 the cured film includes the following curable composition layer formation process and exposure process. The manufacturing method of the cured film preferably further includes a development process. Curable composition layer formation process: a process of forming a curable composition layer on a support. Exposure process: the process of exposing the above-mentioned curable composition layer. Development process: the process of developing the exposed curable composition layer to form a patterned cured film (light-shielding film).

Specifically, the above-mentioned curable composition is applied directly or through other layers on a substrate to form a curable composition layer (curable composition layer formation process), and exposed through a predetermined mask pattern, and only exposed to light The irradiated coating film is partially cured (exposure process), and developed with a developer (development process), whereby the above-mentioned cured film can be manufactured. Hereinafter, the above-mentioned manufacturing processes will be described.

<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 that includes coating a curable composition on a support to form a curable composition layer is preferable, and includes directly coating a curable composition on the support to form a curable composition on the support. The coating process of the layer is better. As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, and photoelectric conversion element substrates used for solid-state imaging devices, etc. (For example, silicone substrates, etc.), CCD (Charge Coupled Device) substrates, and CMOS (Complementary Metal-Oxide Semiconductor (Complementary Metal-Oxide Semiconductor)) substrates, etc. In order to improve adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate, a primer layer can be provided on these substrates as needed.

As a method of coating the curable composition on the 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 black matrix-containing color filters for solid-state imaging devices, 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 preferably less than μm.

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

<Exposure process> The exposure process is a process in which the curable composition layer (coating film) formed in the curable composition layer formation process is exposed through a mask, and only part of the coating film irradiated by light is cured. The exposure is preferably carried out by irradiation of 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 preferred. 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. If the exposure amount is within the above range, the production method of the 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 image sensor, exposure by an i-ray stepper is preferable.

<Development process> The development process is a process of developing the exposed curable composition layer. Through the development process, a patterned cured film can be obtained. The manufacturing method of the above-mentioned cured film preferably includes a development process and the following cleaning process. During the development process, an alkaline development process (development process) is performed, so that the light unirradiated part in the exposure process is dissolved in the alkaline aqueous solution. Thereby, only the light-hardened part (the part of the coating film irradiated by light) remains. As the developer, an organic alkaline developer that does not damage the circuit of the substrate or the like is preferable when producing a black matrix-containing light-shielding color filter for a solid-state image sensor. The development temperature is generally preferably 20 to 30°C, and the development time is preferably 20 to 90 seconds.

As an alkaline aqueous solution, an inorganic type developer and an organic type developer are mentioned, for example. As an inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, or sodium metasilicate, dissolved in a concentration of 0.001-10% by mass, preferably 0.01- 1% by mass alkaline aqueous solution. Examples of organic developers include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8- Organic basic compounds such as diazabicyclo-[5.4.0]-7-undecene are dissolved into an alkaline aqueous solution with a concentration of 0.001-10% by mass, preferably 0.01-1% by mass. In the alkaline aqueous solution, for example, an appropriate amount of water-soluble organic solvents such as methanol and ethanol and/or surfactants can be added. In addition, as a development method, for example, spin immersion development and shower development methods can be utilized.

<Cleaning process> The cleaning process is a process of cleaning (rinsing) the developed curable composition layer with pure water or the like. As a cleaning method, there is no restriction|limiting in particular, A well-known cleaning method can be utilized.

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

The color filter containing the above-mentioned hardened film (black matrix) is suitable for solid-state imaging devices such as CCD image sensors and/or CMOS image sensors. Especially suitable for high-resolution CCD image sensors and/or CMOS image sensors with over 1 million pixels. That is, the color filter containing the above-mentioned cured film is suitable for a solid-state imaging device. The color filter may have a structure in which, for example, a space divided into a grid shape by a partition is embedded with a cured film forming pixels of each color. The above-mentioned cured film (black matrix) is arranged, for example, between the 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 contains a black matrix, and it is preferable to include a color filter including a patterned film of pixels of other colors (three colors or four colors) as necessary. The solid-state imaging element is not particularly limited as long as it contains the above-mentioned black matrix and functions as a solid-state imaging element. A plurality of photodiodes, polysilicon and other light-receiving elements in the light-receiving area of the substrate include the black matrix solid-state imaging element on the surface opposite to the light-receiving element forming surface of the substrate. The color filter may have a structure in which, for example, a space divided into a grid shape by a partition is embedded with a cured film forming pixels of each color. In this case, it is preferable that the partition wall has a low refractive index with respect to each color pixel. As examples of solid-state imaging elements including such a structure, solid-state imaging elements described in Japanese Patent Application Publication No. 2012-227478 and Japanese Patent Application Publication No. 2014-179577 can be cited.

