TW201731927A - Method for producing cured film, cured film, solid-state image capture element, and image display device - Google Patents

Abstract

A cured film manufacturing method using a curable composition that contains a coloring agent, a polymerization initiator, a polymerizable compound, a binder polymer, and a solvent, said cured film manufacturing method comprising: a first step in which the curable composition is applied as a spray with an impact size of D1 so as to form a first coating film; a second step in which the curable composition is applied as a spray with an impact size of D2 so as to form a second coating film; and a step in which a curing process is performed so as to form a cured film, wherein D1 and D2 satisfy the relationship D1 > D2, and the ratio D1/D2 is 5-150.

Description

Method for producing cured film, cured film, solid-state imaging device, and image display device

The present invention relates to a method for producing a cured film, a cured film, a solid-state image sensor, and an image display device.

The solid-state imaging device includes an imaging lens, a solid-state imaging device such as a charge coupled device (CCD) disposed on the back of the imaging lens, and a complementary metal oxide semiconductor (CMOS), and the solid state is mounted thereon. A circuit board of an imaging element. The solid-state imaging device is mounted on a digital camera, a mobile phone with a camera, a smart phone, or the like. In a solid-state imaging device, noise may be generated due to reflection of visible light. Therefore, a predetermined light shielding film is widely provided in the solid-state imaging device. Such a light-shielding film is formed, for example, using a curable composition (photosensitive composition) containing a black pigment such as titanium black. Various methods are known as a film forming method using such a photosensitive resin composition. For example, Patent Document 1 discloses a step of applying a curable composition (black polymerizable composition) by spraying. Method of hardening a film (black cured film) (request 8, claim 9, etc.). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-62446

[Problems to be Solved by the Invention] In recent years, with the miniaturization, thinning, and high sensitivity of a solid-state imaging device, further low reflection of a light-shielding film or lithographic performance when a cured film (light-shielding film) is formed is required. Further improvement. However, when the curable composition is applied by spraying, the reflectance and lithographic performance of the obtained cured film may be insufficient, and the performance required in recent years may not necessarily be satisfied. Specifically, the inventors of the present invention have made a cured film containing a single layer using only the spray method as described in Patent Document 1, and as a result, it has been found that the obtained cured film has insufficient reflectance and lithographic performance, and further development is required. Improvement.

Accordingly, an object of the present invention is to provide a method for producing a cured film having low reflectance and excellent lithography performance, a cured film, and a solid-state image sensor and image display device having the cured film. [Means for solving the problem]

As a result of intensive studies on the above-mentioned problems, the present inventors have found that in the case of producing a cured film, the ratio of the landing size D1 when the first coating film is formed to the landing size D2 when the second coating film is formed is Within the scope, the desired properties can be obtained, thereby completing the present invention. That is, the inventors of the present invention have found that the above problems can be solved by the following configuration.

[1] A method for producing a cured film, which comprises using a cured film comprising a colorant, a polymerization initiator, a polymerizable compound, a binder polymer, and a solvent, wherein the method for producing the cured film comprises: In the first step, the curable composition is spray-coated to form a first coating film so that the landing size is D1. In the second step, the curable composition is spray-coated so that the landing size is D2. a coating film; and a step of forming a cured film by performing a hardening treatment, wherein D1 and D2 satisfy a relationship of D1>D2, and a ratio D1/D2 of the D1 to the D2 is 5 to 150. [2] The method for producing a cured film according to [1], wherein the second step is performed after the first step. [3] The method for producing a cured film according to the above [1], wherein the distance between the tip end of the nozzle of the spray device used in the spray coating of the first step and the surface to be coated is L1. It is smaller than the distance L2 between the tip end of the nozzle of the spray device used in the spray coating described in the second step and the surface to be coated. [4] The method for producing a cured film according to [3], wherein the distance L1 is less than 5 cm, and the distance L2 is more than 10 cm. [5] The method for producing a cured film according to any one of [1] to [4] wherein the D2 is from 1 μm to 30 μm. [6] The method for producing a cured film according to any one of [1] to [5] wherein the D2 is 1 μm to 10 μm. [7] A cured film obtained by using a curable composition containing a colorant, a polymerization initiator, a polymerizable compound, a binder polymer, and a solvent, and formed on a substrate, from the side of the substrate The first surface of the cured film faces the second surface of the cured film facing the first surface, and the void ratio at a position of 10% of the thickness of the cured film is A1. When the void ratio at the position where the second surface faces the first surface and becomes 10% of the thickness of the cured film is A2, the relationship between A1 and A2 satisfies A1 < A2. [8] The cured film according to [7], wherein the A1 is 0.001% or more and less than 3%. [9] The cured film according to [7], wherein the A2 is 0.1% or more and less than 30%. [10] The cured film according to any one of [7], wherein the surface roughness Ra of the second surface of the cured film is from 0.1 μm to 1.2 μm. [11] The cured film according to any one of [7] to [10] wherein the cured film has at least two or more layers. [12] The cured film according to any one of [7] to [11] which is used as a light-shielding film. [13] The cured film according to any one of [7] to [11] which is used as a color filter. [14] A solid-state image sensor, comprising the cured film according to any one of [7] to [11]. [15] An image display device comprising the cured film according to any one of [7] to [11]. [Effects of the Invention]

As described below, according to the present invention, it is possible to provide a method for producing a cured film having low reflectance and excellent lithography performance, a cured film, and a solid-state image sensor and image display device having the cured film.

Hereinafter, preferred embodiments of the method for producing a cured film of the present invention, a cured film, and a solid-state image sensor having the cured film and an image display device will be described in detail. The description of the constituent elements described below may be based on representative embodiments of the present invention, and the present invention is not limited by the embodiments.

In the expression of the group (atomic group) in the present specification, the expression that the substituted or unsubstituted is not described is a group containing a group (atomic group) having no substituent and also containing a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The term "radiation" as used in the present specification means visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene fluorenyl group and The acrylonitrile group, "(meth) acrylamide" means acrylamide and methacrylamide. In the present specification, "single quantity" has the same meaning as "monomer". The monomer of the present specification differs from the oligomer and the polymer in that it means a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

[Method for Producing Cured Film] The method for producing a cured film of the present invention is a method for producing a cured film using a curable composition containing a colorant, a polymerization initiator, a polymerizable compound, a binder polymer, and a solvent, and includes In the first step, the curable composition is spray-coated so that the landing size becomes D1 to form a first coating film, and in the second step, the curable composition is spray-coated so that the landing size is D2. a second coating film; and a step of forming a cured film by performing a curing treatment, wherein D1 and D2 satisfy a relationship of D1>D2, and a ratio D1/D2 of the D1 to the D2 is 5 to 150.

According to the method for producing a cured film of the present invention, a cured film having low reflectance and excellent lithography performance can be produced. The details of this reason are not clear, but the following reasons are presumed. When the curable composition is sprayed from the nozzle of the spray device, the curable composition flies into a plurality of droplets and flies on the coated surface. The droplets that have landed on the surface to be coated are dried to form a granular material containing solid components contained in the droplets. A plurality of the granules are aggregated, thereby forming a film (coating film). In the present invention, the diameter of the granular material is referred to as "landing size", and a more detailed definition of the landing size will be described later. Here, FIG. 1A and FIG. 1B are explanatory views which show an example of the manufacturing method of the cured film of this invention. In the example of FIG. 1B, the coating film 120 is formed on the substrate 100, and includes the first coating film 120A and the second coating film 120B. The coating film 120 is cured by a curing treatment (not shown) to form a cured film. The first coating film 120A composed of a large-sized granular material is formed using droplets having a large size. Since the droplets having a large size easily spread when landing on the surface to be coated, the granular material 120a obtained thereby has a flat and large granular material. Further, the granular materials 120a are in good contact with each other. In this way, since the first coating film 120A including the plurality of granular materials 120a is flat and has a small number of pinholes, it is possible to suppress the defect of the pattern shape of the cured film including the first film formed by curing the first coating film 120A. Or the generation of pinholes, etc. Next, the second coating film 120B composed of the fine particles 120b having a small size is formed using droplets having a small size. The small-sized droplets have a small expansion when they land on the coated surface, so that it is easy to maintain their shape after being behind. Therefore, since the second coating film 120B composed of the plurality of granular materials 120b has a surface having irregularities, the reflectance of the cured film including the second film formed by curing the second coating film 120B can be reduced. In this manner, it is presumed that the functions of the first film formed by the first coating film 120A and the second film formed by the second coating film 120B complement each other, and the cured film has a low reflectance and excellent lithographic performance.

Hereinafter, each step in the method for producing a cured film will be described after explaining the curable composition used in the production of the cured film of the present invention.

<Curable composition> The curable composition used in the method for producing a cured film of the present invention (hereinafter also referred to simply as "the composition of the present invention") contains a coloring agent, a polymerization initiator, a polymerizable compound, and a binder. Polymer and solvent. Hereinafter, the components contained in the composition of the present invention and the components which can be contained will be described.

(a) Colorant The composition of the present invention contains a colorant. Various known coloring pigments and coloring dyes can be used as the coloring agent. As the coloring dye, for example, in the case of producing a color filter, a color dye such as red (R), green (G), or blue (B) which forms a color pixel of a color filter (color dye) In addition to the above, the coloring agent described in paragraph 0027 to paragraph 0200 of JP-A-2014-42375 can also be used. Further, a black dye (black dye) which is generally used for black matrix formation use or light-shielding film formation can be used. As the coloring pigment, for example, in the case of producing a color filter, a color pigment such as red (R), green (G), or blue (B) which forms a color pixel of a color filter can be used (color A pigment), and a black pigment (black pigment) which is generally used for black matrix formation or light-shielding film formation.

As the color-based pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, regardless of whether the inorganic pigment or the organic pigment is preferably high in transmittance, it is preferably used as fine as possible, and if the handling property is also considered, the average primary particle diameter of the pigment is preferred. It is from 0.01 μm to 0.1 μm, more preferably from 0.01 μm to 0.05 μm.

Further, the average primary particle diameter of the pigment can be measured using a Transmission Electron Microscope (TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-technologies Co., Ltd. can be used. Measuring the maximum length of the particle image obtained using a transmission electron microscope (Dmax: maximum length of 2 points on the contour of the particle image), and the maximum length vertical length (DV-max: 2 in parallel with the maximum length) When the image is held in a straight line, the shortest length between the two straight lines is connected vertically, and the multiplied average value (Dmax ́DV-max) ^{1/2 is taken} as the particle diameter. The particle diameter of 100 particles was measured by this method, and the arithmetic mean value thereof was defined as the average particle diameter as the average primary particle diameter of the pigment. The "average primary particle diameter" in the embodiment of the present specification is also the same as the arithmetic mean value described above.

Examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. An oxide, and a composite oxide of the metal.

[Pigment] Examples of the pigment include various conventionally known inorganic pigments or organic pigments. Examples of the inorganic pigment include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals. The following are mentioned as an organic pigment. However, the present invention is not limited to these. As the organic pigment, a color index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18 can be cited. , 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 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 :4,4 9, 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 (Pigment Green) 7, 10, 36, 37, 58, 59, etc., Pig Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc., CI Pigment Blue 1, 2 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. These organic pigments may be used singly or in various combinations for the purpose of improving color purity.

(Black Pigment) A black pigment can also be used as the pigment in the present invention. Hereinafter, the black pigment will be described in further detail. Various known black pigments can be used for the black pigment. In particular, from the viewpoint of achieving a high optical density in a small amount, carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, graphite, or the like is preferable, and among them, carbon black and titanium black are preferably contained. At least one, in particular, titanium black is preferred from the viewpoint that the absorption of the light-absorbing wavelength region of the initiator in the curing efficiency due to exposure is small. Specific examples of the carbon black include an organic pigment such as C.I. Pigment Black 1 which is a commercially available product, and an inorganic pigment such as C.I. Pigment Black 7, but are not limited thereto.

(Other pigments) In the present invention, in addition to the pigment described as the black pigment, a pigment having infrared absorbing property may be used as the pigment. The pigment having an infrared absorbing property is preferably a tungsten compound or a metal boride. Among them, a tungsten compound is preferred because it has excellent light blocking properties in the wavelength of the infrared region. In particular, a tungsten compound is preferred from the viewpoint of excellent light transmittance wavelength region of the initiator and curing light transmittance in the visible light region due to exposure.

These pigments may be used in combination of two or more kinds, or may be used in combination with a dye described later. In order to adjust the color tone or to improve the light-shielding property in a desired wavelength region, for example, a color pigment such as red, green, yellow, orange, purple, or blue, a dye described later, a black pigment, or an infrared ray blocking property may be mentioned. The aspect in which the pigment is mixed. It is preferable to contain a red pigment or a dye having an infrared ray blocking property, a red pigment or a dye, a purple pigment or a dye, and particularly preferably a black pigment or a pigment having an infrared ray blocking property.

The black pigment preferably contains titanium black. The term "titanium black" refers to black particles containing titanium atoms. It is preferably low-order titanium oxide or titanium oxynitride or the like. The surface of the titanium black particles may be modified as needed for the purpose of improving dispersibility and suppressing cohesiveness. The coating may be carried out by using cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide or zirconium oxide, or by using a water-repellent substance as shown in JP-A-2007-302836. Titanium black is typically titanium black particles, and is preferably one having a primary particle diameter and a small average primary particle diameter per particle. Specifically, particles having a range of 10 nm to 45 nm in terms of average primary particle diameter are preferred.

The specific surface area of titanium black is not particularly limited, and the value measured by the Brunauer-Emmett-Teller (BET) method is preferably such that the water repellency after surface treatment with titanium dioxide by the water repellent has a predetermined performance. 5 m ² /g to 150 m ² /g, more preferably 20 m ² /g to 120 m ² /g. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade name, manufactured by Mitsubishi Materials Co., Ltd.), Dilla Tilack D (trade name, manufactured by Akohosei Co., Ltd.) and the like.

Further, it is also preferred to contain titanium black in the form of a dispersion containing titanium black and Si atoms. In this form, titanium black is contained in the composition as a dispersion, and the content ratio of Si atoms to Ti atoms in the dispersion (Si/Ti) is preferably 0.05 or more, more preferably 0.05. ～0.5, and further preferably 0.07 to 0.4. Here, the dispersion includes both a state in which titanium black is a primary particle and a state in which titanium black is agglomerated (secondary particle). In order to change the Si/Ti of the dispersion (for example, 0.05 or more), the following method can be used. First, a titanium oxide and cerium oxide particles are dispersed by using a dispersing machine, whereby a dispersion is obtained, and the dispersion is subjected to a reduction treatment at a high temperature (for example, 850 ° C to 1000 ° C), whereby titanium black particles can be obtained. It is a main component and contains a dispersion of Si and Ti. The reduction treatment can also be carried out in an environment of a reducing gas such as ammonia. Examples of the titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo Co., Ltd.). As a commercial item of the cerium oxide particle, AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik), etc. are mentioned. A dispersing agent can also be used for the dispersion of the titanium oxide and the cerium oxide particles. The dispersing agent can be mentioned in the column of the dispersing agent mentioned later. The dispersion can be carried out in a solvent. Examples of the solvent include water and an organic solvent. Further, the one described in the column of the organic solvent described later can be mentioned. Titanium black in which Si/Ti is adjusted to, for example, 0.05 or more, can be produced, for example, by the method described in paragraph number [0005] and paragraph number [0016] to paragraph number [0021] of JP-A-2008-266045. .

By adjusting the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a preferred range (for example, 0.05 or more), the composition containing the dispersion is used. When the light shielding film is formed, the residue derived from the composition outside the formation region of the light shielding film is reduced. Further, the residue contains a component derived from a composition such as titanium black particles or a resin component. The reason for the reduction of the residue is not clear, and it is presumed that the dispersion as described above tends to have a small particle diameter (for example, the particle diameter is 30 nm or less), and the component containing the Si atom in the dispersion increases. The adsorption of the entire film to the substrate is lowered, which contributes to improvement in development removability of the uncured composition (particularly titanium black) in the formation of the light-shielding film. Further, since light having a wide range of wavelength regions from ultraviolet light to infrared light has excellent light-shielding properties, the dispersion containing titanium black and Si atoms (preferably Si/Ti) is used. The light-shielding film formed by the mass conversion of 0.05 or more exhibits excellent light-shielding property. In addition, the content ratio (Si/Ti) of the Si atom to the Ti atom in the dispersion can be, for example, the method (1-1) or the method (1) described in paragraph 0033 of JP-A-2013-249417. 2) Perform the measurement. In addition, the dispersion to be contained in the light-shielding film obtained by curing the composition is used to determine whether the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more. The method (2) described in paragraph 0035 of the publication No. 2013-249417.

Among the dispersions containing titanium black and Si atoms, the titanium black can be used. In addition, in the dispersion, a composite oxide containing Cu, Fe, Mn, V, Ni, or the like, cobalt oxide, iron oxide, carbon black, aniline black, or the like may be used for the purpose of adjusting dispersibility, coloring, and the like. One or a combination of two or more black pigments is used in combination with titanium black in the form of a dispersion. In this case, it is preferred that the dispersion containing titanium black accounts for 50% by mass or more of all the dispersions. Further, in the dispersion, for the purpose of adjusting the light-shielding property, other coloring agents (organic pigments, dyes, etc.) may be used together with titanium black as long as the effects of the present invention are not impaired. Hereinafter, the material used when introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a substance containing Si such as cerium oxide may be used. Examples of the cerium oxide which can be used include precipitated cerium oxide, gas phase cerium oxide, colloidal cerium oxide, and synthetic cerium oxide, and these may be selected as appropriate. Further, when the light-shielding film is formed, if the particle diameter of the cerium oxide particles is smaller than the film thickness, the light-shielding property is more excellent. Therefore, it is preferable to use fine-particle type cerium oxide as the cerium oxide particles. In addition, as an example of the fine particle type cerium oxide, for example, cerium oxide described in paragraph 0039 of JP-A-2013-249417, the contents of which are incorporated herein by reference.

