JP7083887B2 - Curable composition, cured film, optical element, solid-state image sensor, color filter - Google Patents

Description

The present invention relates to a curable composition, a cured film, an optical element, a solid-state image sensor, and a color filter.

As a method for producing a cured film used in a solid-state image sensor or the like, a method in which a curable composition layer is formed on a substrate and then cured is generally used. Typically, the curable composition layer is irradiated with light through a predetermined mask pattern, and then a development process is performed.

For example, Patent Document 1 describes a photopolymerizable resin laminate in which a photopolymerizable resin layer or the like is laminated, wherein the photopolymerizable resin layer has an alkali-soluble polymer and an ethylenically unsaturated bond. A photopolymerizable resin laminate comprising a photopolymerizable resin composition containing a compound, a photopolymerizable initiator, and a black pigment is disclosed.

Re-table 2008/078707

When the present inventor examined the photopolymerizable resin composition disclosed in Patent Document 1, the photopolymerizable resin composition had a line width stability when a cured film was formed in a pattern (hereinafter referred to as “s)”. , Simply referred to as "line width stability" or "line width stability of the cured film") was found to have room for improvement.

Therefore, it is an object of the present invention to provide a curable composition capable of producing a cured film having excellent line width stability. Another object of the present invention is to provide a cured film formed by using such a curable composition, and a color filter, an optical element, and a solid-state imaging device having the cured film. ..

[1]
Contains a black colorant, a polymerizable compound, a resin A, a photopolymerization initiator, and a polymerization inhibitor.
A curable composition in which the resin A satisfies one of the requirements of having an acid value of 120 to 350 mgKOH / g and having a weight average molecular weight of 3000 to 7500.
[2]
The curable composition according to [1], wherein the mass ratio of the content of the polymerization inhibitor to the content of the polymerizable compound is more than 0.0005.
[3]
Further, it contains resin B, which is a resin different from the above resin A and has one or more groups selected from the group consisting of an oxyalkylene group and an oxyalkylene carbonyl group, [1] or [2]. ] The curable composition according to.
[4]
The curable composition according to any one of [1] to [3], wherein the polymerizable compound has four ethylenically unsaturated groups.
[5]
The curable composition according to any one of [1] to [4], wherein the acid value of the resin A is 170 to 300 mgKOH / g.
[6]
The curable composition according to any one of [1] to [5], wherein the resin A has a weight average molecular weight of 3000 to 5000.
[7]
The curable composition according to any one of [1] to [6], wherein the content of the repeating unit derived from the (meth) acrylic monomer is 50 mol% or more in all the repeating units of the resin A.
[8]
The curable composition according to any one of [1] to [7], wherein the resin A is a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.
[9]
The curable composition according to any one of [1] to [8], wherein the double bond equivalent of the polymerizable compound is 11.0 mmol / g or more.
[10]
The curable composition according to any one of [1] to [9], wherein the photopolymerization initiator is an oxime ester-based polymerization initiator.
[11]
The curable composition according to any one of [1] to [10], wherein the photopolymerization initiator is a compound represented by the general formula (A) described later.
[12]
The curable composition according to any one of [1] to [11], wherein the black color material is a black pigment.
[13]
A cured film formed by using the curable composition according to any one of [1] to [12].
[14]
The cured film according to [13], which is a light-shielding film.
[15]
An optical element having the cured film according to [13] or [14].
[16]
A solid-state image sensor having the cured film according to [13] or [14].
[17]
A color filter having the cured film according to [13] or [14].

According to the present invention, it is possible to provide a curable composition capable of producing a cured film having excellent line width stability. Further, the present invention can provide a cured film formed by using such a curable composition, and a color filter, an optical element, and a solid-state imaging device having the cured film.

It is a schematic sectional drawing which shows the structural example of the solid-state image sensor. FIG. 3 is a schematic cross-sectional view showing an enlarged image of the image pickup unit of FIG.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range in which the numerical values described before and after "-" are included as the lower limit value and the upper limit value.

Further, in the notation of a group (atomic group) in the present specification, the notation not describing substitution or non-substitution includes a group containing a substituent as well as a group containing no substituent. For example, the "alkyl group" includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).

Further, the term "active light" or "radiation" in the present specification means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV: Extreme ultraviolet lithium), X-rays, electron beams and the like. Further, in the present specification, light means active light rays and radiation. Unless otherwise specified, the term "exposure" as used herein includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams.

Further, in the present specification, "(meth) acrylate" represents acrylate and methacrylate. Further, in the present specification, "(meth) acrylic" means acrylic and methacrylic. Further, in the present specification, "(meth) acryloyl" represents acryloyl and methacryloyl. Further, in the present specification, "(meth) acrylamide" represents acrylamide and metaacrylamide. Further, in the present specification, "monomer" and "monomer" are synonymous.

Further, in the present specification, "ppm" means "parts-per-million ( ^10-6 )", "ppb" means "parts-per-billion ( ^10-9 )", and "ppt". Means "parts-per-thrillion ( ^10-12 )".

In the present specification, the weight average molecular weight (Mw) is a polystyrene-equivalent value obtained by a GPC (Gel Permeation Chromatography) method.
In the present specification, the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as an eluent, and THF (tetrahydrofuran) as an eluent. ) Is used.

[Cursable composition]
The curable composition of the present invention contains a black colorant, a polymerizable compound, a resin A, a photopolymerization initiator, and a polymerization inhibitor.
The resin A has an acid value of 120 to 350 mgKOH / g (hereinafter also referred to as "requirement 1") and a weight average molecular weight of 3000 to 7500 (hereinafter also referred to as "requirement 2"). It is a resin that meets one of the requirements.

Although the mechanism by which a cured film having excellent line width stability can be formed by using such a curable composition is not always clear, the present inventors consider as follows.
In the formation of the cured film, usually, the curable composition layer formed by using the curable composition is cured through exposure and further developed. During the above exposure, the irradiated light may be diffracted and / or scattered, so that a small amount of light leaks around the original exposed area, and the curable composition layer may be partially cured. As described above, the portion where the curable composition layer is partially cured around the original exposed region causes unintended enlargement of the cured film, which adversely affects the line width stability of the cured film.
On the other hand, since the curable composition of the present invention contains a polymerization inhibitor, it is possible to reduce the occurrence of partial curing due to a slight amount of light leaking from the exposed region. Further, since the curable composition of the present invention contains a resin A that satisfies either requirement 1 or requirement 2, the curable composition layer formed by using the curable composition of the present invention is developable. Even if a partially cured part is generated, it is removed during development. As a result, it is considered that a cured film having excellent line width stability can be produced by using the curable composition of the present invention.

[Ingredients of curable composition]
First, the components of the curable composition of the present invention will be described.

<Black color material>
The curable composition contains a black colorant.
Examples of the black color material include one or more selected from the group consisting of black pigments and black dyes.
The black color material may be used alone or in combination of two or more.
The content of the black color material in the curable composition is not particularly limited, but is preferably 1 to 99% by mass, more preferably 5 to 55% by mass, based on the total solid content of the curable composition.
The total solid content of the curable composition is intended as a component forming a cured film and does not contain a solvent. Further, if the component forms a cured film, even if the property is liquid, it is regarded as a solid content.

Further, a plurality of colorants that cannot be used alone as a black color material may be combined and adjusted so as to be black as a whole to obtain a black color material.
For example, in addition to using a pigment that expresses black alone as a black pigment, a plurality of pigments having a color other than black alone may be combined and used as a black pigment. Similarly, in addition to using a dye that expresses black alone as a black dye, a plurality of dyes having a color other than black alone may be used as a black dye in combination.
The black color material refers to a color material that absorbs over the entire range of a wavelength of 400 to 700 nm.
More specifically, for example, a black color material that meets the evaluation criteria Z described below is preferable.
First, a composition containing a coloring material, a transparent resin matrix (acrylic resin, etc.), and a solvent, and the content of the coloring material with respect to the total solid content is 60% by mass is prepared. The obtained composition is applied onto a glass substrate so that the film thickness of the coating film after drying is 1 μm to form a coating film. The light-shielding property of the coating film after drying is evaluated using a spectrophotometer (UV-3600, etc. manufactured by Hitachi, Ltd.). If the maximum value of the transmittance of the dried coating film at a wavelength of 400 to 700 nm is less than 10%, it can be determined that the coloring material is a black coloring material conforming to the evaluation standard Z.