[Image Display Device] The cured film described above is suitable for use in image display devices (for example, liquid crystal display devices, organic electroluminescence display devices, etc.).

The definition of image display devices and the details of each image display device are described in, for example, "Electronic Display Devices (by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)" and "Display Devices (Junaki Ibuki) Books, Industrial Books (published in the first year of Heisei)" etc. For liquid crystal display devices, for example, it is described in "Second Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, issued by Kogyo Chosakai Publishing Co., Ltd. in 1994)". The above-mentioned cured film is suitable for a liquid crystal display device of the method described in the above-mentioned "Second Generation Liquid Crystal Display Technology", for example.

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

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

The color filter containing the above-mentioned cured film is suitable for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT Liquid Crystal Display (KYORITSU SHUPPAN CO., LTD. issued in 1996)". Moreover, the above-mentioned color filter is also suitable for lateral electric field driving methods such as IPS (In Plane Switching); pixel division methods such as MVA (Multi-domain Vertical Alignment); Expanded LCD device, 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), etc.

The above-mentioned color filter is suitable for a bright and high-definition COA (Color-filter On Array) liquid crystal display device. Regarding the liquid crystal display device of the COA method, in addition to the usual required characteristics for the color filter, the required characteristics for the interlayer insulating film, that is, low dielectric constant and peeling liquid resistance, are sometimes required. The COA mode liquid crystal display device containing the above-mentioned color filter has better resolution or better durability. In addition, in order to satisfy the required characteristics of low dielectric constant, a resin coating film may be further included on the color filter layer.

For these image display methods, for example, it is described on page 43 of "EL, PDP, LCD display-latest trends in technology and market-(issued by TORAY Research Center, Inc. in 2001)". In addition, in the above, EL stands for Electroluminescence, PDP stands for Plasma Display Panel, and LCD stands for Liquid Crystal Display.

The above-mentioned liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle protective film in addition to the above-mentioned color filter. The above-mentioned color filter can be applied to a liquid crystal display device composed of these known members. These components are described in, for example, "'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Shima Kentaro CMC-Group. Issued in 1994)" and "2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)" (Table Ryoshi Fuji) Chimera Research Institute, Inc., issued in 2003)”. Regarding the backlight, it is described in SID meeting Digest 1380 (2005) (A. Konno et.al) and/or pages 18-24 of the December 2005 issue of the monthly display (Yoshihiro Shima), and described in SID meeting Digest 1380 (2005) 25 ~ 30 pages (Yagi Takaaki) etc.

The above hardened film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smart phones and digital cameras; OA (Office Automation) equipment such as multifunction printers and scanners; surveillance cameras, barcode readers, and Industrial equipment such as automated teller machine (ATM: automated teller machine), high-speed cameras, and personal authentication using facial image authentication; automotive camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters ; Biological sensors, biosensors, military reconnaissance cameras, stereo map cameras, meteorological and ocean observation cameras, terrestrial resources reconnaissance cameras, and space equipment such as exploration cameras for astronomical and deep-space targets in the universe The light-shielding members and light-shielding layers of optical filters and modules used in etc. are further suitable for anti-reflection members and anti-reflection layers.

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

The above-mentioned cured film is suitable as an optical filter and an optical film used in a quantum dot display. In addition, the above-mentioned cured film is suitable as a member imparting a light-shielding function and an anti-reflection function. As examples of quantum dot displays, 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 amount, ratio, processing content, processing steps, etc. shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the examples shown below.