Further, as the pigment, a tungsten compound or a metal boride can also be used. Hereinafter, the tungsten compound and the metal boride will be described in detail. As the curable composition of the present invention, a tungsten compound and/or a metal boride can be used. The tungsten compound and the metal boride are high in absorption with respect to infrared rays (light having a wavelength of about 800 nm to 1200 nm) (that is, high light-shielding property (shielding property) with respect to infrared rays), and low-infrared shielding with respect to absorption of visible light. material. Therefore, the curable composition of the present invention can form a pattern having high light-shielding property in the infrared region and high light transmittance in the visible light region by containing a tungsten compound and/or a metal boride. Further, the tungsten compound and the metal boride have a small absorption of light of a short wave with respect to a visible region used for exposure of a high pressure mercury lamp for forming an image, KrF, ArF or the like. Therefore, by combining with a polymerizable compound, an alkali-soluble resin, and a photopolymerization initiator which will be described later, an excellent pattern can be obtained, and when a pattern is formed, development residue can be further suppressed.

Examples of the tungsten compound include a tungsten oxide-based compound, a tungsten boride-based compound, and a tungsten sulfide-based compound, and a tungsten oxide-based compound represented by the following general formula (composition formula) (I) is preferable. M _x W _y O _z (I) M represents a metal, W represents tungsten, and O represents oxygen. 0.001≦x/y≦1.1 2.2≦z/y≦3.0

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

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

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

Specific examples of the tungsten oxide-based compound represented by the above formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 ,} etc., preferably Cs _0.33 WO _{3 .} Or Rb _0.33 WO ₃ , more preferably Cs _0.33 WO ₃ .

The tungsten compound is preferably fine particles. The average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. Since the average particle diameter is in such a range, the tungsten fine particles are difficult to block visible light by light scattering, and thus the light transmittance in the visible light region can be made more reliable. In view of avoiding light and acid, the average particle diameter is preferably as small as possible, and the average particle diameter of the tungsten fine particles is usually 1 nm or more for reasons such as ease of handling during production.

Further, two or more kinds 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 a tungsten compound in an inert gas atmosphere or a reducing gas atmosphere ( Refer to Japanese Patent No. 4096205). Further, the tungsten oxide-based compound can be obtained, for example, as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Further, as the metal boride include: lanthanum boride (LaB _6), praseodymium boride (PrB _6), neodymium boride (NdB _6), cerium boride (CeB _6), yttrium boride (YB _6), Titanium boride (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), One or two or more kinds of molybdenum boride (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), etc., are preferably lanthanum boride (LaB ₆ ).

The metal boride is preferably a microparticle. The average particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. Since the average particle diameter is in such a range, the metal boride fine particles are difficult to block visible light by light scattering, and thus the light transmittance in the visible light region can be made more reliable. In view of avoiding light and acid, the average particle diameter is preferably as small as possible, and the average particle diameter of the metal boride fine particles is usually 1 nm or more for reasons such as ease of handling during production.

Further, two or more kinds of metal borides may be used.

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

[Dye] As the dye, for example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, and JP-A-6-11614 can be used. Bulletin, Japanese Patent No. 2592207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,568, 520, U.S. Patent No. 5,567, 920, U.S. Patent No. 5,505,950, U.S. Patent No. 5,567,920, Japanese Patent Laid-Open No. Hei 5-333207, Japanese Patent Laid-Open No. Hei 6-35183 The pigment disclosed in Japanese Laid-Open Patent Publication No. Hei 6-51115, and the like. If it is distinguished by a chemical structure, a pyrazole azo compound, a pyrrolemethylene compound, an anilino azo compound, a triphenylmethane compound, a hydrazine compound, a benzylidene compound, or an oxophthalocyanine compound can be used. And a pyrazolotriazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, and the like. Further, as the dye, a dye polymer can also be used. The compound described in Japanese Laid-Open Patent Publication No. JP-A-2011-041097, and JP-A-2013-041097.

Further, in the present invention, as a coloring agent, a coloring agent having a maximum absorption in a wavelength range of 800 nm to 900 nm can be used. Examples of the coloring agent having such a spectral characteristic include a pyrrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an iminium compound, a thiol complex compound, and a transition metal oxide system. A compound, a squarylium compound, a naphthalocyanine compound, a quaterrylene compound, a dithiol metal complex compound, a croconium compound, or the like. The phthalocyanine compound, the naphthalocyanine compound, the iminium compound, the cyanine compound, the squaraine ylide compound, and the keto acid compound may also be those disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750. This content is incorporated into the present specification. The cyanine compound can be referred to, for example, "Functional Colorings, Okawa Shinshin / Matsuoka Hyun / Kitajima Jiro / Hiratsuka Hiroshi, Kodansha Technology", and the contents are incorporated into the specification of the present application.

As the coloring agent having the above-mentioned spectral characteristics, the compound disclosed in paragraphs 0004 to 0016 of JP-A-2007-164729, and the disclosure of paragraph 0027 to paragraph 0062 of JP-A-2002-146254 can also be used. The near-infrared absorption including the crystallite containing Cu and/or P oxide and the number average agglomerated particle diameter of 5 nm to 200 nm disclosed in paragraph 0034 to paragraph 0067 of JP-A-2011-164583 particle.

In the present invention, the coloring agent having the maximum absorption in the wavelength range of 800 nm to 900 nm is preferably a pyrrolopyrrole compound. The pyrrolopyrrole compound may be a pigment or a dye, and is preferably a pigment because it is easy to obtain a curable composition capable of forming a film excellent in heat resistance. For details of the pyrrolopyrrole compound, the description of Paragraph No. 0017 to Paragraph No. 0047 of JP-A-2009-263614 is incorporated herein by reference. In addition, as a specific example, the compound described in Paragraph No. 0049 to Paragraph No. 0058 of JP-A-2009-263614 is incorporated herein by reference.

Further, the dye polymer described in paragraph 0027 to paragraph 0200 of International Publication No. 2014/142144 or the dye polymer of paragraph 0018 to paragraph 0078 of JP-A-2011-242752 can also be preferably used. .

Further, the curable composition of the present invention may contain an extender pigment as needed. Examples of such an extender pigment include barium sulfate, barium carbonate, calcium carbonate, cerium oxide, basic magnesium carbonate, alumina white, gloss white, titanium white, hydrotalcite, and the like. These extender pigments may be used singly or in combination of two or more. The amount of the extender pigment used is usually from 0 part by mass to 100 parts by mass, preferably from 5 parts by mass to 50 parts by mass, more preferably from 10 parts by mass to 40 parts by mass, per 100 parts by mass of the coloring agent. In the present invention, the coloring agent and the extender pigment may be used by modifying the surface of the polymer as the case may be. In addition, in addition to a black pigment or a pigment having a high wavelength of light in a visible light region and a function of shielding light having a wavelength of an infrared region, it is also possible to include a colored organic such as red, blue, yellow, green, or purple. Pigment or dye. When a coloring organic pigment, a dye, a black pigment, or a light having a wavelength of light in a visible light region is used in combination, and a pigment having a function of shielding light of a wavelength in an infrared region is used, it is preferable to use a black pigment or visible light. The pigment having excellent wavelength in the wavelength of the region is excellent in the function of shielding the light of the wavelength of the infrared region, and the red pigment or dye is preferably 1% by mass to 40% by mass, and the red or dye is preferably Pigment Red 254.

The content of the color former (particularly preferably a black pigment) in the composition is preferably from 20% by mass to 80% by mass, more preferably from 30% by mass to 70% by mass, based on the total solid content in the composition, and further preferably 35 mass% to 60 mass%.

[Dispersant] The composition of the present invention preferably contains a dispersant. The dispersant contributes to the improvement of the dispersibility of the colored pigment such as titanium black. As the dispersing agent, for example, a known pigment dispersing agent can be appropriately selected and used. Among them, a polymer compound is preferred. The dispersing agent may, for example, be a polymer dispersing agent [for example, polyamidoamine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, and a modified product. A poly(meth)acrylate, a (meth)acrylic copolymer, a naphthalenesulfonic acid formalin condensate, a polyoxyalkyleneethylalkyl phosphate, a polyoxyalkyleneamine, a pigment derivative, and the like. The polymer compound can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure.

The polymer compound functions to prevent re-aggregation by being adsorbed on a surface of the dispersion by a coloring agent such as a black pigment or a pigment which is used in combination as needed. Therefore, a terminal modified polymer having a graft site on the surface of the pigment, a graft polymer, and a block polymer are preferable. On the other hand, by modifying the surface of the titanium black and the dispersion containing titanium black and Si atoms, the adsorptivity of the polymer compound to these can be promoted.

The polymer compound preferably contains a structural unit having a graft chain. In the present specification, the "structural unit" has the same meaning as the "repeating unit". Since such a polymer compound containing a structural unit having a graft chain has affinity with a solvent by a graft chain, it is excellent in dispersibility of a color pigment such as a black pigment and dispersion stability after passage. Further, since the composition has affinity with a polymerizable compound or other reusable resin or the like by the presence of a graft chain, it is difficult to generate a residue in alkali development. When the graft chain becomes long, the steric repellency effect is improved and the dispersibility is improved. On the other hand, if the graft chain is too long, the adsorption force against a color pigment such as a black pigment is lowered, and the dispersibility tends to be lowered. Therefore, the graft chain preferably has a number of atoms other than the hydrogen atom in the range of 40 to 10,000, more preferably 50 to 2,000 atoms other than the hydrogen atom, and more preferably 60 atoms other than the hydrogen atom. 500. Here, the graft chain is represented by the root of the main chain of the copolymer (the atom bonded to the main chain from the group branched by the main chain) up to the end of the group branched from the main chain.

The graft chain preferably has a polymer structure, and examples of such a polymer structure include a poly(meth)acrylate structure (for example, a poly(meth)acrylic acid structure), a polyester structure, and a polyamine group. Acid ester structure, polyurea structure, polyamine structure and polyether structure. In order to enhance the interaction of the graft chain with the solvent and thereby improve the dispersibility, the graft chain preferably has a group selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure. The graft chain of at least one of the graft chains is more preferably a graft chain having at least any one of a polyester structure and a polyether structure.

The structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited, and a macromonomer having a reactive double bond group is preferably used.

Corresponding to a structural unit having a graft chain contained in a polymer compound, as a commercially available macromonomer which is preferably used in the synthesis of a polymer compound, AA-6 (trade name, East Asia Synthetic Co., Ltd.) can be used. )), AA-10 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AB-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AS-6 (trade name, East Asian Synthetic (Share)), AN-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AW-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AA-714 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AY-707 (trade name, East Asia) Synthetic (manufactured by the company), AY-714 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AK-5 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AK-30 (trade name, manufactured by East Asia Synthetic Co., Ltd.) ), AK-32 (trade name, manufactured by East Asia Synthetic Co., Ltd.), Blemmer PP-100 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer PP-500 (trade name) , manufactured by Nippon Oil Co., Ltd., Blemmer PP-800 (trade name, manufactured by Nippon Oil Co., Ltd.), cloth Blemmer PP-1000 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer 55-PET-800 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer PME- 4000 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer PSE-400 (trade name, manufactured by Nippon Oil Co., Ltd.), Blemmer PSE-1300 (trade name, Nippon Oil ( () manufacturing), Blemmer 43PAPE-600B (trade name, manufactured by Nippon Oil Co., Ltd.), etc. Among them, AA-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), AA-10 (trade name, East Asian Synthetic Co., Ltd.), and AB-6 (trade name, manufactured by East Asian Synthetic Co., Ltd.) are preferably used. , AS-6 (trade name, East Asia Synthetic Co., Ltd.), AN-6 (trade name, manufactured by East Asia Synthetic Co., Ltd.), Blemmer PME-4000 (trade name, manufactured by Nippon Oil Co., Ltd.) Wait.

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

[Chemical 1]

In the formulae (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ and W ^{4 are} preferably oxygen atoms. In the formulae (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ and X ⁵ are preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably independently. The ground is a hydrogen atom or a methyl group, and it is preferably each independently a methyl group.

In the formulae (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the connection is not particularly limited depending on the structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following (Y-1) to (Y-21) linking groups. In the structures shown below, A and B refer to the bonding sites of the left terminal group and the right terminal group in the formulae (1) to (4), respectively. Among the structures shown below, it is more preferably (Y-2) or (Y-13) in terms of ease of synthesis.

[Chemical 2]

In the formulae (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, and a heteroaryl group. Sulfether groups and amine groups, and the like. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ , in particular, from the viewpoint of improving dispersibility, a group having a steric repulsion effect is preferable, and it is preferable to independently independently An alkyl group or alkoxy group having 5 to 24 carbon atoms, particularly preferably a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms or a carbon number of 5 to 24, respectively. Alkoxy. Further, the alkyl group contained in the alkoxy group may be any of a linear chain, a branched chain, and a cyclic group.

In the formulae (1) to (4), n, m, p and q are each independently an integer of from 1 to 500. Further, in the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. From the viewpoints of dispersion stability and developability, j and k in the formulae (1) and (2) are preferably an integer of 4 to 6, more preferably 5.

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

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

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of the dispersion stability and the developability. In addition, the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of the dispersion stability and the developability.

[Chemical 3]

In the formula ^{(1A), X 1, Y} 1, Z 1 and n of formula X (1) is ^1, Y ^1, Z ¹ and n have the same meaning as the preferred range is also the same. In formula ^{(2A), X 2, Y} 2, Z 2 and ^2, Y ² m of formula X (2) is, Z ² and m are the same meaning as the preferred range is also the same.

In addition, the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of the dispersion stability and the developability.

[Chemical 4]

In formula (3A) or the formula ^{(3B), X 3, Y} 3, Z 3 and p of formula X (3) is ^3, Y ^3, Z ³ and p have the same meaning as the preferred range is also the same.

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

In the polymer compound, a structural unit having a graft chain is preferably contained in a range of 2% to 90% in terms of mass, based on the total mass of the polymer compound (for example, the formula (1) to the formula (4) The structural unit represented) more preferably contains a structural unit having a graft chain in a range of 5% to 30%. When a structural unit having a graft chain is contained in this range, the coloring pigment such as a black pigment (especially titanium black particles) has high dispersibility, and the developability at the time of forming a cured film is good.

Further, the polymer compound preferably contains a hydrophobic structural unit which is different from the structural unit having a graft chain (that is, does not correspond to a structural unit having a graft chain). In the present invention, the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, or the like).

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

The ClogP value is a value calculated by a program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "calculated logP" calculated by the fragment approach of Hansch and Leo (see the following document). The fragment method divides the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and sums the logP contribution values assigned to the fragments, thereby estimating the logP value of the compound. The details are described in the following documents. The present invention uses the ClogP value calculated by the program CLOGP v4.82. AJ Leo's "Comprehensive Medicinal Chemistry" Volume 4, C. Hansch, PG Sammnens, JB Taylor and CA Ram Edited by CA Ramsden, page 295, Pergamon Press, 1990; C. Hansch and AJ Leo, "Analysis of correlations in chemistry and biology." SUBstituent Constants For Correlation Analysis in Chemistry and Biology, John Wiley &Sons; AJ Leo "Calculating log Poct from structure" Chemical Review (Chem. Rev.) 93, 1281-1306, 1993.

logP refers to the common logarithm of the partition coefficient P (Partition Coefficient), which is a quantitative numerical value indicating how the organic compound is distributed under the balance of two phases of oil (usually 1-octanol) and water. The expression of the formula. logP = log (Coil / Cwater) wherein Coil represents the molar concentration of the compound in the oil phase and Cwater represents the molar concentration of the compound in the aqueous phase. When the value of logP increases toward a positive number from 0, it means that the oil solubility increases. If it is a negative number and the absolute value becomes large, it means that the water solubility increases and is negatively correlated with the water solubility of the organic compound. It is widely used as a parameter for evaluating the hydrophilicity of organic compounds.

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

[Chemical 5]

In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, etc.) or an alkane having 1 to 6 carbon atoms. Base (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} further preferably a hydrogen atom. X represents an oxygen atom (-O-) or an imido group (-NH-), preferably an oxygen atom.

L is a single bond or a divalent linking group. The divalent linking group may, for example, be a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenyl group, a substituted alkenyl group, an alkynylene group or a substituted alkynyl group). a divalent aromatic group (for example, an extended aryl group, a substituted aryl group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imido group (-NH-) And a substituted imido group (-NR ³¹ - wherein R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), or a combination thereof.