(Black pigment)
The black color material is preferably a black pigment from the viewpoint that a cured film having a reduced reflectance can be obtained.
As the black pigment, various known black pigments can be used. The black pigment may be an inorganic pigment or an organic pigment.

As the black pigment, a pigment that develops black color by itself is preferable.
Further, as the black pigment, for example, a pigment that absorbs infrared rays is preferable.
Here, the black pigment that absorbs infrared rays has absorption in, for example, a wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm). It is also preferable to have a maximum absorption wavelength in the wavelength region of 675 to 900 nm.

Examples of the inorganic pigment that absorbs infrared rays and develops black color by itself include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), and Group 5 such as vanadium (V) and niobium (Nb). Metal elements of, cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag). Examples thereof include metal oxides, metal nitrides, and metal oxynitrides containing one or more kinds of metal elements selected from the group consisting of two or more kinds of metal elements. The inorganic pigment may be surface-modified. Examples thereof include inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, and examples thereof include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.). Further, the metal oxide, the metal nitride, and the metal oxynitride may be used as particles in which other atoms are further mixed. For example, it may be used as metal nitride-containing particles further containing an atom (preferably an oxygen atom and / or a sulfur atom) selected from the elements of Groups 13 to 17 of the Periodic Table.
Carbon black is also mentioned as a pigment that absorbs infrared rays and develops black color by itself. Specific examples of carbon black include commercially available products, C.I. I. Pigment Black 1 and other organic pigments, and C.I. I. Examples thereof include inorganic pigments such as Pigment Black 7. Further, as the carbon black, carbon black whose surface is coated with a resin may be used.

Among them, as the black pigment, the nitride or oxide of the metal element of Group 4 or the nitride of the metal element of Group 5 or the nitride of the metal element of Group 5 can be suppressed from the viewpoint of suppressing the occurrence of undercut when forming the cured film. Oxynitrides are preferred, titanium nitrides or oxynitrides, zirconite nitrides or oxynitrides, vanadium nitrides or oxynitrides, or niobium nitrides or oxynitrides are more preferred, and titanium nitrides are preferred. Substances or oxynitrides are more preferred.
The titanium nitride is titanium nitride, the zirconium nitride is zirconium nitride, the vanadium nitride is vanadium nitride, and the niobium nitride is niobium nitride. Further, the oxynitride of titanium is titanium oxynitride, the oxynitride of zirconium is zirconium oxynitride, the oxynitride of vanadium is vanadium oxynitride, and the oxynitride of niobium is oxynitride. Nitride.

In the present specification, titanium nitride is intended for TiN and may contain oxygen atoms that are unavoidable in production (for example, the surface of TiN particles is unintentionally oxidized, etc.).
As used herein, the titanium nitride is intended to be a compound in which the diffraction angle 2θ of the peak derived from the (200) plane when CuKα ray is used as an X-ray source is 42.5 ° to 42.8 °.
Further, in the present specification, titanium nitride is intended to be a compound having a peak diffraction angle 2θ of more than 42.8 ° derived from the (200) plane when CuKα ray is used as an X-ray source. The upper limit of the diffraction angle 2θ of titanium oxynitride is not particularly limited, but is preferably 43.5 ° or less.
Examples of titanium oxynitride include titanium black and the like, and more specifically, for example, TIO ₂ , low-order titanium oxide represented by Tin O _2n-1 (1 ≦ _n ≦ 20), and /. Alternatively, a form containing titanium oxynitride represented by TiN _x Oy (0 <x <2.0, 0.1 < _y <2.0) can be mentioned. In the following description, titanium nitride (the diffraction angle 2θ is 42.5 ° to 42.8 °) and titanium oxynitride (the diffraction angle 2θ is more than 42.8 °) are collectively referred to as titanium nitride. The form will be described.
Further, the titanium nitride may be used as particles in which other atoms are mixed. For example, the titanium nitride may be used as titanium nitride-containing particles further containing an atom (preferably a silicon atom, a sulfur atom, etc.) selected from the elements of Groups 13 to 17 of the Periodic Table. The same applies to other metal nitrides, and the metal nitride, which is a combination of the metal nitride and the oxynitride metal, may be used as particles in which other atoms are further mixed. For example, the metal nitride may be used as metal nitride-containing particles further containing an atom (preferably a silicon atom, a sulfur atom, etc.) selected from the elements of Groups 13 to 17 of the Periodic Table.

When the X-ray diffraction spectrum of titanium nitride is measured using CuKα ray as an X-ray source, the peak derived from the (200) plane is close to 2θ = 42.5 ° for TiN as the peak with the strongest intensity, and TiO is ( 200) A peak derived from the plane is observed near 2θ = 43.4 °. On the other hand, although it is not the strongest peak, the peak derived from the (200) plane is in the vicinity of 2θ = 48.1 °, and the peak derived from the ( _{200) plane is 2θ = 39 in the rutile type TiO 2 .} It is observed near 2 °. Therefore, as the titanium oxynitride contains a large amount of oxygen atoms, the peak position shifts to a higher angle side with respect to 42.5 °.

When the titanium nitride contains titanium oxide TiO ₂ , the peak derived from anatase-type TiO ₂ (101) is derived from rutile-type TiO ₂ (110) in the vicinity of 2θ = 25.3 ° as the strongest peak. The peak is seen near 2θ = 27.4 °. However, TiO ₂ is white and is a factor that lowers the light-shielding property of the light-shielding film obtained by curing the curable composition, so it is preferable that the amount is reduced to the extent that it is not observed as a peak.

From the half width of the peak obtained by the above-mentioned measurement of the X-ray diffraction spectrum, the crystallite size constituting the titanium nitride can be obtained. The crystallite size can be calculated using Scherrer's equation.

The crystallite size constituting the titanium nitride is preferably 50 nm or less, preferably 20 nm or more. When the crystallite size is 20 to 50 nm, the cured film formed by using the curable composition tends to have higher ultraviolet (particularly i-ray (wavelength 365 nm)) transmittance, and has higher photosensitivity. The composition is obtained.

The specific surface area of the titanium nitride is not particularly limited, but can be determined by the BET (Brunauer, Emmett, Teller) method. The specific surface area of the titanium nitride is preferably 5 to 100 m ² / g, more preferably 10 to 60 m ² / g.

The method for producing the black pigment is not particularly limited, and a known production method can be used, and examples thereof include a gas phase reaction method. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable in that impurities are less mixed, the particle size is easily uniform, and the productivity is high.
In the thermal plasma method, the method for generating thermal plasma is not particularly limited, and examples thereof include DC arc discharge, multi-layer arc discharge, high frequency (RF) plasma, hybrid plasma, and the like, and there is little contamination of impurities from the electrodes. High frequency plasma is more preferred.
The specific method for producing the black pigment by the thermal plasma method is not particularly limited, but for example, as a method for producing the titanium nitride, a method of reacting titanium tetrachloride with ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 2-22110). No.), a method of evaporating titanium powder with high-frequency thermal plasma, introducing nitrogen as a carrier gas, nitriding and synthesizing in the cooling process (Japanese Patent Laid-Open No. 61-11140), and ammonia gas at the periphery of the plasma. Examples thereof include a method of blowing (Japanese Patent Laid-Open No. 63-85007).
However, the method for producing a black pigment is not limited to the above, and the production method is not limited as long as a black pigment having desired physical properties can be obtained.

Further, the (acid) nitride of the metal atom as described above may be coated with a silicon-containing compound to obtain a black pigment.
The method for coating the (acid) nitride of the metal atom is not particularly limited, and a known method can be used. Method (using (acid) nitride of metal atom instead of titanium oxide), method described in paragraphs 0015 to 0043 of JP-A-2008-69193 (instead of fine particle titanium dioxide, (acid) of metal atom). (Using a nitride), paragraph 0020 of JP-A-2016-74870, and the method described in paragraphs 0124 to 0138 (using (acid) nitride of a metal atom instead of the metal oxide fine particles). And the above contents are incorporated herein.