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

<Titanium Nitride Particles (TiN-1)> First, Ti particles (TC-200, manufactured by TOHO TECHNICAL SERVICE CO., LTD.) are plasma treated in Ar gas to form Ti nanoparticles . The Ti nanoparticles after the plasma treatment were allowed to stand for 24 hours under the conditions of an _{O 2 concentration of 50 ppm or less and 30° C. in an Ar atmosphere.} After that _{, in a state where O 2} gas was introduced in an Ar atmosphere so that the _{O 2} concentration became 100 ppm, it was allowed to stand at 30° C. for 24 hours (pretreatment of Ti particles). After that, using a TTSP separator manufactured by Hosokawa Micron Corporation, under the condition that the yield becomes 10%, the obtained Ti nanoparticle is classified to obtain Ti particle powder. The primary particle size of the obtained powder was observed by TEM, and the average particle size of 100 particles was calculated by arithmetic average, and the result was 120 nm. The titanium nitride-containing particles TiN-1 were manufactured using the apparatus according to the black composite particle manufacturing apparatus described in FIG. 1 of International Publication No. 2010/147098. Specifically, in the black composite particle manufacturing device, a high-frequency voltage of about 4MHz and about 80kVA is applied to the high-frequency oscillation coil of the plasma torch, and 50L/min of argon gas is supplied as the plasma gas from the plasma gas supply source. The mixed gas of 50L/min and nitrogen produces an argon-nitrogen thermal plasma flame in the plasma torch. A carrier gas of 10 L/min was supplied from the spray gas supply source of the material supply device. For the Ti particles obtained as described above, Fe powder (JIP270M, JFE STEEL CORPORATION) and Si powder (Silicon powder SI006031) are mixed so that each mass ratio becomes Ti/Fe/Si=balance/0.05/0.05 . The mixture is supplied to the thermoplasma flame in the plasma torch together with argon as the carrier gas, and is vaporized in the thermoplasma flame to be highly dispersed in a gas phase state. In addition, nitrogen was used as the gas supplied into the chamber by the 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. In addition, the pressure in the cyclone was set to 50 kPa, and the supply speed of each raw material from the chamber to the cyclone was set to 10 m/s (average value). Thus, TiN-1 containing titanium nitride particles was obtained.

For 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 addition, in the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analysis device "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used. The oxygen and nitrogen analyzer "EMGA-620W/C" (trade name) manufactured by HORIBA, Ltd. was used to measure and calculate the nitrogen content by the inert gas fusion thermal conductivity method. From the above results, the mass ratio of the atoms contained in the titanium nitride-containing particles TiN is Ti/N/Fe/Si=57/34/0.0030/0.0020.

Regarding the X-ray diffraction of TiN-1 containing titanium nitride particles, the powder sample was filled in an aluminum standard sample holder, and the wide-angle X-ray diffraction method (manufactured by Rigaku Corporation, trade name "RU-200R") ) Perform the measurement. As the measurement conditions, the X-ray source is set to CuKα rays, the output is set to 50kV/200mA, the slit system is set to 1°-1°-0.15mm-0.45mm, the measurement step (2θ) is set to 0.02°, and the scanning speed is set It is 2°/min. In addition, the diffraction angle 2θ derived from the peak of the TiN (200) plane observed in the vicinity of the diffraction angle 2θ (42.6°) was measured. Furthermore, by using the half-width of the peak derived from the (200) plane, the size of the crystallites of the constituent particles was obtained using Scherrer's formula. As a result, the diffraction angle of the peak was 42.62°, and the crystallite size was 10 nm. In addition, X-ray diffraction peaks caused by _{TiO 2} were not observed at all.

<TiN-2 containing titanium nitride particles> As Ti particles, instead of "TC-200" manufactured by TOHO TECHNICAL SERVICE CO., LTD., "578347" manufactured by Sigma-Aldrich Co. LLC. is used, and each mass ratio becomes Ti/ Fe/Si=remainder/0.5/1, Fe powder and Si powder were mixed, except that the same method as TiN-1 was used to obtain TiN-2 containing titanium nitride particles. In addition, the diffraction angle of the peak measured by X-ray diffraction is 42.81°, and the crystallite size is 12 nm.