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

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

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocyclic ring. Other heterocyclic rings, aliphatic rings or aromatic rings may also be condensed in the heterocyclic ring. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (=O), a thioketone group (=S), an imido group (=NH), a substituted imido group (=NR ³² , this Wherein 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 oxygen-extended alkyl structure. The oxygen-extended alkyl structure is more preferably an oxygen-extended ethyl structure or an oxygen-extended propyl structure. Further, L may also contain a polyoxyalkylene structure having a repeating structure containing two or more oxygen-extended alkyl groups. The polyoxyalkylene structure is preferably a polyoxyalkylene structure or a polyoxyalkylene structure. The polyoxyalkylene structure is represented by -(OCH ₂ CH ₂ )n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

As Z, an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, or the like) may be mentioned. An aryl group, a substituted aryl group, a heterocyclic group, or a combination thereof. The base may also contain an oxygen atom (-O-), a sulfur atom (-S-), an imido group (-NH-), a substituted imine group (-NR ³¹ -, where R ³¹ is An aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-).

The aliphatic group may also have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and still more preferably from 1 to 10. The aliphatic group may further contain a cyclic hydrocarbon group or a crosslinked cyclic hydrocarbon group, and examples of the cyclic hydrocarbon group include a dicyclohexyl group, a perhydronaphthyl group, a biphenyl group, a 4-cyclohexylphenyl group and the like. Examples of the crosslinked cyclic hydrocarbon ring include decane, decane, norbornane, norbornane, and bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring. And other bicyclic hydrocarbon rings, tricyclo[5.2.1.0 ^3,8 ]decane (Homobredane), adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[4.3.1.1 ^2,5 a tricyclic hydrocarbon ring such as undecane ring, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane, perhydro-1,4-methyl bridge-5,8-methylnaphthalene ring, etc. A tetracyclic hydrocarbon ring or the like. In addition, the crosslinked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydrohydroquinone, perhydrophenanthrene, perhydroindene, perhydroindene, perhydroindene, perhydroindole ring A condensed ring obtained by condensing a plurality of 5-membered cycloalkane rings to 8-membered cycloalkane rings. In the case of a less unsaturated aliphatic group, the aliphatic group is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

The number of carbon atoms of the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, more preferably from 6 to 10. Further, 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 has a 5-membered or 6-membered ring as a heterocyclic ring. Other heterocyclic rings, aliphatic rings or aromatic rings may also be condensed in the heterocyclic ring. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (=O), a thioketone group (=S), an imido group (=NH), a substituted imido group (=NR ³² , this Wherein 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, fluorine, chlorine, bromine, etc.) or an alkyl group having 1 to 6 carbon atoms (for example, Methyl, ethyl, propyl, etc.), Z, or LZ. Here, L and Z have the same meanings as the above-mentioned L and Z. R ⁴ , R ⁵ and R ^{6 are} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

In the present invention, as the monolith represented by the above formula (i), R ¹ , R ² and R ³ are preferably a hydrogen atom or a methyl group, L is a single bond or an alkylene group or contains an alkylene oxide. A divalent linking group of a radical structure, a compound wherein X is an oxygen atom or an imine group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. Further, as the monomer of the above formula (ii), a compound wherein R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, Z is an aliphatic group, a heterocyclic group or an aromatic group is preferred. . Further, as the monomer of the above formula (iii), a compound wherein R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferred. .

Examples of the representative compound represented by the formula (i) to the formula (iii) include a radical polymerizable compound selected from the group consisting of acrylates, methacrylates, and styrenes. In addition, as an example of the representative compound represented by the formula (i) to the formula (iii), the compound described in paragraphs 0089 to 0093 of JP-A-2013-249417 can be referred to. Incorporated into this specification.

In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10% to 90% by mass, and more preferably in a range of 20% to 80%, based on the total mass of the polymer compound. When the content is in the above range, sufficient pattern formation can be performed.

A functional group capable of interacting with a coloring pigment such as a black pigment (particularly, titanium black) can be introduced into the polymer compound. Here, the polymer compound preferably further contains a structural unit having a functional group capable of interacting with a coloring pigment such as a black pigment. Examples of the functional group that can interact with a coloring pigment such as a black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group. In the case where the polymer compound contains an acid group, a basic group, a coordinating group or a reactive functional group, it is preferred to respectively contain a structural unit having an acid group, a structural unit having a basic group, and having a coordination group. A structural unit or a reactive structural unit. In particular, by using a polymer compound and an alkali-soluble group such as a carboxylic acid group as an acid group, developability can be imparted to the polymer compound, and the developability is used for pattern formation by alkali development. In other words, in the composition of the present invention, the polymer compound which is a dispersant which contributes to the dispersion of the color pigment such as a black pigment is made alkaline-soluble by introducing an alkali-soluble group into the polymer compound. The exposed portion of the composition containing such a polymer compound is excellent in light blocking property, and the alkali developability of the unexposed portion is improved. Further, since the polymer compound contains a structural unit having an acid group, the polymer compound is easily compatible with the solvent, and the coating property tends to be improved. It is presumed that the acid group in the structural unit having an acid group easily interacts with a coloring pigment such as a black pigment, and the polymer compound stably disperses a coloring pigment such as a black pigment, and a polymer in which a coloring pigment such as a black pigment is dispersed. The viscosity of the compound is lowered, and the polymer compound itself is easily dispersed stably.

Wherein, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the structural unit having a graft chain, or may be a different structural unit, but has a structural unit of an alkali-soluble group as an acid group. It is a structural unit different from the hydrophobic structural unit (that is, does not correspond to the hydrophobic structural unit).

The acid group which can interact with a coloring pigment such as a black pigment, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group or a phenolic hydroxyl group, is preferably a carboxylic acid group, a sulfonic acid group or a phosphoric acid group. At least one of them is a carboxylic acid group which has a good adsorption force to a coloring pigment such as a black pigment and has high dispersibility. In other words, the polymer compound preferably further contains a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may contain one or two or more structural units having an acid group. The polymer compound may contain a structural unit having an acid group or may not contain a structural unit having an acid group. In the case of containing, the content of the structural unit having an acid group is preferably in mass conversion with respect to the total mass of the polymer compound. From 5% to 80%, it is more preferably from 10% to 60% from the viewpoint of suppressing damage of image strength due to alkali development.

a basic group which can interact with a coloring pigment such as a black pigment, for example, a primary amino group, a secondary amino group, a tertiary amino group, a hetero ring containing a N atom, a guanamine group, etc., particularly preferred It is a tertiary amine group which has a good adsorption force to a coloring pigment such as a black pigment and has high dispersibility. The polymer compound may have one or two or more kinds of such basic groups. The polymer compound may contain a structural unit having a basic group or may not contain a structural unit having a basic group. In the case of containing, the content of the structural unit having a basic group is based on the total mass of the polymer compound. The conversion amount is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppressing the inhibition of developability.

Examples of the coordinating group and the reactive functional group which can interact with a coloring pigment such as a black pigment include, for example, an ethenethyloxy group, a trialkoxyalkyl group, an isocyanate group, and an acid anhydride. , 醯 chloride, etc. Particularly preferred is an ethyl fluorenyloxy group having a good adsorptivity to a coloring pigment such as a black pigment and having high dispersibility. The polymer compound may have one or two or more kinds of such groups. The polymer compound may contain a structural unit having a coordinating group or a structural unit containing a reactive functional group, or may not contain a structural unit having a coordinating group or a structural unit containing a reactive functional group. In the case of the content of the polymer compound, the content of the structural unit is preferably 10% or more and 80% or less in terms of mass, and more preferably 20 from the viewpoint of suppressing the hindrance to developability. More than % and less than 60%.

In the case where the polymer compound of the present invention has a functional group capable of interacting with a coloring pigment such as a black pigment other than the graft chain, it is preferable to contain a function capable of interacting with a coloring pigment such as various black pigments as described above. The polymerizable compound is not particularly limited, and the polymer compound preferably contains a structure selected from the group consisting of the following single formulas (iv) to (vi). More than one structural unit in a unit.

[Chemical 6]

In the general formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or a carbon number of 1 An alkyl group of -6 (for example, methyl, ethyl, propyl, etc.). In the general formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably independently hydrogen. Atom or methyl. In the formula (iv), R ¹² and R ^{13 are} further preferably a hydrogen atom.

X ₁ in the formula (iv) represents an oxygen atom (-O-) or an imido group (-NH-), preferably an oxygen atom. Further, Y in the formula (v) represents a methine group or a nitrogen atom.

Further, L ₁ in the general formula (iv) to the general formula (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkyl group, a substituted alkylene group, an alkenyl group, a substituted alkenyl group, an alkynylene group, and a substituted alkyne group). a divalent aromatic group (for example, an extended aryl group and a substituted aryl group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imido group (- NH-), substituted imine bond (-NR ^{31 '} -, where R ^{31 '} is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), or a combination thereof Wait.

The divalent aliphatic group may also have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and still more preferably from 1 to 10. In the case of a less unsaturated aliphatic group, the aliphatic group is preferably a saturated aliphatic group. Further, 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 number of carbon atoms of the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, more preferably from 6 to 10. Further, 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 has a 5-membered or 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. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (=O), a thioketone group (=S), an imido group (=NH), a substituted imido group (=NR ³² , this Wherein 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 oxygen-extended alkyl structure. The oxygen-extended alkyl structure is more preferably an oxygen-extended ethyl structure or an oxygen-extended propyl structure. Further, L ₁ may also contain a polyoxyalkylene structure having a repeating structure containing two or more oxygen-extended alkyl groups. The polyoxyalkylene structure is preferably a polyoxyalkylene structure or a polyoxyalkylene structure. The polyoxyalkylene structure is represented by -(OCH ₂ CH ₂ )n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

In the general formulae (iv) to (vi), Z ₁ represents a functional group which can interact with a coloring pigment such as a black pigment other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, more preferably Carboxylic acid group.

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

In the present invention, as the monolith represented by the 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 an alkyloxy group is contained. A divalent linking group of a structure, a compound wherein X ₁ is an oxygen atom or an imido group, and Z ₁ is a carboxylic acid group. Further, as the monomer of the formula (v), a compound wherein R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine group is preferable. Further, as the monomer of the formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkyl group, and Z is a carboxylic acid. Base compound.

Hereinafter, representative examples of the monomeric (compound) represented by the general formula (iv) to the general formula (vi) are shown. Examples of the monovalent body include methacrylic acid, crotonic acid, methacrylic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate), and succinic anhydride. a reactant, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in a molecule with phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule, and tetrahydroxyphthalic anhydride a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule, and a reaction product of pyromellitic anhydride, acrylic acid, and acrylic acid Polymer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinyl phenol, 4-hydroxyphenylmethacrylamide, and the like.

From the viewpoint of interaction with a coloring pigment such as a black pigment, dispersion stability, and permeability to a developing solution, it has a functional group capable of interacting with a coloring pigment such as a black pigment with respect to the total mass of the polymer compound. The content of the structural unit is preferably from 0.05% by mass to 90% by mass, more preferably from 1.0% by mass to 80% by mass, even more preferably from 10% by mass to 70% by mass.

Further, for the purpose of improving performance such as image strength, the polymer compound may further contain other structural units having various functions as long as the effects of the present invention are not impaired (for example, inclusion and dispersion used in the dispersion) a structural unit having an affinity functional group or the like), the structural unit having a graft chain, a hydrophobic structural unit, and a structural unit having a functional group capable of interacting with a colored pigment such as a black pigment different. Examples of such other structural units include structural units derived from a radically polymerizable compound selected from the group consisting of acrylonitriles and methacrylonitriles. The polymer compound may be one or two or more kinds of the other structural units, and the content of the other structural units is preferably 0% or more and 80% or less by mass, based on the total mass of the polymer compound, more preferably 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability can be maintained.

The acid value of the polymer compound is preferably in the range of 0 mgKOH/g or more and 160 mgKOH/g or less, more preferably 10 mgKOH/g or more and 140 mgKOH/g or less, and further preferably 20 mgKOH/g or more and 120. The range of mgKOH/g or less. When the acid value of the polymer compound is 160 mgKOH/g or less, pattern peeling at the time of development at the time of forming a cured film can be more effectively suppressed. In addition, when the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability is further improved. In addition, when the acid value of the polymer compound is 20 mgKOH/g or more, sedimentation of a colored pigment such as a black pigment (particularly titanium black) or a dispersion containing titanium black and Si atoms can be further suppressed, and coarse particles can be obtained. The number is further reduced, so that the stability over time of the composition can be further improved.

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

When the cured film is formed, the weight average molecular weight of the polymer compound in the present invention is polyphenylene by gel permeation chromatography (GPC) method from the viewpoint of suppressing pattern peeling and developability at the time of development. The ethylene equivalent value is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, still more preferably 6,000 to 100,000, particularly preferably 10,000 to 50,000. The GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh Co., Ltd.), manufactured using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (Tosoh), 4.6 mmID. ×15 cm) was used as a column, and tetrahydrofuran (THF) was used as a solution.

The polymer compound can be synthesized by a known method. Examples of the solvent used in the synthesis of the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, and propanol. Butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate Ester, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylhydrazine, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. These solvents may be used singly or in combination of two or more.

Specific examples of the polymer compound which can be used in the present invention include "DA-7301" manufactured by Phoebe Chemical Co., Ltd.; and "Disperbyk" manufactured by BYK Chemie Co., Ltd. 101 (polyamidoamine phosphate), 107 (carboxylate), 110 (copolymer containing acid group), 111 (phosphate dispersant), 130 (polyamine), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)"; "Evka" (made by EFKA) EFKA) 4047, 4050～4010～4165 (polyurethane type), Efka (EFKA) 4330～Evka (EFKA) 4340 (block copolymer), 4400～4402 (modified polyacrylate ), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative); Ajinomoto fine chemistry "Ajisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine-Techno "Flowlen TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300 (acrylic copolymer) manufactured by Kyoeisha Chemical Co., Ltd." "Disparlon KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705 manufactured by Nanben Chemical Co., Ltd. , DA-725"; Demol RN, N (formalin condensation system of naphthalenesulfonate), MS, C, SN-B (aromatic polycondensate of aromatic sulfonate) manufactured by Kao Corporation, " Homogenol L-18 (polymer polycarboxylic acid), "Emulgen 920, 930, 935, 985 (polyoxyethylidene phenyl ether)", "A Acetamin 86 (stearylamine acetate); "Solsperse 5000 (phthalocyanine derivative), 22000 (even) manufactured by Lubrizol, Japan Nitrogen pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional portion at the terminal portion), 24000, 28000, 32000, 38500 (grafting) Copolymer)" Nikol T106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylidene monostearate) manufactured by Nikko Chem. "Hinoact T-8000E" manufactured by Chuanyan Fine Chemicals Co., Ltd.; "Organic alkane polymer KP341" manufactured by Shin-Etsu Chemical Co., Ltd.; manufactured by Yusho Co., Ltd. W001: cationic surfactant] polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxygen Nonionic surfactants such as ethyl nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; "W004, W005, W017" Anionic surfactants; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymers manufactured by Morishita Industries Co., Ltd. 100, Efka (EFKA) polymer 400, Efka (EFKA) polymer 401, Efka (EFKA) polymer 450"; San Nopco "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Despas Ed (") Disperse Aid) 9100" and other polymer dispersing agents; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95 manufactured by ADEKA , F77, P84, F87, P94, L101, P103, F108, L121, P-123"; and "Ionet (trade name) S-20" manufactured by Sanyo Chemical Co., Ltd. In addition, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, Cyclomer P can also be used. . Further, as a commercial product of the amphoteric resin, for example, DISPERBYK-130, DISPERBYK-140, and Dispabbi manufactured by BYK Chemie Co., Ltd. DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191 , DISPERBYK-2001, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK -9076, Ajisper PB821, Ajisper PB822, Ajisper PB881, etc. manufactured by Ajinomoto Fine-Techno. These polymer compounds may be used singly or in combination of two or more.

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

Further, as the dispersing agent, in addition to the polymer compound, grafting of paragraph 0037 to paragraph 0115 of the Japanese Patent Laid-Open Publication No. 2010-106268 (corresponding to paragraphs 0075 to 0133 of US2011/0124824) may be used. Copolymers may be cited and incorporated into the present specification. In addition, in addition to the above, the inclusion of an acidic group via a linking group may also be used in paragraphs 0928 to 0084 of the Japanese Patent Laid-Open Publication No. 2011-153283 (corresponding to paragraphs 0075 to 0133 of US2011/0279759). The polymer compound of the constituent components of the side chain structure can be referred to and incorporated in the present specification.

The content of the dispersant in the composition of the present invention is preferably from 0.1% by mass to 50% by mass, and more preferably from 0.5% by mass to 30% by mass based on the total solid content of the composition.

(b) Polymerization initiator The composition of the invention contains a polymerization initiator. The polymerization initiator is not particularly limited and may be appropriately selected from known polymerization initiators. For example, those having photosensitivity (so-called photopolymerization initiators) are preferred. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred that the ultraviolet region is sensitive to visible light. Further, it may be an active agent which generates a living radical by a certain action with a photo-excited sensitizer, or may be an initiator which initiates cationic polymerization in accordance with the kind of the monomer. Further, the photopolymerization initiator is preferably a compound having at least one molar absorption coefficient of at least about 50 in the range of from about 300 nm to 800 nm, more preferably from 330 nm to 500 nm.

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, a hexaarylbiimidazole or an anthracene. An anthracene compound such as a derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone. Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in "Bull. Chem. Soc. Japan" (42, 2924 (1969)), and a British patent. The compound described in the specification of No. 1388492, the compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the "Journal of Organic Chemistry (J. Org. Chem) by FC Schaefer et al. The compound described in the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in the publication, the compound described in the specification of U.S. Patent No. 4,212,976, and the like.