Further, when the curable composition contains titanium black, it is also preferable to contain titanium black as a dispersant containing titanium black and Si atoms.
In this form, titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is further preferable.
Here, the dispersant includes both those in which titanium black is in the state of primary particles and those in which titanium black is in the state of aggregates (secondary particles).
In order to change the Si / Ti of the dispersion to be dispersed (for example, to make it 0.05 or more), the following means can be used.
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is reduced at a high temperature (for example, 850 to 1000 ° C.) to mainly produce titanium black particles. A dispersant containing Si and Ti as components can be obtained. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).
Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik) and the like.
A dispersant may be used to disperse the titanium oxide and the silica particles. Examples of the dispersant include those described below as dispersants.
The above dispersion may be carried out in a solvent. Examples of the solvent include water and organic solvents. Examples thereof will be described in the column of organic solvent described later.
Titanium black having Si / Ti adjusted to, for example, 0.05 or more can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of JP-A-2008-266045.

By adjusting the content ratio (Si / Ti) of Si atom and Ti atom in the dispersant containing titanium black and Si atom to a suitable range (for example, 0.05 or more), the composition containing this disperse is included. When the cured film is formed using the material, the residue derived from the composition outside the formed region of the cured film is reduced. The residue contains components derived from the composition such as titanium black particles and resin components.
The reason why the residue is reduced is not yet clear, but the dispersion as described above tends to have a small particle size (for example, the particle size is 30 nm or less), and further, the Si atom of the dispersion tends to have a small particle size. By increasing the contained components, the adsorptivity of the entire film with the substrate is reduced. It is presumed that this contributes to the improvement of the developability of the uncured composition (particularly titanium black) in the formation of the cured film.
Further, since titanium black is excellent in light shielding property against light in a wide wavelength range from ultraviolet light to infrared light, the above-mentioned titanium black and a dispersion containing Si atoms (preferably Si / Ti are in terms of mass). A light-shielding film formed by using (0.05 or more) exhibits excellent light-shielding properties.
The content ratio (Si / Ti) of Si atom to Ti atom in the dispersion is, for example, the method (1-1) or method (1-2) described in paragraph 0033 of JP2013-249417A. ) Can be measured.
Further, with respect to the dispersant contained in the cured film obtained by curing the composition, whether or not the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersant is 0.05 or more. When determining the above, the method (2) described in paragraph 0035 of JP2013-249417A is used.

In the dispersant containing titanium black and Si atom, the above-mentioned titanium black can be used.
Hereinafter, the materials used when introducing Si atoms into the dispersion to be dispersed will be described. When introducing a Si atom into the dispersion, a Si-containing substance such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, synthetic silica and the like, and these may be appropriately selected and used.
Further, when the particle size of the silica particles is smaller than the film thickness when the light-shielding film (cured film) is formed, the light-shielding property is more excellent. Therefore, it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.

Further, as described above, a plurality of pigments having a color other than black alone may be combined and used as a black pigment.
As described above, the pigment having a color other than black by itself may be an inorganic pigment or an organic pigment. As the pigment having a color other than black by itself, for example, chromatic pigments (chromatic pigments) such as R (red), G (green), and B (blue) can also be used.

The inorganic pigment having a color other than black by itself is not particularly limited, and a known inorganic pigment can be used.
Examples of the inorganic pigment include titanium oxide, chromium oxide, iron oxide, lead tan, iron oxide red, yellow lead, zinc yellow (zircon 1 type, zinc yellow 2 type), ultramarine blue, and Prussian blue (ferrussian blue). You can choose from Zircon Gray, Placeojim Yellow, Chrome Titanium Yellow, Chrome Green, Peacock, Victoria Green, Prussian Blue (unrelated to Prussian Blue), Vanadium Zircon Blue, Chrome Tin Pink, Ceramic Trial Red, and Salmon Pink. ..
The inorganic pigment may be surface-modified. For example, an inorganic pigment which has been surface-modified with a surface treatment agent having both a silicone group and an alkyl group can be mentioned, and examples thereof include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).

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

The pigment may be used in combination with a dye described later.
In order to adjust the color and to enhance the light-shielding property in the desired wavelength region, for example, a pigment that expresses black color by itself and / or a pigment that has a color other than black by itself, red, green, etc. A chromatic pigment such as yellow, orange, purple, and blue or a dye described later may be mixed.
Further, it is also preferable to mix a red pigment or dye, or a purple pigment or dye with a pigment that absorbs infrared rays and develops black color by itself, and it is more preferable to mix the red pigment.
Further, an infrared absorber described later may be added.

Further, as a pigment having a color other than black by itself and absorbing infrared rays, a tungsten compound, a metal boride or the like can also be used. Of these, a tungsten compound is preferable because it has excellent light-shielding properties at wavelengths in the infrared region. The tungsten compound is excellent in the light absorption wavelength region of the oxime-based polymerization initiator, which is related to the curing efficiency by exposure, and the translucency in the visible light region.

Considering the handleability, the average primary particle size of the black pigment is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm. When the black pigment is composed of a combination of a plurality of types of pigments, it is preferable that one or more of the pigments constituting the black pigment are within the above range, and all of the pigments constituting the black pigment are within the above range. More preferred.

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

(Black dye)
As the black dye, a dye that develops black color by itself can be used. Further, as described above, a plurality of dyes having a color other than black alone may be combined and used as a black dye.
Examples of such coloring dyes include chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), as well as paragraphs 0027 of JP-A-2014-42375. The colorant described in 0200 can also be used.

Examples of the dye include JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A-2592207, and US Pat. No. 4,808,501. Japanese Patent No. 5667920, US Pat. No. 505950, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-Open No. 6-51115, and Japanese Patent Application Laid-Open No. 6-194828. Dyes disclosed in publications and the like can be used. When classified as a chemical structure, pyrazole azo compound, pyromethene compound, anilino azo compound, triphenylmethane compound, anthraquinone compound, benzylidene compound, oxonol compound, pyrazolotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, or pyrrolopyrazole azomethin. Compounds and the like can be used. Moreover, you may use a dye multimer as a dye. Examples of the dye multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097. Further, a polymerizable dye having a polymerizable property in the molecule may be used, and examples of commercially available products include the RDW series manufactured by Wako Pure Chemical Industries, Ltd.

(Infrared absorber)
The black color material may further contain an infrared absorber as a color material having a color other than black by itself.
The infrared absorber means a compound having absorption in a wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferable.
Examples of the colorant having such spectral characteristics include a pyrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an iminium compound, a thiol complex type compound, a transition metal oxide type compound, a squarylium compound, a naphthalocyanine compound, and a quaterylene. Examples thereof include compounds, dithiol metal complex-based compounds, and croconium compounds.
As the phthalocyanine compound, the naphthalocyanine compound, the iminium compound, the cyanine compound, the squarylium compound, and the croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-11750 may be used, and the contents thereof are described in the present specification. Incorporated into the book. As the cyanine compound, for example, "functional dye, Shin Ogawara / Ken Matsuoka / Eijiro Kitao / Tsuneaki Hirashima, Kodansha Scientific" can be referred to, and this content is incorporated in the present specification.

As the colorant having the above spectral characteristics, the compound disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or the compound disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP-A-2011-164583 Near-infrared absorbing particles having a number average aggregated particle diameter of 5 to 200 nm, which are composed of crystallites of an oxide containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication, can also be used.

As the compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm, at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound is preferable.
The infrared absorber is preferably a compound that dissolves in water at 25 ° C. in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25 ° C. in an amount of 10% by mass or more. By using such a compound, the solvent resistance is improved.
For the pyrrolopyrrole compound, paragraphs 0049 to 0062 of JP-A-2010-222557 can be referred to, and the contents thereof are incorporated in the present specification. The cyanine compound and the squarylium compound are described in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of Japanese Patent Application Laid-Open No. 2014-59550, and International Publication 2012 /. Paragraphs 0013 to 0091 of JP-A-169447, paragraphs 0019 to 0033 of JP-A-2015-176046, paragraphs 0053 to 00099 of JP-A-2014-63144, paragraphs 0083 to 0150 of JP-A-2014-52431, JP-A. Paragraphs 0076 to 0124 of JP-A-2014-444301, paragraphs 0045 to 0078 of JP-A-2012-8532, paragraphs 0027 to 0067 of JP-A-2015-172102, paragraphs 0029-0067 of JP-A-2015-172004, Paragraphs 0029 to 805 of JP-A-2015-40895, paragraphs 0022-0036 of JP-A-2014-126642, paragraphs 0011-0017 of JP-A-2014-148567, paragraphs 0010 to JP-A-2015-157893. 0025, paragraphs 0013 to 0026 of JP-A-2014-095007, paragraphs 0013-0047 of JP-A-2014-80487, paragraphs 0007-0028 of JP-A-2013-227403, etc. can be referred to. Incorporated herein.