<TiN-3 containing titanium nitride particles> Fe powder and Si powder are mixed so that each mass ratio becomes Ti/Fe/Si=balance/1/2, except for this, the same method as TiN-1 TiN-3 containing titanium nitride particles was obtained. In addition, 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> Weigh 100 g of titanium oxide MT-150A (trade name, manufactured by TAYCA CORPORATION) with an average particle diameter of 15 nm, and measure BET (Brunauer, Emmet, Teller) specific surface area of 300 m ² /g of silicon dioxide Particle AEROSIL300 (registered trademark) 300/30 (manufactured by Evonik Japan Co., Ltd.) 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. A mixture is obtained. After that, MAZERSTAR KK-400W manufactured by KURABO was used, and the mixture was processed for 30 minutes at a revolution speed of 1,360 rpm and a rotation speed of 1,047 rpm, thereby obtaining a uniform aqueous mixture solution. 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). After that, the small rotary kiln was replaced with nitrogen, and ammonia gas was flowed at 100 mL/min for 5 hours at the same temperature, thereby performing the nitridation reduction treatment. The powder recovered after completion was pulverized with a mortar to obtain a powdery ^{titanium black containing Si atoms and a specific surface area of 73 m 2} /g [a dispersion containing titanium black particles and Si atoms] (hereinafter, labeled as "Ti Black A-1”).

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

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

Next, the Nb nano particles and Fe nano particles obtained as described above were mixed to obtain raw metal powder. The raw metal powder was subjected to plasma treatment in nitrogen, thereby obtaining 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. In addition, the device uses the same thing as the plasma treatment (1).・The high-frequency voltage applied to the high-frequency oscillation coil: frequency is about 4MHz, voltage is about 80kVA. ・Plasma gas: argon and nitrogen (supply volume of 50L/min respectively) ・Carrier gas: nitrogen (supply volume 10L/min)・Indoor atmosphere: nitrogen (supply rate 1,000L/min, chamber flow rate 5m/sec) ・Inside cyclone atmosphere: nitrogen, internal pressure 50kPa ・Material supply speed from the chamber to the cyclone: 10m/s ( average value)

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

<Production of Fe atom-containing vanadium nitride particles (VN)> In the production of Fe atom-containing niobium nitride particles, instead of niobium (powder) manufactured by Mitsuwa Chemicals Co., Ltd. <100-325mesh>, used TAIYO KOKO Co., LTD. manufactures metal vanadium powder VHO. Except for this, the same method is used to produce vanadium nitride particles (VN) containing Fe atoms. For the obtained vanadium nitride-containing particles, the content of iron (Fe) atoms was measured by ICP emission spectrometry, and the result was 50 ppm by mass.

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

・SH-4 (Pentaerythritol tetrakis (3-mercaptopropionate), equivalent to a 4-functional thiol compound.) [Chemical formula 28]

・SH-3 (Trimethylolpropane tris(3-mercaptopropionate), equivalent to a trifunctional thiol compound.) [Chemical formula 29]

・SH-2 (1,4-butanediol bis(thioglycolate), 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]

[Binder Resin] As the binder resin, the following resin A was used. The numerical value described in each structural unit represents the mole% of each structural unit with respect to all structural units. In addition, in the formula of resin A, each abbreviation represents 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 the following formula) [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-tert-butyl-4-methylphenol Ih-3: 4-hydroxy-2,2,6,6 -Tetramethylpiperidine 1-oxyl radical

[Surfactant] ・F-1: A compound represented by the following formula (weight average molecular weight (Mw)=15,311) where, in the following formula, the structural units represented by formulas (A) and (B) are respectively 62 mol%, 38 mol%. In the structural unit represented by formula (B), a, b, and c satisfy the relationship 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, the colorant, the dispersant, and the organic solvent were mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA Corporation) to obtain a mixed liquid of the above-mentioned components. Next, the obtained mixed liquid was subjected to 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, (Zirconium oxide beads manufactured by NIKKATO CORPORATION, YTZ) ・Bead filling rate: 65% by volume ・Grinding peripheral speed: 10m/sec ・Separator peripheral speed: 13m/s ・Dispersing Processed mixed liquid volume: 15kg ・Circulation flow rate (pump supply volume): 90kg/hour ・Processing fluid temperature: 19～21℃ ・Cooling water: water ・Processing time: about 22 hours

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

[Evaluation] The following evaluation tests were performed for each curable composition of the examples and comparative examples. The results are collectively shown in Table 1-1 and Table 1-2.