Further, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, and a mercaptophosphine compound. , phosphine oxide compound, metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene a compound of the group consisting of an iron complex and a salt thereof, a halogenated methyl oxadiazole compound, and a 3-aryl substituted coumarin compound.

More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, mercaptophosphine compounds, phosphine oxide compounds, antimony compounds, triallyl imidazole dimers, antimony compounds, benzophenone compounds, benzene The ethyl ketone compound is further preferably at least selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound. a compound.

In particular, when the curable composition of the present invention is used for the production of a light-shielding film of a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape. Therefore, it is important that the curable property and the unexposed portion have no residue. Development is carried out. From this point of view, it is particularly preferred to use a ruthenium compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, exposure for curing is performed by stepwise exposure, but the exposure machine is damaged by halogen, and the amount of photopolymerization initiator added must be suppressed low. Therefore, in consideration of these aspects, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator when forming a fine pattern like a solid-state image sensor. In addition, color mobility can be improved by using a ruthenium compound. As a specific example of the photopolymerization initiator, for example, reference is made to paragraph 0265 to paragraph 0268 of JP-A-2013-29760, which is incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be preferably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a mercaptophosphine-based initiator described in Japanese Patent No. 4,258,899 can be used. As a hydroxyacetophenone-based initiator, it can be used: IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, Yan IRGACURE-127 (trade name, manufactured by BASF). As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names, both of which are commercially available) can be used. Made by BASF). The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matching a long-wavelength source such as 365 nm or 405 nm. As the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name, all manufactured by BASF) can be used as a commercial product.

As a photopolymerization initiator, a ruthenium compound is more preferable. In particular, the oxime-based initiator is highly sensitive and has high polymerization efficiency, and can be hardened regardless of the concentration of the colored material, and is preferable because the concentration of the colored material is easily designed to be high. As a specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used. In the present invention, examples of the ruthenium compound which can be preferably used include, for example, 3-benzylideneoxyiminobutan-2-one and 3-ethyloxyiminobutan-2-one. , 3-propenyloxyiminobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropane- 1-ketone, 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-B Oxycarbonyloxyimino-1-phenylpropan-1-one and the like. In addition, "JCS Perkin II" (June 1653-1660) and "JCS Perkin II" are also listed. ((1979) pp. 156-162), Journal of Photopolymer Science and Technology ((1995) pp. 202-232), Japanese Patent Laid-Open No. 2000-66385 The compound described in each of the publications of Japanese Laid-Open Patent Publication No. Hei. No. 2000-800. In the commercial product, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be preferably used. In addition, you can also use TR-PBG-304 (made by Changzhou Power Electronic New Materials Co., Ltd.), Adeka Cruise NCI-831, and Adeka Cruise NCI-930 (ADEKA) ))))

In addition, as the ruthenium compound other than the above-mentioned one, the compound described in Japanese Patent Laid-Open Publication No. 2009-519904, in which the carbazole is bonded to the N-position of the carbazole, and the United States having a hetero substituent introduced into the benzophenone moiety may be used. The compound described in Japanese Patent Publication No. 7626957, the compound described in Japanese Patent Laid-Open Publication No. 2010-15025, and the Japanese Patent Publication No. 2009-292039, the disclosure of which is incorporated herein by reference. A ketone oxime compound, a compound described in US Pat. No. 7,569,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption at 405 nm and has a good sensitivity to a g-ray source, and is disclosed in Japanese Patent Laid-Open No. 2009-221114 A compound or the like described in the publication. For example, it is preferable to refer to paragraph 0274 to paragraph 0275 of Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2013-29760, the disclosure of which is incorporated herein. Specifically, the quinone compound is preferably a compound represented by the following formula (OX-1). Further, it may be an anthracene compound in which the N-O bond of ruthenium is (E), a ruthenium compound of (Z), or a mixture of (E) and (Z).

[Chemistry 7]

In the 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. The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. In addition, the groups may have one or more substituents. Further, the substituent may be further substituted with another substituent. The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or 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. The groups may also have more than one substituent. The substituent may be exemplified as the substituent. In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having a carbon number of 1 to 12, a cycloalkylene group or an alkynylene group. The groups may also have more than one substituent. The substituent may be exemplified as the substituent.

The present invention can also use a ruthenium compound having a fluorine atom as a photopolymerization initiator. Specific examples of the ruthenium compound having a fluorine atom include a compound described in JP-A-2010-262028, a compound 24 described in JP-A-2014-500852, a compound 36 to a compound 40, and a Japanese patent. Compound (C-3) or the like described in Japanese Patent Publication No. 2013-164471. This content is incorporated into the present specification.

In the present invention, a compound represented by the following formula (1) or formula (2) can also be used as a photopolymerization initiator.

[化8]

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

Formula ^{(2), R 1, R 2, R} 3 and R ⁴ of the formula R (1) is ^1, R ^2, R ³ and R ⁴ are the same meanings, 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 a hydroxyl group, and R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or A carbonyl group, a represents an integer of 0-4.

In the formulae (1) and (2), R ¹ and R ² are 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 a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ^{4 is} preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ^{5 is} preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond. Specific examples of the compound represented by the formula (1) and the formula (2) include the compounds described in Paragraph No. 0076 to Paragraph No. 0079 of JP-A-2014-137466. This content is incorporated into the present specification.

Specific examples of the ruthenium compound which can be preferably used in the present invention are shown below, but the present invention is not limited to these specific examples.

[Chemistry 9]

The ruthenium compound preferably has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, more preferably a wavelength having a maximum absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably a high absorbance at 365 nm and 405 nm. . From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, particularly preferably from 5,000 to 200,000. The molar absorption coefficient of the compound can be measured by a known method, and is preferably, for example, by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and used. The ethyl acetate solvent was measured at a concentration of 0.01 g/L. The photopolymerization initiator used in the present invention may be used in combination of two or more kinds as needed.

The content of the polymerization initiator is preferably from 0.1% by mass to 50% by mass, more preferably from 0.5% by mass to 30% by mass, even more preferably from 1% by mass to 20% by mass based on the total solid content of the curable composition. By this range, more excellent sensitivity and pattern formation property can be obtained. The curable composition of the present invention may contain only one polymerization initiator, and may contain two or more types. In the case where two or more types are contained, it is preferable that the total amount thereof is the above range.

The content of the polymerization initiator in the composition of the present invention is preferably from 0.1% by mass to 30% by mass, more preferably from 1% by mass to 25% by mass, even more preferably 1% by mass based on the total solid content of the composition. % to 10% by mass.

(c) Polymerizable compound The composition of the present invention contains a polymerizable compound. The polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or more at normal pressure. It is particularly preferable to contain two or more and ten or less ethylenically unsaturated groups in the polymerizable compound, and a so-called polyfunctional polymerizable compound is preferable. Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or more at normal pressure include polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(methyl). a monofunctional acrylate or methacrylate such as acrylate or phenoxyethyl (meth) acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tris(methyl) Acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (methyl) Acrylate, trimethylolpropane tris(propylene decyloxypropyl) ether, tris(propylene decyloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. a compound obtained by adding (meth) acrylate to a polyfunctional alcohol, and a compound obtained by poly (meth) acrylate of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho 50-6034, Japanese Patent Laid-Open No. 51-37193 A urethane acrylate described in each of the publications of Japanese Laid-Open Patent Publication No. SHO-49-64183, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52-30490 A polyfunctional acrylate or methacrylate such as an epoxy acrylate such as a reaction product of an oxygen resin and (meth)acrylic acid. Further, as the photocurable monomer and oligomer, the compounds described in "Japan Next Association", Vol. 20, No. 7, and pages 300 to 308 can also be used. In addition, after the polyfunctional alcohol described in the general formula (1) and the general formula (2) and the specific examples thereof, the ethylene oxide or the propylene oxide can be used as the polyfunctional alcohol described in Japanese Patent Application Laid-Open No. Hei 10-62986 A compound obtained by (meth)acrylation. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryl oxime groups are bonded to dipentaerythritol via an ethylene glycol residue or a propylene glycol residue are preferable. These types of oligomers can also be used. In addition, the urethanes described in the publications of Japanese Patent Publication No. Sho-48-41708, JP-A-53-37193, Japanese Patent Application No. Hei 2-32293, and Japanese Patent Publication No. Hei 2-16765 Ethylene acrylates described in the respective publications of the ester acrylates, or the Japanese Patent Publication No. Sho 58-49860, the Japanese Patent Publication No. SHO 56-17654, the Japanese Patent Publication No. Sho 62-39417, and the Japanese Patent Publication No. Sho 62-39418 A urethane compound of a skeleton is also preferred. Further, an amine group structure or a thioether is contained in the molecule as described in each of the publications of JP-A-63-277653, JP-A-63-260909, and JP-A-10-1-5238. The addition polymerizable compound of the structure can obtain a photopolymerizable composition which is excellent in the photospeed. As a commercial item, a urethane oligomer UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemical Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name, manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (trade name, Kyoeisha Chemical Co., Ltd.) Manufacturing) and so on. Further, an ethylenically unsaturated compound having an acid group is also preferable, and as a commercially available product, for example, TO-756 which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing five are mentioned. Functional acrylate TO-1382 and the like. The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound. Examples of the tetrafunctional or higher acrylate compound include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.).

The polymerizable compounds may be used alone or in combination of two or more. When two or more types of polymerizable compounds are used in combination, the combination form can be appropriately set depending on the physical properties required for the composition and the like. One of the preferable combinations of the polymerizable compounds is, for example, a combination of two or more kinds of polymerizable compounds selected from the above-mentioned polyfunctional acrylate compounds. A combination of pentaerythritol hexaacrylate and pentaerythritol triacrylate. The content of the polymerizable compound is preferably 3% by mass to 55% by mass, and more preferably 7% by mass to 50% by mass, based on the total solid content of the curable composition of the present invention.

(d) Binder polymer The composition of the present invention contains a binder polymer. As the binder polymer, a linear organic polymer is preferably used. As such a linear organic polymer, a known one can be used arbitrarily. It is preferred to select a linear organic polymer which is soluble or swellable to water or weakly alkaline water in order to enable water development or weak alkaline water development. Among them, as the binder polymer, an alkali-soluble resin (a resin having a base which promotes alkali solubility) is particularly preferred. The binder polymer is suitably selected from the group consisting of alkali-soluble resins which are linear organic high molecular polymers and which are mainly composed of an acrylic copolymer and a styrene copolymer. The molecule has at least one group that promotes alkali solubility. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable, and the viewpoint of controlling developability is preferable. In particular, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable. Examples of the base which promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are preferably soluble in an organic solvent and can be made by a weakly basic aqueous solution. As the developer, (meth)acrylic acid is particularly preferred. These acid groups may be used alone or in combination of two or more.

Examples of the binder polymer include a radical polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho-58- No. 12,577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. Sho 54-92723, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048, a resin obtained by separately or copolymerizing a monomer of a carboxyl group, a resin obtained by hydrolyzing or semi-esterifying or semi-esterifying an acid anhydride unit obtained by copolymerizing a monomer having an acid anhydride, or an unsaturated monocarboxylic acid and an acid anhydride. An epoxy acrylate or the like obtained by modifying an epoxy resin. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene, and examples of the monomer having an acid anhydride. A maleic anhydride etc. are mentioned. Further, an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified as an example. In addition to this, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group. In addition, the film strength and development of an acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in each of the publications of the European Patent No. 993, 966, the European Patent No. PCT No. The balance of sex is excellent and thus better. Further, as the water-soluble linear organic polymer other than the above, polyvinylpyrrolidone or polyethylene oxide is useful. Further, in order to increase the strength of the hardened film, alcohol-soluble nylon or a polyether which is 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin is also useful.

Among these, in particular, [(meth)acrylic acid methacrylate/(meth)acrylic acid/optionally other addition polymerizable vinyl monomer] copolymer, and [(meth)acrylic acid allyl ester/(A) The acrylic acid/other addition polymerizable vinyl monomer as needed is excellent in the balance of film strength, sensitivity, and developability. As a commercial item, Acrybase FF-187, FF-426 (made by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Japan catalyst (share)) are mentioned, for example. ), Cyclomer P (ACA) 230AA manufactured by Daicel-Allnex (share).

For the production of the binder polymer, for example, a method using a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, the kind of the solvent, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and can also be experimentally conducted. Determine the conditions sexually.

Further, as the binder polymer, a polymer containing a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group) is also preferably used. The definition of the structural unit having a graft chain has the same meaning as the structural unit having a graft chain contained in the dispersing agent, and the preferred range is also the same. The acid group is preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group or a phenolic hydroxyl group, and is preferably at least one of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group, and particularly preferably a carboxylic acid group.

The structural unit having an acid group preferably has one or more structural units selected from the structural units derived from the unitary bodies represented by the following general formulae (vii) to (ix).

[化10]

In the general formulae (vii) to (ix), R ^{2 1} , R ^{2 2} and R ^{2 3} each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or a carbon atom. The number is 1 to 6 alkyl groups (e.g., methyl, ethyl, propyl, etc.). In the general formulae (vii) to (ix), R ^{2 1} , R ^{2 2} and R ^{2 3} are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably independently. The ground is a hydrogen atom or a methyl group. In the formula (vii), R ²¹ and R ^{23 are} further preferably a hydrogen atom.

X ₂ in the formula (vii) represents an oxygen atom (-O-) or an imido group (-NH-), preferably an oxygen atom. Further, Y in the formula (viii) represents a methine group or a nitrogen atom.

Further, L ₂ in the general formula (vii) to the general formula (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkyl group, a substituted alkylene group, an alkenyl group, a substituted alkenyl group, an alkynylene group, and a substituted alkyne group). a divalent aromatic group (for example, an extended aryl group and a substituted aryl group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imido group (- NH-), substituted imine bond (-NR ^{4 1 '} -, where R ^{4 1 '} is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), or these The combination and so on.

The divalent aliphatic group may also have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and still more preferably from 1 to 10. In the case of a less unsaturated aliphatic group, the aliphatic group is preferably a saturated aliphatic group. Further, 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 number of carbon atoms of the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, more preferably from 6 to 10. Further, 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 has a 5-membered or 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. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (=O), a thioketone group (=S), an imido group (=NH), a substituted imido group (=NR ^{4 2} , Here, R ^{4 2} 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 single bond, an alkylene group or a divalent linking group containing an oxygen-extended alkyl structure. The oxygen-extended alkyl structure is more preferably an oxygen-extended ethyl structure or an oxygen-extended propyl structure. Further, L ₂ may also contain a polyoxyalkylene structure having a repeating structure containing two or more oxygen-extended alkyl groups. As the polyoxyalkylene structure, a polyoxyalkylene structure or a polyoxyalkylene structure is preferred. The polyoxyalkylene structure is represented by -(OCH ₂ CH ₂ )n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

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

In the formula (ix), R ^{2 4} , R ^{2 5} and R ^{2 6} each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.) or an alkyl group having 1 to 6 carbon atoms (for example). , methyl, ethyl, propyl, etc.), - Z ₂ or L ₂ -Z _2. Here, L ₂ and Z ₂ have the same meanings as the above-mentioned L ₂ and Z ₂ , and preferred examples are also the same. R ^{2 4} , R ^{2 5} and R ^{2 6} are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably each independently a hydrogen atom.

In the present invention, as the monomer of the formula (vii), R ^{2 1} , R ^{2 2} and R ^{2 3} are each independently a hydrogen atom or a methyl group, L ₂ is an alkylene group or contains oxygen. A divalent linking group having an alkyl structure, a compound wherein X ₂ is an oxygen atom or an imine group, and Z ₂ is a carboxylic acid group. Further, as the monomer of the formula (vii), a compound wherein R ^{2 1} is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is a methine group is preferable. Further, as the unitary substance represented by the formula (ix), a compound in which R ^{2 4} , R ^{2 5} and R ^{2 6} are each independently a hydrogen atom or a methyl group and Z ₂ is a carboxylic acid group is preferable.

The binder polymer can be synthesized by the same method as the above-described pigment dispersant containing a structural unit having a graft chain, and further preferably has the same acid value and weight average molecular weight.

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

The content of the binder polymer in the composition of the present invention is preferably from 0.1% by mass to 30% by mass, and more preferably from 0.3% by mass to 25% by mass based on the total solid content of the composition.

(e) Solvent The composition of the present invention contains a solvent. As a solvent, water or an organic solvent is mentioned. Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene. Alcohol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetyl ketone acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, Glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Diol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, Dimethyl sulfonium, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc., but are not limited thereto.

The solvent may be used singly or in combination of two or more. In the case where two or more solvents are used in combination, it is particularly preferred to comprise a solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve acetate. Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl Two or more of the group consisting of carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. The amount of the solvent contained in the composition of the present invention is preferably from 10% by mass to 90% by mass, and more preferably from 20% by mass to 85% by mass based on the total mass of the composition.

<Other optional components> The composition of the present invention may contain other components than the above-described main components. Hereinafter, various arbitrary components will be described in detail.