<Polymerizable compound>
The curable composition contains a polymerizable compound. As used herein, the polymerizable compound is intended to be a compound that polymerizes under the action of a photopolymerization initiator described later.

The content of the polymerizable compound in the curable composition is not particularly limited, but is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 15 to 15 to the total solid content of the curable composition. 23% by mass is more preferable. The polymerizable compound may be used alone or in combination of two or more. When two or more kinds of polymerizable compounds are used in combination, the total content is preferably within the above range.
The molecular weight of the polymerizable compound is preferably 2000 or less.

The polymerizable compound is a group containing an ethylenically unsaturated bond (hereinafter, also simply referred to as "ethylenically unsaturated group") from the viewpoint that a cured film having an appropriately roughened surface and a reduced reflectance can be obtained. A compound containing 1 to 15 of is preferable, a compound containing 3 to 6 is more preferable, a compound containing 4 to 5 is more preferable, and a compound containing 4 is particularly preferable.
When a plurality of types of polymerizable compounds are used, the content of the polymerizable compound, which is a compound containing 4 to 5 (preferably 4) ethylenically unsaturated groups, is the total polymerizable in the curable composition. It is preferably 80% by mass or more, more preferably 95% by mass or more, based on the compound.
Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group and the like.

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

The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer, and a mixture thereof, and a multimer thereof.
The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.

As the polymerizable compound, a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100 ° C. or higher under normal pressure is also preferable. For example, the compounds described in paragraphs 0227 of JP2013-29760A and paragraphs 0254 to 0257 of JP2008-292970 can be referred to, and the contents thereof are incorporated in the present specification.

The polymerizable compounds are dipentaerythritol triacrylate (commercially available KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), and di. Pentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues (for example, SR454, SR499 commercially available from Sartmer) are preferable. .. These oligomer types can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.
The preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A polymerizable compound having a group is more preferable, and in this ester, those in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol are further preferable. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing and dissolving characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

As the polymerizable compound, a compound containing a caprolactone structure is also a preferred embodiment.
The compound containing a caprolactone structure is not particularly limited as long as the caprolactone structure is contained in the molecule, but for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta. Ε-caprolactone-modified polyfunctional (meth) obtained by esterifying a polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelan with (meth) acrylic acid and ε-caprolactone. ) Acrylate can be mentioned. Of these, a compound having a caprolactone structure represented by the following formula (Z-1) is preferable.

In the formula (Z-1), all 6 Rs are groups represented by the following formula (Z-2), or 1 to 5 of the 6 Rs are the following formulas (Z-2). It is a group represented by, and the residue is a group represented by the following formula (Z-3).

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

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

The polymerizable compound containing a caprolactone structure is commercially available, for example, from Nippon Kayaku as the KAYARAD DPCA series, and DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, formula (Z). -2) Number of groups represented by 2) = 2, compound in which R ¹ is all hydrogen atom), DPCA-30 (same formula, m = 1, number of groups represented by formula (Z-2) = 3 , R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, R ¹ is all hydrogen atoms), And DPCA-120 (m = 2 in the same formula, the number of groups represented by the formula (Z-2) = 6, a compound in which R ¹ is all a hydrogen atom) and the like can be mentioned.

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

In equations (Z-4) and (Z-5), E is independently − ((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-. , Y each independently represents an integer of 0 to 10, and X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In the formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each of m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In the formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each of n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

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

The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. In particular, in the form (Z-5), all 6 Xs are acryloyl groups, in the formula (Z-5), all 6 Xs are acryloyl groups, and among the 6 Xs, It is preferable that the mixture is a mixture with a compound in which at least one is a hydrogen atom. With such a configuration, the developability can be further improved.

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

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

The polymerizable compound has a double bond equivalent (content of ethylenically unsaturated group. More specifically, ethylenically unsaturated group in the polymerizable compound) because the obtained cured film has more excellent ability to suppress retention defects. The number of groups is intended to be the value obtained by dividing the number of groups by the molecular weight (g / mol) of the polymerizable compound) is preferably 7.0 mmol / g or more, and more preferably 11.0 mmol / g or more. The upper limit is not particularly limited, but is generally 20.0 mmol / g or less.
When the curable composition contains a plurality of types of polymerizable compounds and their double bond equivalents are not the same, the mass ratio of each polymerizable compound in the total polymerizable compound and each polymerizable compound. It is preferable that the total value of the product of the compound with the double bond equivalent is within the above range.

In the present specification, the double bond equivalent may be referred to as "C = C value".
When the curable composition contains a plurality of types of polymerizable compounds and the C = C value of each polymerizable compound is clear, the curable composition is contained from the blending ratio of each polymerizable compound. The C = C value as the total mass of the polymerizable compound may be calculated and obtained.
The C = C value (content of ethylenically unsaturated group) of the polymerizable compound contained in the curable composition can be measured by, for example, the following method when the ethylenically unsaturated group is a (meth) acryloyl group. ..
First, a solid component (black pigment or the like) in the curable composition is precipitated by a centrifugation method, and the remaining liquid component is separated. Further, the polymerizable compound is separated from the obtained liquid component by a liquid chromatography method, and the structure of the polymerizable compound is specified by analysis using an NMR (nuclear magnetic resonance) method, a GPC method, or the like, and C. = Find the C value. The C = C value (content of ethylenically unsaturated group) is calculated as a value obtained by dividing the number of polymerizable groups contained in one molecule by the molecular weight.

<Resin A>
The curable composition of the present invention contains resin A.
Resin A is a resin that satisfies either one of "(requirement 1) acid value of 120 to 350 mgKOH / g" and "(requirement 2) weight average molecular weight of 3000 to 7500". be.
Since the resin A satisfies either requirement 1 or requirement 2, the curable composition of the present invention containing the resin A can obtain a cured film having good developability and excellent line width stability.
The resin A may be a resin that satisfies only one of Requirement 1 and Requirement 2, or may be a resin that satisfies both of them at the same time. Above all, it is preferable that the resin satisfies only one of the requirements 1 and 2 and does not satisfy the other requirement.

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

The resin A is not particularly limited as long as it is a resin that satisfies either requirement 1 or requirement 2, but preferably contains a repeating unit derived from a (meth) acrylic monomer. The content of the repeating unit derived from the (meth) acrylic monomer of the resin A is preferably 10 mol% or more, more preferably 50 mol% or more, still more preferably 75 mol% or more, based on all the repeating units. More than 90 mol% is particularly preferred.

As the repeating unit derived from the (meth) acrylic monomer, for example, the repeating unit represented by the following general formula (AA) is preferable.

In the general formula (AA), _RM represents a hydrogen atom or a methyl group.
L represents a single bond or a divalent linking group.
The divalent linking group may be, for example, a hydrocarbon group having a substituent (may be linear, may be branched, or may have a cyclic structure. The number of carbon atoms is 1 to 1). 5. The substituent is preferably a hydroxyl group). Of these, an alkylene group having 1 carbon atom is preferable.
X represents a hydrogen atom or a substituent.
Examples of the substituent include an aromatic ring group (preferably a phenyl group), an alkyl group (preferably 1 to 3 carbon atoms), a (meth) acryloyl group, a (meth) acryloyloxy group, a hydroxyl group, a carboxy group and the like. Be done. Among them, X is preferably a hydrogen atom or a phenyl group.

The repeating unit derived from the (meth) acrylic monomer contained in the resin A (preferably the repeating unit represented by the general formula (AA)) may be only one type, two or more types, or two or more types. Is preferable.
When there are two or more, it is preferable that at least one is a repeating unit derived from (meth) acrylic acid. As the repeating unit other than the repeating unit derived from (meth) acrylic acid, for example, the repeating unit derived from benzyl (meth) acrylate is preferable.

The resin A preferably contains both the repeating unit derived from the benzyl (meth) acrylate and the repeating unit derived from the (meth) acrylic acid, and the repeating unit derived from the benzyl (meth) acrylate and the repeating unit described above. It is more preferable that it consists only of a combination of repeating units derived from (meth) acrylic acid.
In other words, the resin A is preferably a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.