[OD value] On a glass plate (EagleXG, manufactured by Corning Incorporated) with a thickness of 0.7 mm and a square of 10 cm, each curable composition was used to form a coating film by spin coating. At this time, the rotation speed was adjusted to obtain a cured film with a thickness of 1.5 μm. The formed coating film was dried by heat treatment at 100°C for 2 minutes on a hot plate, and exposed at an exposure amount of ^{500 mJ/cm 2 to obtain a cured film.} For the glass substrate containing the obtained cured film, the OD value was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The greater the OD value, the more excellent the light-shielding property of the cured film is. The results are collectively shown in Table 1-1, Table 1-2, and Table 2. In addition, the OD values shown in Table 1-1, Table 1-2, and Table 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 value shown in Table 1-1, Table 1-2, and Table 2 in the entire wavelength range of 400 to 800 nm.

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

[Stability with time] Each curable composition after preparation was sealed in a 100 cc Bloom bottle and stored in a thermostat at 45°C for 7 days. After that, the pattern shape was evaluated in the same method as described above. The results are shown in Table 2.

[Table 1-1]

[Table 1-2]

[Table 2]

According to the results shown in Table 1-1 and Table 1-2, the curable composition of each example is a curable composition containing a coloring agent, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound. The cured film obtained by curing the curable composition has an optical density of 4.0 or more per 1.5 μm film thickness in the visible light region, and 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 the desired effect. The curable composition of Example 48 in which the content of the colorant is 55% by mass or more relative to the total solid content of the curable composition is the same as the content of the dispersant and the content of the colorant is 53% of Example 49 Compared with the curable composition, the obtained cured product has a better pattern shape. Compared with the curable composition of Example 4, the curable composition of Example 1, Example 2 and Example 3 in which the content of the polyfunctional thiol compound is 1 to 5.5% by mass relative to the content of the colorant The pattern shape of the obtained hardened product is more excellent. The curable composition of Example 45 containing two or more types of phenolic compounds as a polymerization inhibitor was cured with 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, which contains a phenolic compound and a hindered amine compound as a polymerization inhibitor, is cured with a lower exposure than the curable composition of Example 36 and has an excellent pattern shape of the cured product. The polyfunctional thiol compound is a trifunctional curable composition of Example 5, and compared with the curable composition of Example 9, the pattern shape of the cured product is more excellent. The polyfunctional thiol compound is the tetrafunctional curable composition of Example 1, and compared with the curable compositions of Example 9 and Example 5, the pattern shape of the cured product is more excellent. The photopolymerization initiator is the curable composition of Example 34, which is an oxime compound. Compared with the curable composition of Example 25, the cured product has a better pattern shape. 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. Compared with the sexual composition, the pattern shape of the cured product is more excellent. The curable composition of Example 13 and Example 48 in which 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, and the curable composition of Example 50 and Example 51 Compared with the object, the pattern shape of the hardened object is more excellent. The curable compositions of Example 2 and Example 48 in which the content of the dispersant is 17% by mass or more have better pattern shapes of the cured products than the curable compositions of Example 13 and Example 54.

In Example 1, the surfactant F-1 was not used. Except for this, a curable composition was prepared by the same method, and the evaluation was carried out 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 Curable Composition] In the preparation of the above-mentioned coloring agent dispersion, the coloring agent was carbon black (trade name "Color Black S170", Degussa-Hüls AG) , average primary particle diameter of 17nm, BET specific surface area of 200m ² / g, carbon blacks manufactured by the gas black mode), except that, by the same method to obtain a dispersion of carbon black (CB dispersion).

In the preparation of the curable composition of Example 1, instead of the colorant dispersion added so that the curable composition contains 58% by mass of titanium nitride-containing particles TiN-1, TiN containing titanium nitride-containing particles was used. -1 A mixture of the coloring agent dispersion and the above CB dispersion (TiN-1 containing titanium nitride particles in the curable composition: carbon black in the curable composition = 45:13 (mass ratio), the above curable The total content of the titanium nitride-containing particles TiN-1 and carbon black in the composition was 58% by mass.) Except for this, 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 light-shielding property and pattern shape as in Example 1 can be obtained.

[Preparation of color pigment dispersion (PY dispersion) and evaluation of curable composition] In the preparation of the above-mentioned colorant dispersion, the colorant was used as Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., Trade name 6150 Pigment Yellow 5GN), except for this, a color pigment dispersion (PY dispersion) was obtained by the same method.