[Centane Coupling Agent] The decane coupling agent refers to a compound having a hydrolyzable group and a functional group other than the molecule. Further, a hydrolyzable group such as an alkoxy group is bonded to a ruthenium atom. The hydrolyzable group refers to a substituent which is directly bonded to a ruthenium atom and which can form a siloxane chain by a hydrolysis reaction and/or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, a mercaptooxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the carbon number is preferably 6 or less, more preferably 4 or less. It is particularly preferably an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms. Further, in order to improve the adhesion between the substrate and the cured film, the decane coupling agent preferably does not contain a fluorine atom or a ruthenium atom (except for a ruthenium atom to which a hydrolyzable group is bonded), and preferably does not contain a fluorine atom. And a ruthenium atom (excluding a ruthenium atom having a hydrolyzable group bonded thereto), an alkylene group substituted with a ruthenium atom, a linear alkyl group having 8 or more carbon atoms, and a branched alkyl group having 3 or more carbon atoms.

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

The decane coupling agent preferably has one or more types of curable functional groups selected from the group consisting of (meth) acryloyloxy groups, epoxy groups, and oxetanyl groups. The hardening functional group may be directly bonded to the ruthenium atom or may be bonded to the ruthenium atom via the linking group. Further, as a preferred aspect of the curable functional group contained in the decane coupling agent, a radical polymerizable group may also be mentioned.

The molecular weight of the decane coupling agent is not particularly limited, and is usually from 100 to 1,000 in terms of workability, and is preferably 270 or more, and more preferably from 270 to 1,000, in terms of the effect of the present invention being more excellent. .

One of preferred embodiments of the decane coupling agent is a decane coupling agent X represented by the formula (W). Formula (W) R _Z2 -Lz-Si-(R _Z1 ) ₃ R _Z1 represents a hydrolyzable group, and the definition is as described above. R _Z2 represents a hardenable functional group, and the definition is as described above, and the preferred range is also as described above. Lz represents a single bond or a divalent linking group. In the case where Lz represents a divalent linking group, examples of the divalent linking group include an alkyl group which may be substituted by a halogen atom, an extended aryl group which may be substituted by a halogen atom, -NR ¹² -, -CONR ¹² -, -CO -, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, -SO ₂ -, or a combination of these. In particular, it is preferably at least one selected from the group consisting of an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms and an extended alkyl group which may be substituted with a halogen atom having 6 to 12 carbon atoms, or the like. And at least one selected from the group consisting of -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, and -SO ₂ - The group of the combination of the group, more preferably an alkyl group substituted with a halogen atom having 2 to 10 carbon atoms, -CO ₂ -, -O-, -CO-, -CONR ¹² -, or a combination of these groups base. Here, R ¹² represents a hydrogen atom or a methyl group.

Examples of the decane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602), and N-β. -Aminoethyl-γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603), N-β-aminoethyl-γ-aminopropyl-triethyl Oxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602), γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903), γ-aminopropyl - Triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903), 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503), Glycidoxyoctyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-4803).

Another preferable aspect of the decane coupling agent is a decane coupling agent Y having at least a ruthenium atom, a nitrogen atom, and a curable functional group in the molecule and having a hydrolyzable group bonded to a ruthenium atom. The decane coupling agent Y may have at least one ruthenium atom in the molecule, and the ruthenium atom may be bonded to the following atoms or substituents. These may be the same atom, a substituent, or may be different. Examples of the bondable atom and the substituent include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, and an amine group which may be substituted with an alkyl group and/or an aryl group. And a decyl group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group or the like. The substituents may further be substituted with a decyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy group, an amine group which may be substituted by an alkyl group and/or an aryl group, a halogen atom A sulfonamide group, an alkoxycarbonyl group, a decylamino group, a ureido group, an ammonium group, an alkylammonium group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or the like. Further, at least one hydrolyzable group is bonded to a ruthenium atom. The definition of the hydrolyzable group is as described above. The group represented by the formula (Z) may also be contained in the decane coupling agent Y.

The decane coupling agent Y has at least one or more nitrogen atoms in the molecule, and the nitrogen atom preferably exists in the form of a secondary amino group or a tertiary amino group, that is, preferably, the nitrogen atom has at least one organic group as a substituent. . Further, the structure of the amine group may be present in the form of a partial structure containing a nitrogen hetero ring, or may be in the form of a substituted amine group such as aniline. Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent. Examples of the substituent which may be introduced include a fluorenyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amine group, and a halogen atom. And a sulfonylamino group, an alkoxycarbonyl group, a carbonyloxy group, a decylamino group, a ureido group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxyl group or a salt thereof, a sulfo group or the like. Further, the nitrogen atom is preferably bonded to the curable functional group via an arbitrary organic linking group. Preferred examples of the organic linking group include a substituent which can be introduced into the nitrogen atom and an organic group bonded thereto.

The definition of the curable functional group contained in the decane coupling agent Y is as described above, and the preferred range is also as described above. The decane coupling agent Y may have at least one or more curable functional groups in one molecule, and may have a form having two or more curable functional groups. From the viewpoint of sensitivity and stability, it is preferably It has 2 to 20 hardening functional groups, more preferably 4 to 15 carbon atoms, and most preferably has 6 to 10 hardening functional groups in the molecule.

The molecular weight of the decane coupling agent X and the decane coupling agent Y is not particularly limited, and the above range (preferably 270 or more) is exemplified.

The content of the decane coupling agent in the composition of the present invention is preferably from 0.1% by mass to 10% by mass, more preferably from 0.5% by mass to 8% by mass, even more preferably 1.0% by mass, based on the total solid content in the composition. ～6% by mass.

The composition of the present invention may contain a single decane coupling agent, or may contain two or more kinds. When the composition contains two or more kinds of decane coupling agents, the total amount may be within the above range.

[Others] The composition of the present invention may also contain an ultraviolet absorber. Thereby, the shape of the pattern can be made more excellent (fine). As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based or triazine-based ultraviolet absorber can be used. As a specific example of these, a compound of paragraph 0137 to paragraph 0142 of the Japanese Patent Laid-Open Publication No. 2012-068418 (corresponding to paragraphs 0251 to 0254 of US2012/0068292) can be used, and the contents can be cited and incorporated into In this manual. In addition to this, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) or the like can be preferably used. The ultraviolet absorbing agent may, for example, be a compound exemplified in paragraphs 0134 to 0148 of JP-A-2012-32556. The composition of the present invention may contain an ultraviolet absorber or may not contain an ultraviolet absorber. In the case of inclusion, the content of the ultraviolet absorber is preferably from 0.001% by mass to 15% by mass based on the total solid content of the composition. It is preferably from 0.01% by mass to 10% by mass, and more preferably from 0.1% by mass to 5% by mass.

[Interfacial Agent] The composition of the present invention may contain various surfactants from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

When the fluorine-based surfactant is contained in the composition of the present invention, the solution characteristics (particularly fluidity) when the coating liquid is prepared are further improved, and the uniformity of the coating thickness or the liquid-saving property can be further improved. In other words, when a film is formed by using a coating liquid containing a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is lowered to wet the surface to be coated. The properties are improved and the coatability to the coated surface is improved. Therefore, film formation of a uniform thickness having a small thickness unevenness can be more preferably performed.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-containing content ratio of the fluorine-based surfactant in this range is effective in the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac. F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac RS-72-K (above produced by Di Aisheng (DIC)); Froude (Fluorad) FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3M (share)); Surfolon S-382, Surflon SC-101 , Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, sand Surflon SC-383, Surflon S393, sand Long (Surflon) KH-40 (Asahi Glass (shares) manufactured); PF636, PF656, PF6320, PF6520, PF7002 (OMNOVA (OMNOVA) Co., Ltd.). As the fluorine-based surfactant, the compound described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used. As the fluorine-based surfactant, a block polymer can also be used. Specific examples thereof include a compound described in JP-A-2011-89090. The fluorine-based surfactant may preferably be a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound having a fluorine atom and having two or more origins ( A repeating unit of a (meth) acrylate compound preferably having five or more alkyleneoxy groups (preferably an ethyl ethoxy group, a propyloxy group), and the following compounds may also be used in the present invention. The fluorine-based surfactant to be used is exemplified.

[11]

The weight average molecular weight of the compound is preferably from 3,000 to 50,000, for example, 14,000. Further, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain may also be used as the fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, Megafac RS-101 manufactured by Diane Health (DIC) Co., Ltd. , RS-102, RS-718K, RS-72-K, etc.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerin C). Oxylate, glycerol ethoxylate, etc.), polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether , polyoxyethylene ethyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pullonik manufactured by BASF) (Pluronic) L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic, 304, 701, 704, 901, 904, 150R1), Solsperse 20000 (Japan Lubo Run (Lubrizol) (manufacturing) and so on. In addition, NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industries Co., Ltd.), and an organic siloxane polymer KP341 (Shin-Etsu Chemical Industry ( (manufacturing)), (meth)acrylic (co)polymers Polyflow No.75, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yu Shang ( Share) manufacturing) and so on.

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

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

The surfactant may be used singly or in combination of two or more. The content of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass based on the total solid content of the composition of the present invention.

In addition to the above components, the following components may be further added to the composition of the present invention. For example, a sensitizer, a co-sensitizer, a crosslinking agent, a hardening accelerator, a filler, a thermosetting accelerator, a polymerization inhibitor, a plasticizer, a diluent, a sensitizer, etc. are mentioned, and further, as needed And adding an adhesion promoter to the surface of the substrate and other auxiliary agents (for example, conductive particles, a filler, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, a surface tension adjuster, A known additive such as a chain transfer agent or the like. For example, Japanese Patent Laid-Open No. 2012-003225, Paragraph No. 0183 to Paragraph No. 0228 (corresponding U.S. Patent Application Publication No. 2013/0034812, [0237] to [0309]), Japanese Patent Laid-Open JP-A-2008-250074, paragraph number 0101 to paragraph number 0102, paragraph number 0103 to paragraph number 0104, paragraph number 0107 to paragraph number 0109, and paragraph number 0159 to paragraph number 0184 of JP-A-2013-195480 This content is incorporated into the specification of the present application.

The solid content concentration of the composition of the present invention is preferably from 5% by mass to 50% by mass, and more preferably from 15% by mass to 40% by mass in terms of the balance between the thickness of the cured film to be formed and the light-shielding property.

[Method for Preparing Composition] The composition of the present invention can be prepared by mixing the various components by a known mixing method (for example, a stirrer, a homogenizer, a high pressure emulsifier, a wet pulverizer, or a wet disperser). The composition of the present invention is preferably filtered by a filter for the purpose of removing foreign matter or reducing defects. The filter is not particularly limited as long as it is used for a filter or the like since the prior art. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon, or a polyolefin resin such as polyethylene or polypropylene (including high density and ultrahigh molecular weight) may be used. Filter. Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred. The pore diameter of the filter is suitably from about 0.1 μm to about 7.0 μm, preferably from about 0.2 μm to about 2.5 μm, more preferably from about 0.2 μm to about 1.5 μm, and even more preferably from 0.3 μm to 0.7 μm. By setting it as this range, it is possible to suppress the filtration clogging of the pigment, and it is possible to reliably remove fine foreign matter such as impurities or aggregates contained in the pigment. Different filters can also be combined when using filters. In this case, the filtration by the first filter may be performed only once or twice or more. In the case where different filters are combined to perform two or more filtrations, it is preferred that the pore size of the second and subsequent filtrations is the same as the pore diameter of the first filtration or larger than the pore diameter of the first filtration. Further, the first filters of different pore sizes may be combined within the above range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from Pall Co., Ltd., Advantec Toyo Co., Ltd., and Entegris Co., Ltd. (formerly Mi Curry, Japan) (Mykrolis) Co., Ltd.) or Kitez Microfilter (Kitz Microfilter) Co., Ltd. and other filters are available. As the second filter, a filter formed of the same material or the like as the first filter can be used. The pore diameter of the second filter is suitably from about 0.2 μm to about 10.0 μm, preferably from about 0.2 μm to about 7.0 μm, and more preferably from about 0.3 μm to about 6.0 μm.

<Step of Producing Cured Film> The method for producing a cured film according to the present invention includes the first step of spray coating the curable composition to form a first coating film so that the landing size is D1, and the second step of landing The step of applying D2 to the curable composition to form a second coating film, and performing a curing treatment to form a cured film. In this way, a cured film is obtained. Here, the "first coating film" is cured by the curing treatment to become a "first film". Similarly, the "second coating film" is cured by the curing treatment to become a "second film." In other words, the cured film having the first film and the second film is obtained by the method for producing a cured film of the present invention. Hereinafter, an example of a method for producing a cured film of the present invention will be described with reference to FIGS. 1A and 1B. 1A and 1B are explanatory views showing an example of a method of producing a cured film of the present invention as described above.

(First Step) The first step is a step of spray-coating the curable composition so that the landing size becomes D1 to form a first coating film. Specifically, as shown in FIG. 1A, when the curable composition is ejected from the nozzle 210 of the spray device, the curable composition flies into a plurality of droplets, and the plurality of droplets land on the surface of the substrate 100. (coated surface). The droplets adhering to the coated surface are dried to form a granular material 120a. A plurality of the granules 120a are aggregated to form a first coating film 120A. Furthermore, the type of the substrate to be used is not particularly limited. In the case where the cured film is disposed in the solid-state imaging device, various components in the solid-state imaging device (for example, an infrared light-cut filter, an outer peripheral portion of the solid-state imaging device, and a wafer) are preferably used as the substrate. The outer peripheral portion of the lens, the back surface of the solid-state imaging device, etc.). Further, the spray device is not particularly limited, and a known device can be used.

Here, the term "landing size" as used in the present invention refers to a diameter of a granular material obtained by drying a droplet when a droplet generated by spraying a curable composition from a nozzle of a spray device adheres to a glass substrate. . Specifically, the landing size is obtained by observing the granular material attached to the glass substrate by an optical microscope, and assuming that the granular material is a circle (a circular approximate diameter), the granular material at 500 is measured and subjected to Arithmetic average. In addition, the drying conditions at the time of measuring the landing size are not particularly limited, and may be carried out under the condition that 80% by mass or more of the volatile components (solvent or the like) contained in the droplets are volatilized.

The landing size D1 is preferably from 35 μm to 150 μm, more preferably from 40 μm to 145 μm, and even more preferably from 45 μm to 140 μm. By the landing size D1 being within the above range, the lithographic performance of the cured film is further improved.

The landing size can be controlled by appropriately setting the conditions of the spray coating. Preferred conditions for controlling the landing size include nozzle height, atomization pressure, hydraulic pressure, nozzle opening diameter, and the like at the time of spray coating.

The nozzle height at the time of spray coating refers to the distance between the nozzle tip end (portion from the nozzle jet curable composition) and the coated surface (the surface of the substrate 100 in FIG. 1A). In the first step, the nozzle height L1 (distance L1) is preferably 10 cm or less, more preferably less than 5 cm, further preferably 4 cm or less, and particularly preferably 3 cm or less. Further, the lower limit is preferably 1 cm or more, and more preferably 2 cm or more. By setting the nozzle height L1 to less than 5 cm, it is possible to suppress the volatilization of the volatile components during the flight of the droplets, so that the landing size can be further increased. Thereby, the lithographic performance of the cured film is further improved. In addition, by setting the nozzle height L1 to 1 cm or more, it is possible to suppress the flow of the dropped droplets, and it is possible to suppress the surface roughness of the first coating film and the occurrence of pinholes in the cured film.

The atomization pressure refers to a pressure applied to the curable composition in order to eject the curable composition from the nozzle of the spray device. The atomization pressure in the first step is preferably from 300 g/cm ² to 500 g/cm ² , more preferably from 350 g/cm ² to 490 g/cm ² , and still more preferably from 380 g/cm ² to 480 g/ Cm ² . When the atomization pressure is 500 g/cm ² or less, the amount of gas mixed in when the curable composition is ejected from the nozzle can be reduced, so that it is difficult to dry the droplets. Thereby, since the landing size can be increased, the lithographic performance of the cured film can be further improved. By the atomization pressure of 300 g/cm ² or more, the curable composition can be more efficiently sprayed from the nozzle.

The hydraulic pressure refers to the pressure applied to the curable composition in order to supply the curable composition to the nozzle. The hydraulic pressure in the first step is preferably from 10 g/cm ² to 32 g/cm ² , more preferably from 10 g/cm ² to 30 g/cm ² , even more preferably from 15 g/cm ² to 28 g/cm ^{2 .} Particularly preferred is 18 g/cm ² to 25 g/cm ² . When the hydraulic pressure is 32 g/cm ² or less, the drooping of the droplets can be suppressed, so that the surface roughness of the first coating film can be suppressed, so that the surface roughness Ra of the first film can be made small. When the hydraulic pressure is 10 g/cm ² or more, the landing size can be increased, so that the lithographic performance of the cured film can be further improved.

As described above, the first coating film is cured by the curing treatment described later to become the "first film". The film thickness T1 of the first film is preferably from 1 μm to 5 μm, more preferably from 2.2 μm to 4.0 μm, still more preferably from 2.5 μm to 3.8 μm. When the film thickness T1 is 2.2 μm or more, there is an advantage that the occurrence of pinholes can be further suppressed. Since the film thickness T1 is 4.0 μm or less, there is an advantage that the device can be made low-profile. Here, the film thickness T1 is an average thickness, and is a value obtained by measuring the thickness of any five or more places of the first film and arithmetically averaging these. In addition, the film thickness of the first film refers to the thickness of the film obtained by curing only the first coating film obtained by performing the first step without performing the second step. The film thickness can be adjusted by the number of times the coating film is repeatedly applied, the moving speed of the nozzle, the pitch, and the like.