Examples of the other repeating unit that is expected to be contained in the main chain of the resin A include a repeating unit derived from a styrene-based monomer (hydroxystyrene or the like) and a repeating unit derived from an ether dimer.
Examples of the ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).

In the general formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.

In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of JP-A-2010-168539 can be referred to.

As a specific example of the ether dimer, for example, paragraph 0317 of JP2013-29760A can be referred to, and the content thereof is incorporated in the present specification. The ether dimer may be only one kind or two or more kinds.

(Resin A that meets Requirement 1)
The resin A having an acid value of 120 to 350 mgKOH / g (resin A satisfying Requirement 1) is prepared to have an acid value in an appropriate range.
The acid value of the resin satisfying Requirement 1 is preferably 170 to 300 mgKOH / g, more preferably 200 to 270 mgKOH / g, from the viewpoint of more excellent line width stability and undercut suppression property of the obtained cured film.
The weight average molecular weight of the resin A satisfying the requirement 1 is preferably more than 7,500, more preferably 8,000 to 30,000, and even more preferably 10,000 to 15,000.

(Resin A that meets Requirement 2)
The resin A having a weight average molecular weight of 3000 to 7500 (resin A satisfying Requirement 2) is prepared in an appropriate molecular weight range.
The weight average molecular weight of the resin satisfying the requirement A is preferably 3000 to 6500, more preferably 3000 to 5000, and 4000 to 4000, because the cured film has more excellent line width stability, undercut inhibitory property, and residue inhibitory property. 5000 is more preferred.
The acid value of the resin A satisfying Requirement 2 is preferably less than 120 mgKOH / g, more preferably 30 to 110 mgKOH / g, and even more preferably 60 to 100 mgKOH / g.

As the resin A, one type may be used alone, or two or more types may be used in combination. For example, the curable composition may contain both the resin A satisfying the requirement 1 and the resin A satisfying the requirement 2.
The content of the resin A in the curable composition is not particularly limited, but is preferably 1 to 30% by mass, more preferably 5 to 15% by mass, based on the total solid content of the curable composition. When two or more kinds of resins A are used, the total content is preferably within the above range.

The presence or absence of the resin A in the curable composition and its content can be measured by the methods shown below.
First, a solid component (black pigment or the like) in the curable composition is precipitated by a centrifugation method, and the remaining liquid component is separated. Further, a component having a weight average molecular weight of more than 2000 is fractionated from the obtained liquid component by the GPC method, and this is used as the resin to be measured.
Here, when a resin having a weight average molecular weight of 3000 to 7500 is detected, the content of the curable composition with respect to the total solid content is determined by using the resin as the resin A satisfying the requirement 2.
For the resin whose weight average molecular weight deviates from 3000 to 7500, the acid value is measured by a usual method (JISK5601-2-1 or JISK0070, etc.) to confirm whether the acid value is 120 to 350 mgKOH / g. When a resin having an acid value of 120 to 350 mgKOH / g is present, the resin is regarded as a resin A satisfying the requirement 1 (and a resin A not satisfying the requirement 2), and the content of the curable composition with respect to the total solid content. Ask for.
From the total content of the resin A satisfying the requirement 2 and the resin A satisfying the requirement 1 (and the resin A not satisfying the requirement 2) thus obtained, the resin with respect to the total solid content of the curable composition. The content of A can be determined.
Further, the content of the resin A in the curable composition may be obtained by calculation when the composition of the curable composition and the acid value and weight average molecular weight of the raw materials used are known.

<Resin B>
The curable composition may contain a resin other than the above-mentioned resin A.
Examples of the resin other than the resin A include the resin B from the viewpoint that a cured film having a reduced reflectance can be obtained.
The resin B is a resin different from the resin A and has one or more groups selected from the group consisting of an oxyalkylene group and an oxyalkylene carbonyl group.
The resin B is preferably a resin that acts as a so-called pigment dispersant.
The content of the resin B in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, based on the total solid content of the curable composition.
As the resin B, one type may be used alone, or two or more types may be used in combination. When two or more kinds of resins B are used in combination, the total content is preferably within the above range.

The form in which one or more groups selected from the group consisting of an oxyalkylene group and an oxyalkylene carbonyl group in the resin B is present is not particularly limited.
The alkylene moiety in the oxyalkylene group and the oxyalkylene carbonyl group may have a substituent, may be linear or branched, and may have a cyclic structure. Above all, the alkylene moiety is preferably unsubstituted.
The carbon number of the alkylene portion of the oxyalkylene group is preferably 1 to 10, more preferably 2 to 3. The carbon number of the alkylene moiety in the oxyalkylene carbonyl group is preferably 2 to 8, more preferably 4 to 6.
When a plurality of oxyalkylene groups and / or oxyalkylene carbonyl groups are present in one molecule, the plurality of oxyalkylene groups and / or oxyalkylene carbonyl groups may be the same or different from each other.
Further, the resin B has a polyoxyalkylene structure in which a plurality of oxyalkylene groups are continuously bonded (preferably 3 or more, more preferably 10 or more), or a plurality of oxyalkylene carbonyl groups are continuously bonded (preferably 3). It is preferable to have a polyoxyalkylene carbonyl structure in which more than one, more preferably 10 or more) are bonded.

Resin B is a polymer compound [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic co-weight. Combined and naphthalenesulfonic acid formarin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, pigment derivative and the like may be used.
Polymer compounds can be further classified into linear polymers, end-modified polymers, graft-type polymers, and block-type polymers based on their structures.

-Polymer compound The polymer compound is adsorbed on the surface of the object to be dispersed such as the pigment as described above, and acts to prevent the reaggregation of the object to be dispersed. Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, or a block-type polymer containing an anchor site on the pigment surface is preferable.

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

The resin containing a curable group may contain an oxyalkylene group (preferably a polyoxyalkylene carbonyl structure) and / or an oxyalkylene carbonyl group (preferably a polyoxyalkylene carbonyl structure) in the main chain. Further, as described later, when the resin contains a structural unit containing a graft chain, the graft chain has an oxyalkylene group (preferably a polyoxyalkylene structure) and / or an oxyalkylene carbonyl group (preferably poly). It may contain an oxyalkylene carbonyl structure).
As the resin, it is more preferable that the graft chain contains an oxyalkylene carbonyl group.

The polymer compound preferably contains a structural unit containing a graft chain. In addition, in this specification, "structural unit" is synonymous with "repeating unit".
Since the polymer compound containing a structural unit containing such a graft chain has an affinity with a solvent due to the graft chain, the dispersibility of pigments and the like and the dispersion stability after aging (stability over time) It is excellent in. Further, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity with the polymerizable compound or other resin that can be used in combination. As a result, it is less likely that a residue will be generated in alkaline development.
The longer the graft chain, the higher the steric repulsion effect and the better the dispersibility of pigments and the like. On the other hand, if the graft chain is too long, the adsorptive power to the pigment or the like is lowered, and the dispersibility of the pigment or the like tends to be lowered. Therefore, the graft chain preferably has 40 to 10000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and has an atomic number excluding hydrogen atoms. It is more preferably 60 to 500.
Here, the graft chain refers from the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure, and examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure) and a polyester structure (preferably a polyoxyalkylene carbonyl). Structure), polyurethane structure, polyurea structure, polyamide structure, polyether structure (preferably polyoxyalkylene structure) and the like.
The graft chain is composed of a polyoxyalkylene carbonyl structure, a polyoxyalkylene structure, and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby enhancing the dispersibility of the pigment and the like. A graft chain containing at least one selected from the group is preferable, and a graft chain containing at least one of a polyoxyalkylene carbonyl structure and a polyoxyalkylene structure is more preferable.

The macromonomer containing such a graft chain (a monomer having a polymer structure and binding to the main chain of a copolymer to form a graft chain) is not particularly limited, but a reactive double bond group can be used. The contained macromonomer can be preferably used.