In the preparation of the curable composition of Example 1, instead of the colorant dispersion added so that the curable composition contains 58% by mass of titanium nitride-containing particles TiN-1, TiN containing titanium nitride-containing particles was used. -1 A mixture of the coloring agent dispersion and the above-mentioned PY dispersion (TiN-1 containing titanium nitride particles in the curable composition: pigment yellow in the curable composition 150=45:13 (mass ratio), curability The total content of the titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the composition was 58% by mass.) Except for this, a curable composition was prepared in the same manner 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 darker black film can be obtained.

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

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

[Preparation of Color Pigment Dispersion (PV Dispersion)] In the preparation of the above colorant dispersion, the colorant was CIPigment Violet 23 (manufactured by Clariant). Other than that, the color pigment dispersion was obtained by the same method物(PV dispersion).

In the preparation of the curable composition of Example 1, the above-mentioned titanium nitride-containing particles TiN was used instead of the coloring agent dispersion added so that 58% by mass of the titanium nitride-containing particles TiN-1 was contained in the curable composition. -1. Mixture of PY, PR, PB and PV dispersions (the ratio of titanium nitride particles TiN-1, PY, PR, PB and PV in the curable composition; titanium nitride particles TiN-1: PY ：PR:PB:PV=70:17:37:36:10 (mass ratio), the total content of TiN-1, PY, PR, PB, and PV containing titanium nitride particles in the curable composition is 58% by mass .) Except for this, the curable 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 the same pattern shape as in Example 1 can be obtained, and a film having excellent light-shielding property 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 was used instead of the coloring agent dispersion added so that 58% by mass of the titanium nitride-containing particles TiN-1 was contained in the curable composition. -1 and the compound SQ-23 shown below (ratio of titanium nitride-containing particles TiN-1 and compound SQ-23 in the curable 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 curable composition is 58% by mass.), except for this, the curable composition is prepared in the same manner , And used this for evaluation. As a result of the evaluation, it was found that the same light-shielding property and the same pattern shape as in Example 1 can be obtained, and a film having excellent light-shielding property 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 was used instead of the coloring agent dispersion added so that 58% by mass of the titanium nitride-containing particles TiN-1 was contained in the curable composition. -1 and the following compound A-52 (ratio of titanium nitride-containing particles TiN-1 and compound A-52 in the curable composition; titanium nitride-containing particles TiN-1: compound A-52=50: 8 (mass ratio), the total content of titanium nitride-containing particles TiN-1 and compound A-52 in the curable composition is 58% by mass.) Otherwise, the curable composition is 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 in Example 1 can be obtained, and a film having excellent light-shielding property in the infrared region can be obtained.

Compound SQ-23 【Chemical formula 40】

Compound A-52 【Chemical formula 41】

101‧‧‧Support 102‧‧‧curable composition layer 103. ‧Mask shading part 501‧‧‧curing film 601‧‧‧curing film after baking

Fig. 1 is a cross-sectional view schematically showing, for each process, a production process of a cured film using a curable composition that does not contain a polyfunctional thiol compound. 2 is a cross-sectional view schematically showing the manufacturing process of a cured film using a curable composition that does not contain a polyfunctional thiol compound for each process. 3 is a cross-sectional view schematically showing, for each process, a production process of a cured film using a curable composition that does not contain a polyfunctional thiol compound. 4 is a cross-sectional view schematically showing the manufacturing process of a cured film using the curable composition of the embodiment of the present invention for each process. 5 is a cross-sectional view schematically showing, for each process, the manufacturing process of the cured film using the curable composition of the embodiment of the present invention. 6 is a cross-sectional view schematically showing the manufacturing process of a cured film using the curable composition of the embodiment of the present invention for each process.