The surface roughness Ra of the first film is preferably from 0.01 μm to 0.6 μm, more preferably from 0.01 μm to 0.5 μm, still more preferably from 0.01 μm to 0.2 μm, particularly preferably from 0.01 μm to 0.1 μm. When the surface roughness Ra of the first film is within the above range, there is an advantage that the lithography performance is further improved. The surface roughness Ra of the first film can be measured using a surface atomic force microscope (Nanoscope 4A, manufactured by Veeco, Japan). In addition, the surface roughness Ra of the first film is the surface roughness Ra of the film obtained by curing only the first coating film obtained by performing the first step without performing the second step.

The first step may also include a treatment of drying the droplets adhering to the coated surface after spray coating the curable composition. The method of the drying treatment is not particularly limited, and examples thereof include a method of heating the coated surface (substrate) by a hot plate or the like. Such drying treatment is sometimes referred to as a prebaking treatment. The conditions of the drying treatment are not particularly limited, and are usually from 80 ° C to 120 ° C for 1 minute to 5 minutes in the case of a hot plate, and from 80 ° C to 120 ° C for 0.5 hour to 2 hours in the case of an oven.

(Second Step) The second step is a step of spray-coating the curable composition so that the landing size becomes D2 to form a second coating film. The second step can be carried out before the first step, or after the first step, and from the viewpoint of further exerting the effects of the present invention, it is preferably carried out after the first step.

The example of Fig. 1B shows the aspect in which the second step is performed after the first step. Specifically, when the curable composition is ejected from the nozzle 210 of the spray device, the curable composition flies into a plurality of droplets, and the plurality of droplets land on the surface of the first coating film 120A (coated) Cloth). The droplets adhering to the surface of the first coating film 120A are dried to become the pellets 120b. A plurality of the granular materials 120b are aggregated to form a second coating film 120B.

The landing size D2 is preferably from 1 μm to 30 μm, more preferably from 1 μm to 20 μm, and still more preferably from 1 μm to 10 μm. By the landing size D2 being within the above range, the reflectance of the cured film can be further lowered. The landing size D2 here is obtained by observing the granular material attached to the glass substrate by an optical microscope, and assuming that the granular material is a circle (a circular approximate diameter), the granular material at 500 is measured and subjected to Arithmetic average.

In the second step, the nozzle height L2 (distance L2) is preferably 8 cm or more, more preferably more than 10 cm, and further preferably 12 cm or more, particularly preferably 13 cm or more. Further, the upper limit is preferably 20 cm or less, more preferably 15 cm or less. By setting the nozzle height L2 to more than 10 cm, the volatilization of the volatile components during the flight can be promoted, so that the landing size can be further reduced. Thereby, the reflectance of the cured film can be further reduced. Further, by setting the nozzle height L2 to 15 cm or less, there is an effect that the number of repetitions of coating for obtaining a desired film thickness can be reduced, and the step time can be shortened. In FIG. 1B, the nozzle height L2 (distance L2) means the distance between the tip end of the nozzle 210 of the spray device and the surface of the first coating film 120A.

The atomization pressure in the second step is preferably from 300 g/cm ² to 500 g/cm ² , more preferably from 400 g/cm ² to 500 g/cm ² , and further preferably from 410 g/cm ² to 450 g/ Cm ² . When the atomization pressure is 450 g/cm ² or less, the liquid droplets are completely dried from the nozzles until they land, and can be suppressed in the coating machine (in the spray device, the droplets are attached to the coated surface). The form of the particles is suspended, so that the adhesion of the particles to the coated surface can be suppressed. Thereby, it is possible to suppress contamination of other devices by the particles, or to suppress adhesion of the particles to the back surface of the substrate to cause contamination. Further, when the atomization pressure is 300 g/cm ² or more, the amount of gas mixed in when the curable composition is ejected from the nozzle can be increased, so that the droplets are easily dried. Thereby, since the landing size becomes small, the reflectance of the cured film can be further reduced.

The hydraulic pressure in the second step is preferably from 10 g/cm ² to 30 g/cm ² , more preferably from 15 g/cm ² to 25 g/cm ² , and still more preferably from 17 g/cm ² to 24 g/cm ^{2 .} . The landing size can be further reduced by a hydraulic pressure of 25 g/cm ² or less. In addition, when the hydraulic pressure is 10 g/cm ² or more, it is possible to suppress the phenomenon that the curable composition in the nozzle is dried and clogging occurs.

As described above, the second coating film is cured by the curing treatment described later to become the "second film". The film thickness T2 of the second film is preferably 0.1 μm to 2 μm, more preferably 0.1 μm to 1.5 μm, still more preferably 0.1 μm to 1.2 μm. The reflectance can be further reduced by the film thickness T2 being within the above range. Here, the film thickness T2 is an average thickness, and is a value obtained by measuring the thickness of any five or more places of the second film and arithmetically averaging these. In addition, the film thickness of the second film refers to the thickness of the film obtained by curing only the second coating film obtained by performing the second step without performing the first step.

In the case where a cured film is obtained by the method for producing a cured film of the present invention, the film thickness of the obtained cured film is preferably 2.0 μm to 8.0 μm, more preferably 2.5 μm to 6.0 μm, and still more preferably 3.0 μm to 5.0. Mm.

The surface roughness Ra of the second film is preferably from 0.1 μm to 2.0 μm, more preferably from 0.1 μm to 1.5 μm, still more preferably from 0.1 μm to 1.0 μm. When the surface roughness Ra of the second film is within the above range, the reflectance of the cured film is further improved. The surface roughness Ra of the second film can be measured by the same method as the first film. In addition, the surface roughness Ra of the second film refers to the surface roughness Ra of the film obtained by curing only the second coating film obtained by performing the second step without performing the first step.

When the cured film is obtained by the method for producing a cured film of the present invention, the surface roughness Ra of the cured film obtained (the surface roughness Ra of the second film opposite to the first film) is preferably 0.1 μm. ～1.2 μm, more preferably 0.1 μm to 0.8 μm, further preferably 0.1 μm to 0.5 μm, particularly preferably 0.1 μm to 0.3 μm.

The second step may also include a treatment (prebaking treatment) of drying the droplets adhering to the coated surface after spray coating the curable composition. The method and conditions of the drying treatment are the same as those of the first step, and thus the description thereof will be omitted.

(Relationship between spray coating conditions in the first step and the second step, and relationship between the first film and the second film) The landing size D1 and the landing size D2 satisfy the relationship of D1 > D2. The ratio D1/D2 of the landing size D1 to the landing size D2 is 5 to 150, preferably 10 to 140, more preferably 10 to 100, and still more preferably 15 to 85. When the ratio D1/D2 is within the above range, the lithographic performance and reflectance of the cured film are excellent. On the other hand, if the ratio D1/D2 is less than 5, there is a problem that the lithographic performance of the cured film is lowered or the reflectance is too high. Further, when the ratio D1/D2 exceeds 150, the lithographic performance of the cured film is lowered.

The nozzle height L1 (distance L1) in the first step is preferably smaller than the nozzle height L2 (distance L2) in the second step. Thereby, it is easy to control the landing size. The ratio T2/T1 of the film thickness T1 of the first film to the film thickness T2 of the second film is preferably 0.2 to 1.0, more preferably 0.2 to 0.8, still more preferably 0.2 to 0.75. By being in the above range than T2/T1, it is possible to make the lithographic performance and reflectance of the cured film more excellent. The surface roughness Ra of the first film is preferably smaller than the surface roughness Ra of the second film. Thereby, there is an advantage that the lithographic performance of the cured film can be suppressed from being lowered or the reflectance can be suppressed from being increased.

(Step of Forming Cured Film) The method for producing a cured film of the present invention includes a step of forming a cured film by performing a curing treatment (cured film forming step). Thereby, the first coating film is cured to become the first film, and the second coating film is cured to become the second film. In this manner, a cured film having the first film and the second film was obtained. The step of forming the cured film may be carried out at each sequence after the first step and after the second step, or may be performed uniformly after the completion of the two steps of the first step and the second step. The hardening treatment is preferably at least one of photohardening treatment and thermosetting treatment, and is preferably a photocuring treatment (particularly, a curing treatment by irradiation with actinic rays or radiation) in terms of ease of pattern formation. The conditions of the hardening treatment are not particularly limited, and may be carried out according to known conditions.

<Method for Producing Patterned Cured Film> The cured film of the present invention may be a so-called patterned cured film formed by patterning. The method of forming the patterned cured film is, for example, a state in which the development step is performed after the exposure treatment in the form of a pattern (hereinafter also referred to as "exposure step") in the step of forming the cured film. Specifically, after the two steps of the first step and the second step are completed, the coating film (the first coating film and the second coating film) formed on the substrate is irradiated with actinic rays or radiation. In the exposure step, a cured film which is exposed in a pattern is formed, and then a development step of performing alkali development on the cured film which is exposed in a pattern is performed. Hereinafter, each step in the above description will be described. In addition, since the first step and the second step are as described above, the description thereof will be omitted.

(Exposure step) In the exposure step, the coating film (the first coating film and the second coating film) obtained as described above is irradiated with actinic rays or radiation through the mask to expose the light, thereby irradiating only the light. The coated film is partially hardened. Thereby, a portion where the light is not irradiated and a portion which is exposed in a pattern (that is, a cured film which is exposed in a pattern) is formed. The exposure is preferably performed by irradiation of radiation. As the radiation which can be used for exposure, in particular, ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably used, and the light source is preferably a high-pressure mercury lamp. The irradiation intensity is preferably from 5 mJ/cm ² to 1500 mJ/cm ² , more preferably from 10 mJ/cm ² to 1000 mJ/cm ² .

(Developing Step) A developing step (developing treatment) is performed after the exposure step, and the unexposed portion of the light in the exposure step is eluted into the developing solution. Thereby, only the portion where the light hardening is performed remains. Thus, a patterned cured film was obtained. As the developer, it is preferred to use an organic alkaline developer. The development temperature is usually from 20 ° C to 30 ° C, and the development time is from 20 seconds to 90 seconds. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, and aqueous ammonia and ethyl which are organic alkaline developing solutions. Amine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, gall The basic compound such as a base, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene has a concentration of 0.001% by mass to 10% by mass, preferably 0.005% by mass. An alkaline aqueous solution obtained by dissolving in a form of 0.5% by mass. A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution in an appropriate amount. Further, in the case of using a developer containing such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

Further, after the above steps, a step of further hardening by heating and exposing the formed patterned cured film may be carried out as needed.

[Preferred Aspect of Cured Film] Next, one of preferred embodiments of the cured film of the present invention will be described. The cured film of the present embodiment is a cured film obtained by using the curable composition and formed on a substrate, and is oriented from the first surface of the cured film located on the substrate side to the first surface The void ratio at the position where the thickness of the cured film is 10% relative to the second surface of the cured film is A1, and the thickness of the cured film is from the second surface toward the first surface. When the void ratio at the position of 10% is A2, the relationship between A1 and A2 satisfies A1 < A2. Hereinafter, in the present invention, the cured film of the present embodiment is also simply referred to as "cured film".

The porosity A1 and the porosity A2 in the cured film satisfy the above relationship, and the cured film is excellent in reflectance and excellent in lithography performance. Although the details of this reason are not clear, the following reasons are presumed. For example, when the curable composition is sprayed from the nozzle of the spray device, the curable composition flies into a plurality of droplets and flies on the coated surface. The droplets that have landed on the surface to be coated are dried to form a granular material containing solid components contained in the droplets. A plurality of the granules are aggregated, whereby a film (coating film) is formed, and a cured film is obtained by drying the coating film. At this time, a gap of a material which does not constitute a cured film is formed in the cured film. In the present invention, the gap is referred to as a "void", and a more detailed definition of the gap will be described later.

In the cured film of the present embodiment, the void ratio A1 at a position close to the first surface of the cured film on the substrate side is smaller than the void ratio A2 at a position facing the first surface. In other words, it can be said that the gap on the first surface side of the substrate side is small as compared with the second surface side of the surface of the cured film. Then, since the first surface and the region in the vicinity thereof are films having a small number of pinholes, the defects of the pattern shape of the cured film are suppressed in addition to the occurrence of pinholes in the cured film. In addition, since the permeability of the developing solution or the like is different between the periphery of the gap and the other portions, it is estimated that the development in the vicinity of the interface with the substrate is uniformly performed when the number of voids is small. On the other hand, since the refractive index of the voids in the voids of the second surface which is the surface on the surface side and the vicinity thereof is different, the reflectance of the cured film can be lowered, and the penetration of the developer can be promoted. Defects in the pattern shape of the cured film, generation of pinholes, and the like.

In the cured film of the present embodiment, the ratio A1/A2 of the void ratio A1 to the void ratio A2 is preferably 0.00001 or more and less than 0.9, and more preferably 0.0001 or more, from the viewpoint of obtaining the desired effect of the present application. And less than 0.8. From the viewpoint of more remarkably obtaining the desired effect of the present application, it is particularly preferably 0.0001 or more and less than 0.7.

In the cured film of the present embodiment, the void ratio A1 is preferably 3.5% or less, more preferably 0.001% or more and less than 3%, further preferably 0.01% or more and less than 3%, particularly preferably 0.1% or more and less than 3%. By the void ratio A1 being in this range, the desired effect of the present application can be remarkably obtained. In addition, since the void ratio A1 is 0.001% or more and development is promoted, it is easy to further suppress the defects of the pattern shape of the cured film, and if it is less than 3%, the voids are small. Therefore, it is easy to further suppress the pattern shape of the cured film as described above. Defects or pinholes, etc. Furthermore, the method of measuring the void ratio will be described later.

In the cured film of the present embodiment, the porosity A2 is preferably 0.05% to 35%, more preferably 0.1% or more and less than 30%, still more preferably 1% to 20%, particularly preferably 2% to 10%. . By the void ratio A2 being the above range, the desired effect of the present application can be remarkably obtained. In the above range, the refractive index inside and outside the void is different. Therefore, in addition to further reducing the reflectance (particularly, specular reflected light), the void near the surface (second surface) of the cured film is opened by the development process to promote the opening. Since the surface of the cured film is formed into a concavo-convex shape and the light is diffused, the reflectance can be further reduced while maintaining other effects. In addition, when the void ratio is 1% or more, development is more likely to be promoted, and if it is less than 30%, it is easy to further form a fine pattern shape, and it is easy to further suppress the defects of the pattern shape of the cured film. Furthermore, the method of measuring the void ratio will be described later.

The preferred range and measurement method of the surface roughness Ra of the cured film of the present embodiment are the same as the surface roughness Ra of the cured film described in the section of the method for producing a cured film.

The cured film of the present embodiment preferably has at least two or more layers. The cured film of the present embodiment is not limited thereto, and is preferably manufactured by the method described in the section of the method for producing a cured film. In this case, the region (layer) including the first surface and including the position at which the porosity A1 is formed corresponds to the first film. Further, a region (layer) including the second surface and including the position at which the porosity A2 is formed corresponds to the second film.

(Void Ratio) The measurement method of each of the void ratios (A1 and A2) is as follows. The void ratio of the curable composition layer is measured by an image analysis method (for example, a cross-sectional image by a scanning electron microscope) based on a photographic image taken on a cross section of the exposed portion (hardened portion) of the cured film . The obtained cross-sectional image can be image analyzed as needed. Specifically, based on the cross-sectional image of the cured film to be observed, a region other than the cured film (that is, a region in the cured film that is not surrounded by the cured film) is set as a void, and the entire area of the void (number of pixels) is used. The void ratio (%) was determined by dividing the area of the entire cured film (the number of pixels). More specifically, the porosity A1 is calculated based on a cross-sectional image in a region in which the thickness of the cured film is 10% ± 5% from the first surface toward the second surface. In addition, the porosity A2 is calculated based on a cross-sectional image in a region in which the thickness of the cured film is 10%±5% from the second surface toward the first surface. The magnification of the photo image is not particularly limited as long as it is easily discriminated, and is preferably in the range of 3,000 to 20,000.

[Infrared Light Cut Filter with Light-Shielding Film, Solid-State Imaging Device] When a black pigment is used as a coloring agent, the cured film can be preferably used as a so-called light-shielding film. Further, such a light shielding film can be preferably applied to a solid-state image pickup device. Hereinafter, a first embodiment of a solid-state imaging device having the light-shielding film of the present invention will be described in detail. As shown in FIGS. 2 and 3, the solid-state imaging device 2 includes a CMOS sensor 3 as a solid-state imaging device, a circuit board 4 on which the CMOS sensor 3 is mounted, and a ceramic ceramic in which the circuit board 4 is held. Substrate 5. Further, the solid-state imaging device 2 includes an IR cut filter 6 that is held by the ceramic substrate 5 and that cuts off infrared light (IR) of the CMOS sensor 3, and an imaging lens 7 that is attached to the imaging lens 7. The held lens holder 8 and the holding cylinder 9 that holds the lens holder 8 in a freely movable manner. In addition, a CCD sensor or an organic CMOS sensor may be provided instead of the CMOS sensor 3. The ceramic substrate 5 is formed with an opening 5a into which the CMOS sensor 3 is inserted, and is frame-shaped and surrounds the side surface of the CMOS sensor 3. In this state, the circuit board 4 on which the CMOS sensor 3 is mounted is fixed to the ceramic substrate 5 by an adhesive (for example, an epoxy-based adhesive, the same applies hereinafter). Various circuit patterns are formed on the circuit board 4.