Commercially available macromonomers corresponding to the structural unit containing the graft chain contained in the polymer compound and preferably used for the synthesis of the polymer compound include AA-6 (trade name, manufactured by Toa Synthetic Co., Ltd.) and AA-10. (Product name, manufactured by Toa Synthetic Co., Ltd.), AB-6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AS-6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AN-6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AW -6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AA-714 (Product name, manufactured by Toa Synthetic Co., Ltd.), AY-707 (Product name, manufactured by Toa Synthetic Co., Ltd.), AY-714 (Product name, manufactured by Toa Synthetic Co., Ltd.) , AK-5 (trade name, manufactured by Toa Synthetic Co., Ltd.), AK-30 (trade name, manufactured by Toa Synthetic Co., Ltd.), AK-32 (trade name, manufactured by Toa Synthetic Co., Ltd.), Blemmer PP-100 (trade name, manufactured by Nikko). Blemmer PP-500 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PP-800 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PP-1000 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer 55-PET -800 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PME-4000 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PSE-400 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PSE-1300 (trade name, manufactured by Nichiyu Co., Ltd.) Blemmer 43PAPE-600B (trade name, manufactured by Nichiyu Co., Ltd.) or the like is used. Among them, AA-6 (trade name, manufactured by Toagosei), AA-10 (trade name, manufactured by Toagosei), AB-6 (trade name, manufactured by Toagosei), AS-6 (trade name, manufactured by Toagosei), AS-6 (trade name, manufactured by Toagosei). (Product name, manufactured by Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), or Blemmer PME-4000 (trade name, manufactured by Nichiyu Co., Ltd.) is preferable.

The resin B preferably contains at least one structure selected from the group consisting of methyl polyacrylate, methyl polymethacrylate, and cyclic or chain polyester, and methyl polyacrylate and polymethacrylic acid. It is more preferable to contain at least one structure selected from the group consisting of methyl and chain polyester, and it is more preferable to contain a methyl polyacrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. It is more preferable to contain at least one structure selected from the group consisting of. As long as the resin B is a resin other than the resin A and has one or more groups selected from the group consisting of an oxyalkylene group and an oxyalkylene carbonyl group, the above structure can be contained in one resin B. The resin B may be contained alone, or may be a resin B containing a plurality of these structures in one resin B.
Here, the polycaprolactone structure refers to a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opened structure of δ-valerolactone as a repeating unit. These correspond to one aspect of the polyoxyalkylene carbonyl structure.
Specific examples of the repeating unit constituting the polycaprolactone structure contained in the resin B include the repeating unit in which j and k in the following formula (1) and the following formula (2) are 5. Moreover, as a specific example of the repeating unit constituting the polyvalerolactone structure contained in the resin B, the repeating unit in which j and k in the following formula (1) and the following formula (2) are 4 can be mentioned.
Specific examples of the repeating unit constituting the methyl polyacrylate structure contained in the resin B include a repeating unit in which ^X5 in the following formula (4) is a hydrogen atom and ^R4 is a methyl group. Further, as a specific example of the repeating unit constituting the polymethylmethacrylate structure contained in the resin B, a repeating unit in which ^X5 in the following formula (4) is a methyl group and ^R4 is a methyl group can be mentioned. ..

-Structural unit containing a graft chain The polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit containing a graft chain, and the following formula is preferable. It is more preferable to contain the structural unit represented by any of (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4).
Further, the polymer compound preferably contains at least one of the structural units represented by any of the following formulas (1) to (3).
The structural unit represented by the formula (1) and the structural unit represented by the formula (2) are structural units containing an oxyalkylene carbonyl group. The structural unit represented by the formula (3) is a structural unit containing an oxyalkylene group.

In the formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ independently represent an oxygen atom or NH, respectively. It is preferable that W ¹ , W ² , W ³ and W ⁴ are oxygen atoms.
In formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are independent hydrogen atoms or alkyl groups having 1 to 12 carbon atoms (carbon atoms), respectively, from the viewpoint of synthetic constraints. It is preferable, it is more preferable that it is a hydrogen atom or a methyl group independently of each, and a methyl group is further preferable.

In the formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly structurally restricted. Specific examples of the divalent linking groups represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following linking groups (Y-1) to (Y-21). Be done. In the structure shown below, A and B mean the binding sites in the formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable because of the ease of synthesis.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, but specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. And so on. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ , a group containing a steric repulsion effect is preferable from the viewpoint of improving dispersibility, and each group has 5 independent carbon atoms. Alkyl groups or alkoxy groups of to 24 are more preferable, and among them, branched chain-like alkyl groups having 5 to 24 carbon atoms, cyclic alkyl groups having 5 to 24 carbon atoms, or alkoxy groups having 5 to 24 carbon atoms are particularly preferable. Groups are even more preferred. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

In the formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.
Further, in the equations (1) and (2), j and k independently represent integers of 2 to 8, respectively. For j and k in the formulas (1) and (2), an integer of 4 to 6 is preferable, and 5 is more preferable, from the viewpoint of stability over time and developability of the composition.
Further, in the formulas (1) and (2), n and m are preferably integers of 10 or more, and more preferably 20 or more. When the resin B contains a polycaprolactone structure and a polycaprolactone structure, the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of the polyvalerolactone is preferably an integer of 10 or more, preferably 20 or more. Integers are more preferred.

In the formula (3), R ³ represents a branched chain or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of ^R3s 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 group is not particularly structurally limited. As ^R4 , a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom or an alkyl group is more preferable. When R ⁴ is an alkyl group, the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is further preferable. In the formula (4), when q is 2 to 500, a plurality of ^X5 and ^R4 present in the graft copolymer may be the same or different from each other.

In addition, the polymer compound can contain two or more structural units containing graft chains having different structures. That is, the molecule of the polymer compound may contain structural units represented by the formulas (1) to (4) having different structures from each other, and n, m in the formulas (1) to (4). When, p, and q each represent an integer of 2 or more, in the formulas (1) and (2), j and k may contain different structures in the side chain, and the formula (3) may contain different structures. In (4), a plurality of R ³ , R ⁴ , and X ⁵ existing in the molecule may be the same or different from each other.

The structural unit represented by the formula (1) is more preferably the structural unit represented by the following formula (1A) from the viewpoint of stability over time and developability of the composition.
Further, the structural unit represented by the formula (2) is more preferably the structural unit represented by the following formula (2A) from the viewpoint of stability over time and developability of the composition.

In formula (1A), X ¹ , Y ¹ , Z ¹ , and n are synonymous with X ¹ , Y ¹ , Z ¹ , and n in formula (1), and the preferred range is also the same. In formula (2A), X2, Y2, ^Z2 , and ^m are synonymous with X2, ^Y2 , ^Z2 , and ^m in formula ( ² ), and the preferred range is also the same.

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

In formula (3A) or (3B), X ³ , Y ³ , Z ³ , and p are synonymous with X ³ , Y ³ , Z ³ , and p in formula (3), and the preferred ranges are also the same. Is.

The polymer compound more preferably contains the structural unit represented by the formula (1A) as the structural unit containing the graft chain.

In the polymer compound, the structural unit containing the graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% by mass with respect to the total mass of the polymer compound in terms of mass. It is preferable that it is contained in the range of 5 to 30% by mass, and more preferably it is contained in the range of 5 to 30% by mass.
Above all, the total content of the structural units represented by the above formulas (1) to (3) is preferably contained in the range of 2 to 80% by mass with respect to the total mass of the polymer compound, and 5 to 25% by mass. It is more preferable that it is contained in the range of.
When the structural unit containing the graft chain is included in this range, the dispersibility of the pigment is high and the developability when forming the cured film is good.

-Hydrophobic structural unit Further, it is preferable that the polymer compound contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the graft chain). However, in the present specification, 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, etc.).

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

The ClogP value is determined by Daylight Chemical Information System, Inc. It is a value calculated by the program "CLOGP" available from. This program provides the value of "calculated logP" calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which estimates the logP value of the compound by dividing the chemical structure into substructures (fragments) and summing up the logP contributions assigned to the fragments. The details are described in the following documents. In the present specification, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.M. G. Sammnens, J. Mol. B. Taylor and C. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. Leo. Substituent Constituents For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev. , 93, 1281-1306, 1993.

logP means the common logarithm of the partition coefficient P (Partition Cofficient), and quantitatively describes how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is expressed by the following formula.
logP = log (Coil / Water)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Water represents the molar concentration of the compound in the aqueous phase.
When the logP value increases positively across 0, it means that oil solubility increases, and when it becomes negative and the absolute value increases, it means that water solubility increases, and there is a negative correlation with the water solubility of organic compounds, and the intimacy of organic compounds. It is widely used as a parameter for estimating water content.