101‧‧‧Support

102‧‧‧curable composition layer

103‧‧‧Mask

Claims (27)

A curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, wherein the cured film obtained by curing the aforementioned curable composition has a film thickness of 1.5 μm in the visible light region The optical concentration of the colorant is 4.0 or more, the colorant includes at least one selected from the group consisting of titanium nitride-containing particles, niobium nitride and vanadium nitride, and the titanium nitride-containing particles include those selected from Fe atoms and Si atoms. At least one atom of the composition group, when the aforementioned titanium nitride-containing particles include Fe atoms, the content of the aforementioned Fe atoms in the aforementioned titanium nitride-containing particles is more than 0.001 mass relative to the total mass of the aforementioned titanium nitride-containing particles % And less than 0.4% by mass, and when the aforementioned titanium nitride-containing particles include Si atoms, the content of the aforementioned Si atoms in the aforementioned titanium nitride-containing particles is more than 0.002% by mass relative to the total mass of the aforementioned titanium nitride-containing particles, and Less than 0.3% by mass. The curable composition according to the first item of the scope of patent application, wherein the content of the colorant is 55% by mass or more with respect to the total solid content of the curable composition. The curable composition according to the first item of the patent application, wherein the content of the polyfunctional thiol compound relative to the content of the colorant is 1 to 5.5% by mass. The curable composition described in any one of items 1 to 3 in the scope of the patent application further contains a polymerization inhibitor. The curable composition according to the fourth item of the patent application, wherein the content of the polymerization inhibitor is 0.1 to 1.5% by mass relative to the content of the polyfunctional thiol compound. The curable composition described in item 4 of the scope of patent application, wherein the polymerization inhibitor contains a phenolic compound. The curable composition described in item 4 of the scope of the patent application, wherein the polymerization inhibitor contains two or more phenolic compounds. The curable composition described in claim 4, wherein the polymerization inhibitor contains a hindered amine compound. The curable composition described in item 6 of the scope of patent application, wherein the aforementioned phenolic compound is a phenolic compound represented by formula (IH-1),

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 amino group, an aryl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group or an acyl group, and R ₁ to R ₅ may be connected separately to form a ring. The curable composition according to any one of items 1 to 3 in the scope of the patent application, wherein the colorant further contains an infrared absorber. The curable composition according to any one of items 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), -OL ^1- L ² -SH (1) In the 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 items 1 to 3 in the scope of the patent application, wherein the polyfunctional thiol compound is trifunctional or more. The curable composition according to any one of items 1 to 3 in the scope of the patent application, wherein the aforementioned multifunctional thiol compound is selected from the group consisting of pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane At least one of the group consisting of (3-mercaptopropionate). The curable composition according to any one of items 1 to 3 in the scope of the patent application, wherein the content of the photopolymerization initiator is more than 1% by mass relative to the total solid content of the curable composition, and Less than 10% by mass. The curable composition as described in any one of items 1 to 3 of the scope of patent application, wherein The content of the polymerizable compound with respect to the total solid content of the curable composition is more than 3.5% by mass and less than 20% by mass. The curable composition described in any one of items 1 to 3 of the scope of the patent application, which further contains a dispersant, and the content of the dispersant is 17% by mass relative to the total solid content of the curable composition above. The curable composition according to any one of items 1 to 3 in the scope of the patent application, wherein the aforementioned photopolymerization initiator is an oxime compound. The curable composition according to any one of items 1 to 3 in the scope of the patent application, wherein the photopolymerization initiator is an oxime compound containing a fluorine atom. A cured film obtained by curing the curable composition described in any one of items 1 to 18 in the scope of the patent application. A color filter containing the hardened film described in item 19 of the scope of patent application. A light-shielding film containing the cured film described in item 19 of the scope of patent application. A solid-state imaging device containing the cured film described in item 19 of the scope of patent application. An image display device containing the cured film described in item 19 of the scope of patent application. A method for manufacturing a hardened film, comprising: using the hardenable composition described in any one of items 1 to 18 in the scope of the patent application, forming a hardenable composition layer on a support body Manufacturing process; and an exposure process for exposing the aforementioned curable composition layer. The method for manufacturing a cured film as described in claim 24, wherein the exposure amount of the curable composition layer in the exposure process is 200 mJ/cm ² or more. The method for producing a cured film as described in claim 24, wherein the curable composition layer forming process includes directly coating the curable composition on the support to form the curable on the support. The coating process of the composition layer. The method for producing a cured film as described in any one of items 24 to 26 of the scope of the patent application, further comprising: a development process for developing the exposed curable composition layer; and washing the developed aforesaid The cleaning process of the hardening composition layer.

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