The IR cut filter 6 is formed with a reflection film that reflects infrared rays on the plate glass or the blue glass, and the surface on which the reflection film is formed is the incident surface 6a. The IR cut filter 6 is formed to have a size larger than the opening 5a, and is fixed to the ceramic substrate 5 by an adhesive so as to cover the opening 5a. A CMOS sensor 3 is disposed behind the photographic lens 7 (downward in FIGS. 3 and 4), and an IR cut filter 6 is disposed between the photographic lens 7 and the CMOS sensor 3. The light of the subject is incident on the light receiving surface of the CMOS sensor 3 through the photographic lens 7 and the IR cut filter 6. At this time, the infrared ray is cut off by the IR cut filter 6. The circuit board 4 is connected to a control unit provided in an electronic device (for example, a digital camera) on which the solid-state imaging device 2 is mounted, and supplies electric power from the electronic device to the solid-state imaging device 2 . The CMOS sensor 3 two-dimensionally arranges a plurality of color pixels on the light receiving surface, and each color pixel photoelectrically converts the incident light and accumulates the generated signal charges.

As shown in FIG. 3 and FIG. 4, the light shielding film (light shielding layer) 11 is disposed over the entire circumference of the incident surface 6a of the IR cut filter 6, thereby forming an infrared cut filter with a light shielding film. . The reflected light R1 emitted from the photographic lens 7 and reflected by the front surface (the upper surface in FIGS. 3 and 4) of the ceramic substrate 5 is repeatedly reflected or refracted in the device and is incident on the CMOS sensor 3 or When the reflected light R2 emitted from the photographic lens 7 and reflected by the inner wall surface of the lens holder 8 is incident on the CMOS sensor 3, it causes a flare in the photographic image. The light shielding film 11 shields harmful light such as the reflected light R1 and the reflected light R2 toward the CMOS sensor 3 from light. The light shielding film 11 corresponds to the cured film. Further, the thickness of the light shielding film 11 is exaggerated in FIGS. 3 and 4.

FIG. 5 shows a solid-state imaging device 20 according to the second embodiment. The same components as those of the solid-state imaging device according to the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. The solid-state imaging device 20 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, an imaging lens 7, a lens holder 8, and a holding cylinder 9. The light shielding film (light shielding layer) 21 is formed on the side end surface of the IR cut filter 6 over the entire circumference. The reflected light R3 emitted from the photographic lens 7 and reflected by the front surface of the ceramic substrate 5 is repeatedly reflected or refracted in the apparatus and is incident on the CMOS sensor 3, causing a flare in the photographic image. The light shielding film 21 shields harmful light such as the reflected light R3 toward the CMOS sensor 3 from light.

Fig. 6 shows a solid-state imaging device 30 according to a third embodiment. The same components as those of the solid-state imaging device according to the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. The solid-state imaging device 30 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, an imaging lens 7, a lens holder 8, and a holding cylinder 9. The light shielding film (light shielding layer) 31 is formed over the entire circumference of the end surface and the side end surface of the incident surface 6a of the IR cut filter 6. In other words, the solid-state imaging device in which the first embodiment and the second embodiment are combined is used. This embodiment has higher light-shielding performance than the first embodiment and the second embodiment, and thus the occurrence of flare is reliably suppressed.

Fig. 7 shows a solid-state imaging device 40 according to the fourth embodiment. The same components as those of the solid-state imaging device according to the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. The solid-state imaging device 40 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, an imaging lens 7, a lens holder 8, and a holding cylinder 9. The light shielding film (light shielding layer) 31 is formed over the entire circumference of the end surface and the side end surface of the incident surface 6a of the IR cut filter 6. Further, a light shielding film (light shielding layer) 41 is formed on the inner wall surface of the ceramic substrate 5. When the reflected light reflected from the inner wall surface of the ceramic substrate 5 through the IR cut filter 6 and incident on the CMOS sensor 3 is incident on the CMOS sensor 3, it causes a flare in the captured image. Since the light shielding film 41 has higher light blocking performance than the inner wall surface of the ceramic substrate 5, the generation of the light spot is surely suppressed.

[Color Filter] The cured film of the present invention can also be used in a color filter.

The color filter can be preferably used for solid-state imaging elements such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), and is particularly suitable for a high resolution CCD or CMOS of more than one million pixels. The color filter can be used, for example, between a light receiving portion that constitutes each pixel of the CCD or CMOS and a microlens for collecting light.

Further, the color filter can be preferably used for an organic electroluminescence (Electroluminescence) element. As the organic EL element, a white organic EL element is preferable. The organic EL element is preferably a series structure. The tandem structure of the organic EL device is described in the "Top of the development of organic EL technology - high brightness, high precision, long life, and proprietary technology set -" (Technical Information Association, pp. 326-328, 2008), etc. The tantalum structure of the organic EL element is, for example, a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transparency on one surface of the substrate. The lower electrode is preferably made of a material having a sufficient reflectance in a wavelength region of visible light. The organic EL layer includes a plurality of light-emitting layers, and preferably has a laminated structure (series structure) in which the plurality of light-emitting layers are laminated. The organic EL layer may include, for example, a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer among the plurality of light-emitting layers. Moreover, it is preferable to have a plurality of light-emitting layers and a plurality of light-emitting auxiliary layers for causing the light-emitting layers to emit light. The organic EL layer can be, for example, a laminated structure in which a light-emitting layer and a light-emitting auxiliary layer are alternately laminated. The organic EL element having the organic EL layer having such a structure emits white light. In this case, the spectrum of the white light emitted from the organic EL element is preferably strong in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). The maximum illuminating peak. In addition to the luminescence peaks, it is more preferable to have the maximum luminescence peak in the red region (650 nm - 700 nm). By combining an organic EL element (white organic EL element) that emits white light with the color filter of the present invention, spectroscopic excellent in color reproducibility is obtained, and a clearer image or image can be displayed.

The film thickness of the colored pattern (colored pixel) in the color filter is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more. Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more.

[Image Display Device] The cured film (color filter, light-shielding film, etc.) of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device.

The definition of the display device or the details of each display device is described, for example, in "Electronic display devices (sasaki Sasaki, Industrial Research Association (share) issued in 1990)", "Display devices (Ibuki Shunzhang, Industrial Books) ) issued in 1989) and so on. In addition, the liquid crystal display device is described in, for example, "Next-Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Industrial Research Association, Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, a plurality of types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

The color filter of the present invention can also be used in a liquid crystal display device of a Thin Film Transistor (TFT) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". Furthermore, the present invention can also be applied to a liquid crystal display device having an enlarged viewing angle such as a transverse electric field driving method such as In Plane Switching (IPS) or a pixel division method such as multi-domain vertical alignment (MVA). , or Super-Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), on-chip spacer (OCS), fringe field switching (fringe field switching, FFS) and Reflective Optically Compensated Bend (R-OCB). In addition, the color filter of the present invention is also available in a bright and high-definition Color-filter On Array (COA) mode. In the liquid crystal display device of the COA type, in addition to the usual required characteristics as described above, the required characteristics of the color filter may require the characteristics of the interlayer insulating film, that is, the low dielectric constant and the peeling resistance. Liquid. Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer. These image display methods are described, for example, in "EL, Plasma Display Panel (PDP), Liquid Crystal Display (LCD) Display - Technology and Market Trends - (Dongli Research Center) (Toray Research Center, Research and Research Department, issued in 2001), page 43 et al.

The liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. For example, the "94 liquid crystal display peripheral materials - chemicals market (Ichishima Kentaro, CMC (share), issued in 1994)", "2003 liquid crystal related market status and future prospects (volume) (Former Liangji, Fuji Kamelai Institute (share), issued in 2003). The backlight is recorded in the "SID (Society for Information Display) Meeting Digest" 1380 (2005) (A. Konno et al.) or the "Monthly Display" 2005. On pages 18 to 24 of the December issue (Island Kang Yu), pages 25 to 30 of this document (Yamamu Longming), etc. [Examples]

Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to this.

<Preparation of titanium black (A-1)> Weighing 120 g of titanium oxide TTO-51N (trade name, manufactured by Ishihara Sangyo Co., Ltd.) having a BET specific surface area of 110 m ² /g, and a BET surface area of 300 m ² / g of 25 g Antimony oxide particles AEROSIL 300 (registered trademark) 300/30 (manufactured by Evonik), and 100 g dispersant Disperbyk 190 (trade name, BYK) Chemical (manufactured by BYK Chemie), adding 71 g of ion-exchanged water, using MAZERSTAR KK-400W manufactured by KURABO, at a revolution of 1360 rpm and a rotation number of 1047 rpm The treatment was carried out for 30 minutes, whereby a homogeneous aqueous mixture solution was obtained. The aqueous solution was filled in a quartz vessel, and heated to 920 ° C in an oxygen atmosphere using a rotary kiln (manufactured by Benshan Co., Ltd.), and the atmosphere was replaced with nitrogen at a temperature of 100 mL/min. Ammonia gas was passed through for 5 hours to carry out a nitrogen reduction treatment. The powder recovered after completion of the mortar was pulverized to obtain titanium black (A-1) containing a Si atom and having a powder specific surface area of 85 m ² /g [dispersion containing titanium black particles and Si atoms] .

<Preparation of Pigment Dispersion> A component shown in the following composition 1 was mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion a. In addition, the dispersing agent (polymer compound (G1), see the following formula) described below is synthesized by the description of JP-A-2013-249417. Further, the polymer compound (G1) had a weight average molecular weight of 30,000, an acid value of 60 mgKOH/g, and an atomic number of the graft chain (excluding a hydrogen atom) of 117. (Composition 1) ・The titanium black A-1 ・・・25.0 parts by mass ・The polymer compound (G1) propylene glycol monomethyl ether acetate 20% by mass solution ・・・37.5 parts by mass ・Propylene glycol monomethyl ether acetate Ester (PGMEA) (solvent), 10.5 parts by mass, butyl acetate (solvent), and 27.0 parts by mass of NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. The substance a was subjected to dispersion treatment to obtain a pigment dispersion.

[化12]

(Dispersion conditions) ・Bead size: f0.05 mm (YTZ manufactured by NIKKATO) ・Bead filling rate: 65 vol% ・Milling machine peripheral speed: 10 m/sec ・Separator speed: 13 m /s ・The amount of the mixed solution for the dispersion treatment: 15 kg ・Circulating flow rate (pump supply amount): 90 kg/hour ・Processing liquid temperature: 19 °C to 21 °C ・Cooling water: water ・Processing time: 22 hours

<Curable Composition 1> The components shown below were mixed and stirred to obtain a curable composition.・Additional solvent: PGMEA ・・・30.8 parts by mass ・Additional solvent: Ethyl-3-ethoxypropionate ・・・18 parts by mass ・Binder polymer: Acrybase FF-187 ( Manufactured by Fujikura Kasei) 40% PGMEA solution ・・・7.4 parts by mass ・Polymerized compound: DPHA (KAYARAD, manufactured by Nippon Kayaku Co., Ltd.) ・・・1.8 parts by mass ・Polymerization inhibitor: p-methoxyphenol・・・ 0.001 parts by mass ・Interacting agent: Surfactant A of the following structure: ・・・0.1 parts by mass ・Polymerization initiator: IRGACURE OXE-02 (made by BASF) ・・・1.6 parts by mass Dispersion: The pigment dispersion parts by mass · 40.3

[Chemistry 13]

<Production of cured film for evaluation of lithographic performance> Using a spray coater (product name "DC110", manufactured by Sanming Co., Ltd.), the conditions of the first table (formation conditions of the first coating film) will be described below. The curable composition was sprayed onto the surface (coated surface) of a glass substrate of 8 inches to form a coating film. The obtained coating film was heated (prebaking treatment) for 2 hours in an oven at 100 ° C to form a first coating film (first step). Then, using the spray device, the curable composition was sprayed onto the surface (coated surface) of the first coating film under the conditions of the first table (formation conditions of the second coating film) to form a coating film. The obtained coating film was heated (prebaked) in an oven at 100 ° C for 2 hours to form a second coating film (second step). After that, a proximity exposure device EVG610 (manufactured by EV Group Japan) was used to intervene a mask having a line width of 300 μm (300 μm in width and 4 mm in length) to become an irradiation force of 50 mW/cm ² and exposure. The first coating film and the second coating film formed on the substrate were irradiated with light (exposure) in a manner of 600 mJ/cm ² (exposure step). Thus, a cured film (second film/first film/glass substrate) in which the first film and the second film are laminated in the glass substrate is obtained. After the irradiation (exposure), the developing solution CD2060 (trade name, manufactured by FUJIFILM Co., Ltd., tetramethyl ammonium hydroxide (TMAH) concentration: 0.26 mass%) was used for 20 seconds at 23 ° C. Development using a straight nozzle (development step). Then, ultrapure water (DIW) was used as the eluent for washing (rinsing treatment). Finally, a heat treatment (post-baking step) was carried out at 230 ° C for 1 hour using a clean oven CLH-21 CDH (manufactured by Koyo Thermo Co., Ltd.). In this manner, the cured films of the examples and the comparative examples in which the predetermined patterns were formed on the glass substrate were obtained.

In addition, regarding the formation conditions of the first coating film and the second coating film, the details of the items listed in the first table are as follows. Here, the spray coater (product name "DC110", manufactured by Sanming Co., Ltd.) performs the operation shown in FIG. 8 to form a film P of a predetermined size on the substrate 100. Specifically, the coating film P having a predetermined size is formed by sequentially repeating the first operation and the second operation, wherein the first operation is performed by spraying the curable composition from the nozzle 210 of the spray device toward the first direction X. The second movement is such that the nozzle moves in the second direction Y orthogonal to the first direction X. In addition, by repeating the operation of forming the coating film P of such a predetermined size, the coating film P of a predetermined size is laminated (that is, the coating film P is repeatedly applied) to form a first coating film (or a second coating film). [Atomization pressure (g/cm ² ): pressure and hydraulic pressure (g/cm ² ) applied to the curable composition in order to eject the curable composition from the nozzle of the spray device: in order to supply the curable composition to the nozzle Pressure to the curable composition ・Nozzle opening scale: An index indicating the opening diameter of the nozzle. The larger the value, the larger the opening diameter of the nozzle.・Nozzle height (cm): Distance from the tip of the nozzle to the surface to be coated and the speed (mm/s): Movement speed and pitch (mm) of the nozzle during the first operation: The movement distance of the nozzle for each of the second movements・Number of times: The number of executions of the first operation to obtain a coating film of a predetermined size ・Repeat: The number of times the coating film of a predetermined size is repeatedly applied

<The lithography performance> (linearity) The optical microscope (product name "OLS4500", manufactured by Olympus Co., Ltd.) was used to observe the examples and comparative examples in which the predetermined pattern was formed, under the conditions of a magnification of 50 times. The cured film was evaluated for linearity by the following evaluation criteria. The evaluation is "B" and is considered qualified. The evaluation results are shown in the second table. "A": A straight line development of the edge portion of the pattern (the boundary portion between the exposed portion and the unexposed portion). "B": The edge portion of the pattern becomes a straight line. "C": The edge portion of the pattern cannot be straight due to poor development. (Development Residue) The cured film of the examples and the comparative examples in which the predetermined patterns were formed was observed by an optical microscope (product name "OLS 4500", manufactured by Olympus Co., Ltd.) under the conditions of a magnification of 50 times. The development residue was evaluated by the following evaluation criteria. The evaluation is "B" and is considered qualified. The evaluation results are shown in the second table. "A": A trace of the residue as a residue was hardly observed in the developing portion, and a good pattern was formed. "B": A trace of the residue as a residue was slightly observed in the developing unit, and a substantially good pattern was formed. "C": A large amount of landing marks as residues were confirmed in the developing unit, and the analysis was poor.

<Pinholes> The curable composition was sprayed to 8 以 under the conditions of the first table (formation conditions of the first coating film) using a spray coater (product name "DC111", manufactured by Sanming Co., Ltd.). A coating film is obtained on the surface (coated surface) of the glass substrate. The obtained coating film was heated at 200 ° C for 2 hours (prebaking treatment) to obtain a first coating film. Then, using the spray device, the curable composition was sprayed onto the surface (coated surface) of the first coating film under the conditions of the first table (formation conditions of the second coating film) to obtain a coating film. The obtained coating film was heated at 200 ° C for 2 hours (prebaking treatment), and a sample for pinhole evaluation of the examples and the comparative examples in which the second coating film was laminated on the first coating film was obtained. With respect to each sample for evaluation of the pinholes obtained as described above, the number of bright portions, that is, the number of pinholes, in any of the 20 fields of view of the cured film was counted by an optical microscope observation using a transmitted light at a magnification of 50 times. Evaluation was performed by the following criteria. The evaluation is "B" or more and is considered qualified. The evaluation results are shown in the second table. "AA": 0 "A": 1 or more and 2 or less "B": 3 or more and 10 or less "C": More than 10

<Reflectance> The samples for reflectance measurement of the examples and the comparative examples were produced in the same manner as the evaluation of the pinholes. With respect to the samples for reflectance measurement of the obtained examples and comparative examples, the positive reflectance at an incident angle of 5° was measured in the wavelength range of 400 nm to 1200 nm. A spectroscope UV4100 manufactured by Hitachi High-technologies was used for the measurement. The maximum value in the obtained spectrum is set as the reflectance. The reflectance is less than 3% and is considered to be acceptable, more preferably less than 2%, and particularly preferably less than 1%. The evaluation results are shown in the second table.