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

In the above formulas (i) to (iii), R ¹ , R ² and R ³ are independently hydrogen atoms, halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, etc.) or bromine atom, respectively. Represents an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.).
R ¹ , R ² and R ³ are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and more preferably hydrogen atoms or methyl groups. It is more preferable that R ² and R ³ are hydrogen atoms.
X represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

L is a single bond or divalent linking group. The divalent linking group includes a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) and a divalent aromatic group (for example, an arylene group). , Substituent arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ^31- , where R ³¹ Examples include an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and a combination thereof.

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

The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 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, a heterocyclic group and the like.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring, or an aromatic ring may be condensed with the heterocycle. Further, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxyl group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is an aliphatic group. Groups, aromatic groups, or heterocyclic groups), aliphatic groups, aromatic groups, and heterocyclic groups can be mentioned.

L is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. Further, L may contain a polyoxyalkylene structure containing two or more repeated oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by − (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z includes an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group, etc.), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, and the like). Substituted arylene groups, etc.), heterocyclic groups, or combinations thereof can be mentioned. These groups include an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ^{31-, where R 31 is} an aliphatic group and an aromatic group. A group or a heterocyclic group) or a carbonyl group (-CO-) may be contained.

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group further includes a ring-assembled hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -Contains a cyclohexyl phenyl group and the like. As the crosslinked cyclic hydrocarbon ring, for example, pinan, bornan, norbornane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) and the like 2 Cyclic hydrocarbon rings such as homobredane, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane ring. , And tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodecane and 4-cyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene rings can be mentioned. In addition, the crosslinked cyclic hydrocarbon ring includes fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaften, perhydrofluorene, perhydroindene, and the like. A fused ring in which a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenanthrene ring are condensed is also included.
As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, the aliphatic group does not have an acid group as a substituent.

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

The heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle. Further, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxyl group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is an aliphatic group. Groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups, and heterocyclic groups can be mentioned. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ each independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), and a carbon number of 1 to 6. Represents an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Here, L and Z are synonymous with those in the above. As ^R4 , R5, and R6, a hydrogen atom or an alkyl group having ¹ to ³ carbon atoms is preferable, and a hydrogen atom is more preferable.

As the monomer represented by the above formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, and L contains a single bond or an alkylene group or an oxyalkylene structure. A compound having a divalent linking group in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
Further, as the monomer represented by the above formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. The base compound is preferred. Further, as the monomer represented by the above formula (iii), R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or methyl groups, and Z is an aliphatic group, a heterocyclic group or an aromatic group. The base compound is preferred.

Examples of typical compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes and the like.
As examples of the representative compounds represented by the formulas (i) to (iii), the compounds described in paragraphs 0008 to 093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Will be incorporated into.

In the polymer compound, the hydrophobic structural unit is preferably contained in the range of 10 to 90%, more preferably 20 to 80%, based on the total mass of the polymer compound in terms of mass. Sufficient pattern formation can be obtained when the content is in the above range.

-Functional groups capable of forming an interaction with a pigment or the like A polymer compound can introduce a functional group capable of forming an interaction with a pigment or the like. Here, it is preferable that the polymer compound further contains a structural unit containing a functional group capable of forming an interaction with a pigment or the like.
Examples of the functional group capable of forming an interaction with the pigment or the like include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit containing an acid group, a structural unit containing a basic group, and a arrangement, respectively. It is preferable to contain a structural unit containing a positional group or a reactive structural unit.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be imparted with developability for pattern formation by alkaline development.
That is, by introducing an alkali-soluble group into the polymer compound, in the above composition, the polymer compound as the resin B that contributes to the dispersion of the pigment or the like has alkali solubility. The curable composition containing such a polymer compound has excellent light-shielding properties in the exposed portion, and the alkali developability of the unexposed portion is improved.
Further, when the polymer compound contains a structural unit containing an acid group, the polymer compound becomes more compatible with the solvent and the coatability tends to be improved.
This is because the acid group in the structural unit containing the acid group easily interacts with the pigment or the like, the polymer compound stably disperses the pigment or the like, and the viscosity of the polymer compound in which the pigment or the like is dispersed becomes low. It is presumed that this is because the polymer compound itself is likely to be stably dispersed.

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

Examples of the acid group which is a functional group capable of forming an interaction with a pigment or the like include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group and the like, and a carboxylic acid group, a sulfonic acid group, and a sulfonic acid group. , At least one of the phosphate groups is preferable, and a carboxylic acid group is more preferable. The carboxylic acid group has good adsorption power to pigments and the like, and has high dispersibility.
That is, it is preferable that the polymer compound further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or more structural units containing an acid group.
The polymer compound may or may not contain a structural unit containing an acid group, but when it is contained, the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, it is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass from the viewpoint of suppressing damage to the image intensity due to alkaline development.

Examples of the basic group which is a functional group capable of forming an interaction with a pigment or the like include a primary amino group, a secondary amino group, a tertiary amino group, a heterocycle containing an N atom, and an amide. A preferred basic group having a group or the like is a tertiary amino group in that it has a good adsorptivity to a pigment or the like and has a high dispersibility. The polymer compound can contain one or more of these basic groups.
The polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total amount of the polymer compound in terms of mass. 0.01 to 50% by mass is preferable with respect to the mass, and 0.01 to 30% by mass is more preferable from the viewpoint of suppressing developmental inhibition.

Coordinating groups that are functional groups that can interact with pigments and the like, and reactive functional groups include, for example, acetylacetoxy groups, trialkoxysilyl groups, isocyanate groups, acid anhydrides, and acidified groups. Things etc. can be mentioned. A preferable functional group is an acetylacetoxy group in that it has a good adsorptivity to a pigment or the like and has a high dispersibility of the pigment or the like. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it is contained, the content of these structural units is contained. Is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, from the viewpoint of suppressing developmental inhibition.

When the polymer compound contains a functional group capable of forming an interaction with a pigment or the like in addition to the graft chain, it may contain a functional group capable of forming an interaction with the various pigments or the like described above. How these functional groups are introduced is not particularly limited, but the polymer compound is selected from the structural units derived from the monomers represented by the following formulas (iv) to (vi). It preferably contains more than a species of structural unit.

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of carbon atoms. Represents 1 to 6 alkyl groups (eg, methyl group, ethyl group, propyl group, etc.).
In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are preferably hydrogen atoms independently or alkyl groups having 1 to 3 carbon atoms, respectively, and are independently hydrogen atoms or methyl. It is more preferable that it is a group. In the general formula (iv), it is more preferable that R ¹² and R ¹³ are hydrogen atoms, respectively.

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

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

L ₁ is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. Further, L ₁ may contain a polyoxyalkylene structure containing two or more repeated oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by − (OCH ₂ CH ₂ ) _n −, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In the formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with a pigment or the like other than the graft chain, and is preferably a carboxylic acid group and a tertiary amino group, preferably a carboxylic group. It is more preferably an acid group.

In formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are independently hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, and bromine atoms, etc.), and alkyl having 1 to 6 carbon atoms. Represents a group (eg, a methyl group, an ethyl group, a propyl group, etc.), -Z ₁ , or -L ₁ -Z ₁ . Here, L ₁ and Z ₁ have the same meaning as L ₁ and Z ₁ in the above, and the same applies to preferred examples. As R ¹⁴ , R ¹⁵ and R ¹⁶ , respectively, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

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

The following are typical examples of the monomers (compounds) represented by the formulas (iv) to (vi).
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, reactions of compounds containing add-polymerizable double bonds and hydroxyl groups in the molecule (eg, 2-hydroxyethyl methacrylate) with succinic acid anhydride. A product, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and a phthalic acid anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule, and a tetrahydroxyphthalic acid anhydride. Reactive product of, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and a pyromellitic acid anhydride Examples thereof include acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenylmethacrylate and the like.

The content of the structural unit containing a functional group capable of forming an interaction with a pigment or the like is the total mass of the polymer compound from the viewpoint of interaction with the pigment or the like, stability over time, and permeability to the developing solution. On the other hand, 0.05 to 90% by mass is preferable, 1.0 to 80% by mass is more preferable, and 10 to 70% by mass is further preferable.