<Measurement of film thickness> (film thickness of the first film) The following conditions of the first table (formation conditions of the first coating film) will be used in a spray coater (product name "DC111", manufactured by Sanming Co., Ltd.). The curable composition was sprayed onto the surface (coated surface) of a glass substrate of 8 inches to form a coating film. The obtained coating film was heated at 200 ° C for 2 hours (prebaking treatment) to obtain a first coating film. After that, the proximity coating apparatus EVG610 (manufactured by EV Group Japan) was used to irradiate the first coating film formed on the substrate so as to have an irradiation force of 50 mW/cm ² and an exposure amount of 600 mJ/cm ² . Light (exposure) (exposure step). Thus, the first film was formed on the glass substrate. The first film obtained in the manner described above was subjected to physical film thickness measurement using a Decktak XT (manufactured by Bruker). (Thickness of the second film) The curable composition was formed by the following conditions of the first table (formation conditions of the second coating film) using a spray coater (product name "DC111", manufactured by Sanming Co., Ltd.). The surface of the glass substrate (coated surface) of 8 Å was sprayed to form a coating film. The obtained coating film was heated at 200 ° C for 2 hours (prebaking treatment) to obtain a second coating film. After that, the proximity coating apparatus EVG610 (manufactured by EV Group Japan) was used to irradiate the second coating film formed on the substrate so as to have an illuminance of 50 mW/cm ² and an exposure amount of 600 mJ/cm ² . (Perform exposure) (exposure step). Thus, the second film was formed on the glass substrate. The second film obtained in the manner described above was subjected to physical film thickness measurement using a Decktak XT (manufactured by Bruker). (The total film thickness of the first film and the second film) The spray coating machine (product name "DC110", manufactured by Sanming Co., Ltd.) was used, and the conditions of the first table (formation conditions of the first coating film) were used. The curable composition was sprayed onto the surface (coated surface) of a glass substrate of 8 inches to form a coating film. The obtained coating film was heated (prebaking treatment) for 2 hours in an oven at 100 ° C to form a first coating film (first step). Then, using the spray device, the curable composition was sprayed onto the surface (coated surface) of the first coating film under the conditions of the first table (formation conditions of the second coating film) to form a coating film. The obtained coating film was heated (prebaking treatment) for 2 hours using an oven at 100 ° C to form a second coating film (second step). Then, using the proximity exposure apparatus EVG610 (manufactured by EV Group Japan), the first coating film and the first coating film formed on the substrate are illuminating at 50 mW/cm ² and having an exposure amount of 600 mJ/cm ² . 2 The coating film is irradiated with light (exposure) (exposure step). Thus, a cured film (second film/first film/glass substrate) in which the first film and the second film are laminated in the glass substrate is obtained. The cured film (the first film + the second film) obtained as described above was subjected to physical film thickness measurement using a Decktak XT (manufactured by Bruker). Further, each film thickness is an average thickness, and is a value obtained by measuring the thickness of any five places of each film and arithmetically averaging these. The film thickness of each of the first film and the second film is shown in the first table, and the film thickness of the cured film (first film + second film) is shown in the second table.

In the formation conditions of the first coating film shown in the first table, the "number of times" and "repetition" are set to 1, respectively, and the conditions for forming the first coating film shown in the first table are the same. In the manner of using a spray coater (product name "DC110", manufactured by Sanming Co., Ltd.), the curable composition was sprayed onto the surface (coated surface) of a glass substrate of 8 inches to form a coating film. The obtained coating film was heated (prebaking treatment) for 2 hours using an oven at 100 ° C to obtain a sample for measurement of the landing size D1. Five lenses were taken for the measurement sample by an optical microscope at a magnification of 50 times so as to include a total of 500 or more landing marks (granules). The landing marks (granules) observed in the five lenses were regarded as circles, and the diameters of the landing marks (granules) at 500 were measured and arithmetically averaged, and the resultant was set as the landing size D1. In the conditions for forming the second coating film shown in the first table, the "number of times" and the "repetition" are set to 1, respectively, and the same conditions as those for forming the second coating film shown in the first table are used. In a spray coater (product name "DC110", manufactured by Sanming Co., Ltd.), the curable composition was sprayed onto the surface (coated surface) of a glass substrate of 8 inches to form a coating film. The obtained coating film was heated at 200 ° C for 2 hours (prebaking treatment) to obtain a sample for measurement of the landing size D2. Except for this, the landing size D2 was measured in the same manner as the measurement of the landing size D1. The measurement results of the landing size D1 and the landing size D2 are shown in the first table.

<Surface roughness Ra> (surface roughness Ra of the first film) The first film was formed under the same conditions as the above (the film thickness of the first film). The surface roughness Ra was measured by evaluating the surface unevenness of the obtained first film using an atomic force microscope (Nanoscope 4A, manufactured by Veeco, Japan) under a field of view of 10 μm ́10 μm. (Surface roughness Ra of the second film) The first film was formed under the same conditions as the "(film thickness of the second film)". The surface roughness Ra of the obtained second film was measured under the same conditions as those of the first film. The measurement results of the surface roughness Ra of each film are shown in the first table. (The surface roughness of the cured film) is formed by laminating the first film and the second film in the order of the first film and the second film under the same conditions as the above (the total film thickness of the first film and the second film). Film (second film / first film / glass substrate). The surface roughness Ra of the obtained cured film was measured under the same conditions as those of the first film.

[Table 1]

[Table 2]

As shown in the second table, it is understood that the method for producing the cured film of Examples 1 to 10 according to the ratio D1/D2 of the landing size D1 to the landing size D2 is 5 to 150, and the low reflectance and the lithographic performance can be obtained. Excellent curing film for linearity, development residue and pinhole. On the other hand, at least one of the reflectance and the lithographic performance of the cured film of Comparative Example 1 to Comparative Example 5 in which the ratio D1/D2 of the landing size D1 and the landing size D2 is in the range of 5 to 150 is known. Not excellent.

<Examples 11 to 26 and Comparative Example 6> In the first embodiment, the landing size D1 and the landing size D2 were not changed, and only the atomization pressure, the hydraulic pressure, and the number of repetitions were appropriately adjusted, and the example shown in the third table was produced. 11 to the cured film of Example 26, and the same evaluation as in Example 1 was carried out. Further, in Comparative Example 2, the landing size D1 and the landing size D2 were not changed, and only the atomization pressure, the hydraulic pressure, and the number of repetitions were appropriately adjusted, thereby producing the cured film of Comparative Example 6 shown in Table 3, and proceeding with Example 1. The same evaluation. The evaluation results of the respective examples and comparative examples are shown in the third table.

(Void Ratio) The void ratios of the cured films of Examples 11 to 26 and Comparative Example 6 obtained as described above were measured as follows. Specifically, a cross-sectional SEM observation of each cured film was carried out using a scanning electron microscope (SEM (Scanning Electron Microscope); JSM-7401 manufactured by JEOL Ltd.). Using the image software ("Adobe Photoshop" manufactured by Adobe Systems, Inc.), the threshold value of the obtained cross-sectional SEM photograph was adjusted, and white and black were binarized, according to white and black. The ratio of points is used to calculate the void ratio. White dots refer to voids, and black dots refer to cured films. Specifically, the void ratio A1 is obtained by calculating "the number of white dots/black dots" by the image analysis, and the image analysis is based on the first surface (surface on the substrate side). A cross-sectional image in a region in which the thickness of the cured film is 10% ± 5% toward the second surface (the surface facing the substrate). Further, the void ratio A2 is obtained by calculating "the number of white dots/black dots" by the image analysis, and the image analysis is based on the cured film from the second surface toward the first surface. A cross-sectional image of a region having a thickness of 10% ± 5%. An image including white dots and black dots analyzed by image analysis was observed at 10,000 times, and averaged in 10 fields of view in the predetermined region, and the obtained person was set as a void ratio. The calculated void ratio was evaluated based on the following criteria.

(Evaluation Results) The evaluation results are shown in Table 3 below.

[table 3]

As shown in the third table, it is understood that the cured films of Examples 11 to 26 having a relationship between the void ratio A1 and the porosity A2 of A1 < A2 can achieve low reflectance and lithographic properties (linearity, development residue). And pinhole) excellent hardened film. On the other hand, according to the cured film of Comparative Example 6 in which the porosity A1 and the porosity A2 are in the relationship of A1>A2, a cured film having poor lithographic properties (linearity, development residue, and pinhole) can be obtained.

<Example 27> The evaluation was carried out in the same manner as in Example 2 except that the curable composition 2 was used instead of the curable composition 1. As a result, the ratio of the landing size ratio, the film thickness of the cured film, and the film thickness was obtained. A good cured film having the same degree as in Example 2, the reflectance, the surface roughness of the cured film, and the lithographic performance. <Curable Composition 2> The components shown below were mixed and stirred to obtain a curable composition.・Additional solvent: PGMEA ・・・3.8 parts by mass ・Additional solvent: cyclopentanone ・・・21.8 parts by mass ・Binder polymer: Acrycure RD-F8 (made by Nippon Shokubai) 40%PGMEA Solution ・・・6.7 parts by mass ・Polymerized compound: DPHA (KAYARAD, manufactured by Nippon Kayaku Co., Ltd.) 70% PGMEA solution ・・・7.5 parts by mass ・Polymerization inhibitor: p-methoxyphenol ・・・0.003 parts by mass, surfactant: surfactant A (1.0% PGMEA solution) of the above structure ・・・2.1 parts by mass ・Polymerization initiator: IRGACURE OXE-02 (Manufactured by BASF) · 1.6 mass parts Dispersion: The pigment dispersion 56.6 parts by mass was ·

<Example 28> In the production of the pigment dispersion of Example 1, carbon black (trade name "color black S170" was used instead of titanium black, and the average primary particle diameter was produced by Degussa Co., Ltd. Pigment dispersion A was obtained by the same method except that 17 nm, a BET specific surface area of 200 m ² /g, and carbon black produced by a gas black method.

In the curable composition 1 used in the first embodiment, the curable composition 3 was obtained in the same manner except that the pigment dispersion used in the curable composition 1 was changed to the pigment dispersion A.

In the same manner as in Example 1, except that the curable composition 3 was used instead of the curable composition 1, the landing size ratio, the film thickness of the cured film, the film thickness ratio, the reflectance, and the hardening were obtained. A good cured film of the same degree as in Example 1 was used for both the surface roughness and the lithographic performance of the film.

<Example 29> In the production of the pigment dispersion of Example 1, pigment red 254 (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name BK-CF) was used instead of titanium black, and the same was used. The pigment dispersion B was obtained in the same manner.

The curable composition 4 was produced in the same manner as the curable composition 1 except that the pigment dispersion of Example 1 was changed to 33 parts by mass, and 7.3 parts by mass of the pigment dispersion B was further added.

The evaluation was carried out in the same manner as in Example 1 except that the curable composition 4 was used instead of the curable composition 1. As a result, the landing size ratio, the film thickness of the cured film, the film thickness ratio, the reflectance, and the hardening were obtained. A good cured film of the same degree as in Example 1 was used for both the surface roughness and the lithographic performance of the film.

<Example 30> (Synthesis of dye polymer) A dye polymer was obtained by the method for producing a salt-forming compound (A-1) described in paragraph 0165 of JP-A-2011-242752. (呫 tons Xa). In addition, the structure of the monomer and pigment used is shown below. The weight average molecular weight (Mw) of the dye polymer (xanthene Xa) confirmed by GPC measurement was 10,500.

[Chemistry 14]

40.3 parts by mass of the pigment dispersion of Example 1 was changed to 33.0 parts by mass, and 1.8 parts by mass of the dye polymer (xanthene Xa) was further added, and 5.5 parts by mass of PGMEA was further added, and the curability was further improved. The composition 1 was obtained in the same manner as the composition 1.

The evaluation was carried out in the same manner as in Example 1 except that the curable composition 5 was used instead of the curable composition 1. As a result, the landing size ratio, the film thickness of the cured film, the film thickness ratio, the reflectance, and the hardening were obtained. A good cured film of the same degree as in Example 1 was used for both the surface roughness and the lithographic performance of the film.

Based on the results, it is estimated that the effect desired in the present application can be obtained even in the case of changing the coloring agent or in combination.

<Example 31> A curable composition was prepared in the same manner as the curable composition 1 except that the polymerization initiator was changed to IRGACURE-907 (manufactured by BASF Japan Co., Ltd.). .

The evaluation was carried out in the same manner as in Example 1 except that the curable composition 6 was used instead of the curable composition 1. As a result, the landing size ratio, the film thickness of the cured film, the film thickness ratio, the reflectance, and the hardening were obtained. A good film of the same degree as in Example 1 was used for both the surface roughness and the lithographic performance of the film.

<Example 32> The polymerizable compound of the curable composition 1 was changed to KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 0.5 part, and PET-30 (pentaerythritol III) The curable composition 7 was prepared by the same method except that 1.3 parts of acrylate, manufactured by Nippon Chemical Co., Ltd. was used.

In the same manner as in Example 1, except that the curable composition 7 was used instead of the curable composition 1, the landing size ratio, the film thickness of the cured film, the film thickness ratio, the reflectance, and the hardening were obtained. A good cured film of the same degree as in Example 1 was used for both the surface roughness and the lithographic performance of the film.

From the results, it is estimated that the effect desired in the present application can be obtained even when the polymerization initiator or the polymerizable compound is changed.

2, 20, 30, 40‧‧‧ solid camera
3‧‧‧CMOS sensor
4‧‧‧ circuit board
5‧‧‧Ceramic substrate
5a‧‧‧ openings
5b‧‧‧ inner wall
6‧‧‧IR cut filter
6a‧‧‧Incoming surface
7‧‧‧Photographic lens
8‧‧‧ lens holder
9‧‧‧ Keeping the cylinder
11, 21, 31, 41‧‧ ‧ shading film (shading layer)
100‧‧‧Substrate
120‧‧·coating film
120A‧‧‧1st film
120a, 120b‧‧‧ granules
120B‧‧‧2nd film
210‧‧‧Nozzles
P‧‧‧Specified size coating
R1, R2, R3‧‧‧ reflected light
X‧‧‧1st direction
Y‧‧‧2nd direction

FIG. 1A is an explanatory view showing an example of a method of producing a cured film of the present invention. FIG. 1B is an explanatory view showing an example of a method of producing a cured film of the present invention. FIG. 2 is a perspective view showing the solid-state imaging device according to the first embodiment. Fig. 3 is an exploded perspective view of the solid-state imaging device according to the first embodiment. 4 is a cross-sectional view showing a solid-state imaging device according to the first embodiment. Fig. 5 is a cross-sectional view showing a solid-state imaging device according to a second embodiment. Fig. 6 is a cross-sectional view showing a solid-state imaging device according to a third embodiment. Fig. 7 is a cross-sectional view showing a solid-state imaging device according to a fourth embodiment. Fig. 8 is a schematic top view showing a method of forming a coating film using a spray device in an embodiment.

no

Claims (15)

A method for producing a cured film, which comprises using a cured film containing a colorant, a polymerization initiator, a polymerizable compound, a binder polymer, and a solvent, wherein the method for producing the cured film includes: The first coating film is spray-coated by spraying the curable composition so that the landing size is D1. In the second step, the curable composition is spray-coated to form the second coating film so that the landing size is D2. And a step of forming a cured film by performing a hardening treatment, wherein the D1 and the D2 satisfy a relationship of D1>D2, and a ratio D1/D2 of the D1 to the D2 is 5 to 150. The method for producing a cured film according to claim 1, wherein the second step is performed after the first step. The method for producing a cured film according to the first or second aspect of the invention, wherein the distance L1 between the tip end of the nozzle and the surface to be coated of the spray device used in the spray coating in the first step is smaller than The distance L2 between the tip end of the nozzle of the spray device used in the spray coating described in the second step and the surface to be coated. The method for producing a cured film according to claim 3, wherein the distance L1 is less than 5 cm, and the distance L2 exceeds 10 cm. The method for producing a cured film according to the first or second aspect of the invention, wherein the D2 is from 1 μm to 30 μm. The method for producing a cured film according to the first or second aspect of the invention, wherein the D2 is 1 μm to 10 μm. A cured film obtained by using a curable composition containing a colorant, a polymerization initiator, a polymerizable compound, a binder polymer, and a solvent, and formed on a substrate, which will be from the side located on the substrate side The first surface of the cured film faces the second surface of the cured film facing the first surface, and the void ratio at a position of 10% of the thickness of the cured film is A1. When the second surface faces the first surface and the void ratio at the position of 10% of the thickness of the cured film is A2, the relationship between A1 and A2 satisfies A1 < A2. The cured film according to claim 7, wherein the A1 is 0.001% or more and less than 3%. The cured film according to claim 7 or 8, wherein the A2 is 0.1% or more and less than 30%. The cured film according to claim 7 or 8, wherein the second surface of the cured film has a surface roughness Ra of from 0.1 μm to 1.2 μm. The cured film according to claim 7 or 8, wherein the cured film has at least two or more layers. A cured film as described in claim 7 or 8, which is used as a light-shielding film. A cured film as described in claim 7 or 8, which is used as a color filter. A solid-state image sensor having a cured film according to any one of claims 7 to 11. An image display device having the cured film according to any one of claims 7 to 11.