-Other structural units Further, the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a pigment for the purpose of improving various performances such as image intensity, as long as the effect of the present invention is not impaired. Other structural units having various functions (for example, structural units containing functional groups having an affinity with a solvent, which will be described later), which are different from the structural units containing functional groups capable of forming an interaction with the above. You may also have more.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound can use one or more of these other structural units, and the content thereof is preferably 0 to 80% by mass, preferably 10 to 80% by mass, based on the total mass of the polymer compound. More preferably, it is 60% by mass or less. Sufficient pattern formation is maintained when the content is in the above range.

-Physical characteristics of the polymer compound The acid value of the polymer compound is preferably in the range of 10 to 110 mgKOH / g, more preferably in the range of 20 to 100 mgKOH / g, and even more preferably in the range of 30 to 70 mgKOH / g.
When the acid value of the polymer compound is 110 mgKOH / g or less, pattern peeling during development when forming a cured film can be suppressed more effectively. Further, when the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better. Further, when the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of pigments and the like can be further suppressed, the number of coarse particles can be further reduced, and the stability of the composition over time can be further improved.

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

The weight average molecular weight of the polymer compound is preferably more than 7,000 and 300,000 or less, more preferably 8,000 to 200,000, still more preferably 9000 to 100,000, and 10,000 to 50. It is particularly preferable to be 000.
The polymer compound can be synthesized based on a known method.

Examples of the polymer compound include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and polyethylene glycol dilaurate, which do not correspond to resin A. And polyethylene glycol distearate can also be used.
Specific commercial products of the polymer compound include, for example, "Solsperse 12000" manufactured by Japan Lubrizol.

It is also preferable to use an amphoteric resin containing an acid group and a basic group. The amphoteric resin is preferably a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.
These polymer compounds may be used alone or in combination of two or more.

As a specific example of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.

Further, as the resin B, in addition to the above polymer compounds, the graft copolymers of paragraphs 0037 to 0115 (corresponding US 2011/0124824, paragraphs 0075 to 0133) of JP-A-2010-106268 can be used, and these can be used. The contents of are hereby incorporated into this specification.
In addition to the above, it also contains a side chain structure in which the acidic groups of paragraphs 0028 to 0084 of JP-A-2011-153283 (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group. High molecular weight compounds containing constituents can be used, the contents of which can be incorporated and incorporated herein by reference.

The curable composition of the present invention may contain a resin that does not fall under any of the resin A and the resin B.

<Photopolymerization initiator>
The curable composition contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can initiate the polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from an ultraviolet region to a visible light region is preferable. Further, it may be an activator that causes some action with a photoexcited sensitizer to generate an active radical, and is an initiator that initiates cationic polymerization depending on the type of the polymerizable compound (radical polymerization initiator). May be.
Further, the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 in the range of 300 to 800 nm (preferably 330 to 500 nm).

The content of the photopolymerization initiator in the curable composition is not particularly limited, but is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition. As the photopolymerization initiator, one type may be used alone, or two or more types may be used. When two or more kinds of photopolymerization initiators are used in combination, the total content is preferably within the above range.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and the like. Examples thereof include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, hydroxyacetophenone and the like.
As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

More specifically, as the photopolymerization initiator, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone compound, for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used.
As the aminoacetophenone compound, for example, commercially available IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade name, all manufactured by BASF) can be used. As the aminoacetophenone compound, the compound described in JP-A-2009-191179, in which the absorption wavelength is matched with a long wave light source having a wavelength of 365 nm or a wavelength of 405 nm, can also be used.
As the acylphosphine compound, commercially available IRGACURE-819 or IRGACURE-TPO (trade name, both manufactured by BASF) can be used.

-Oxime compound As the photopolymerization initiator, an oxime ester-based polymerization initiator (oxime compound) is more preferable.
As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, or the compound described in JP-A-2006-342166 can be used.
Examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like. 2-Acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Examples thereof include carbonyloxyimino-1-phenylpropane-1-one.
In addition, J. C. S. Perkin II (1979) pp. 1653-1660), J. Mol. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, the compounds described in JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534977, and the compounds described in JP-A-2006-342166 are also listed. Be done.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) is also preferable. In addition, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831, ADEKA ARCULDS NCI-930 (manufactured by ADEKA), or N-1919 (carbazole / oxime ester skeleton-containing light). An initiator (manufactured by ADEKA) can also be used.

Further, as an oxime compound other than the above description, the compound described in JP-A-2009-5199004 in which an oxime is linked to the N-position of carbazole; the compound described in US Pat. No. 7,626,957 in which a heterosubstituted group is introduced into a benzophenone moiety; Compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye moiety; ketooxime compounds described in International Patent Publication No. 2009-131189; The compound described in Japanese Patent No. 7556910 contained in the same molecule; the compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source; etc. may be used. good.
For example, paragraphs 0274-0275 of JP2013-29760A can be referred to, the contents of which are incorporated herein.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. It should be noted that the NO bond of the oxime compound may be the (E) -form oxime compound, the (Z) -form oxime compound, or a mixture of the (E) -form and the (Z) -form. good.

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

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

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

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

In equation (2), R ¹ , R ² , R ³ and R ⁴ are synonymous with R ¹ , R ² , R ³ and R ⁴ in equation (1), and R ⁵ is −R. ⁶ , -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSO R ⁶ , -CN, a halogen atom, or a hydroxyl group, and R6 is an alkyl group having 1 to 20 carbon atoms, an aryl group having ⁶ to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 4 to 4 carbon atoms. 20 represents a heterocyclic group, X represents a direct bond or a carbonyl group, and a represents an integer of 0-4.

In the formula (3), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. Representing an alkyl group, R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon. The number 4 to 20 represents a heterocyclic group, where X represents a direct bond or a carbonyl group.

In equation (4), R ¹ , R ³ , and R ⁴ are synonymous with R ¹ , R ³ , and R ⁴ in equation (3), and R ⁵ is -R ⁶ , -OR ⁶ , ,. -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, Halogen atom, Alternatively, it represents a hydroxyl group, and R ⁶ is 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. Represented, X represents a direct bond or a carbonyl group, and a represents an integer from 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group, respectively. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. ^R4 is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. ^R5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. Direct binding is preferred for X.
Further, in the above formulas (3) and (4), R ¹ is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group, respectively. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. ^R4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. ^R5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. Direct binding is preferred for X.
Specific examples of the compounds represented by the formulas (1) and (2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein by reference.

Specific examples of the oxime compound preferably used in the curable composition are shown below. Among the following specific examples, the oxime compound represented by the general formula (A) (hereinafter, also referred to as “specific photopolymerization initiator”) is preferable because the obtained cured film is more excellent in the peeling inhibitory property. Examples of commercially available products of the specific photopolymerization initiator include IRGACURE-OXE03 (manufactured by BASF). Further, as the oxime compound, the compound described in Table 1 of International Publication No. 2015-036910 can also be used, and the above contents are incorporated in the present specification.

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

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

<Polymerization inhibitor>
The curable composition contains a polymerization inhibitor.
The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used. Examples of the polymerization inhibitor include phenolic polymerization inhibitors (eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-ditert-butyl-4-methylphenol, and the like. 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); Hydroquinone-based polymerization inhibitors (eg, , Hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); Kinone-based polymerization inhibitor (eg, benzoquinone, etc.); Free radical-based polymerization inhibitor (eg, 2,2,6,6-tetramethylpiperidin 1- Oxyl-free radicals, 4-hydroxy-2,2,6,6-tetramethylpiperidin1-oxyl-free radicals, etc.); Nitrobenzene-based polymerization inhibitors (eg, nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors. (For example, phenothiazine, 2-methoxyphenothiazine, etc.); and the like.
Among them, a phenol-based polymerization inhibitor or a free radical-based polymerization inhibitor is preferable because the curable composition has a more excellent effect.

The effect of the polymerization inhibitor is remarkable when it is used together with a resin containing a curable group.
The content of the polymerization inhibitor in the curable composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, preferably 0.001 to 0.2, based on the total solid content of the curable composition. The mass% is more preferable, and 0.008 to 0.05% by mass is further preferable. The polymerization inhibitor may be used alone or in combination of two or more. When two or more kinds of polymerization inhibitors are used in combination, the total content is preferably within the above range.
The ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the curable composition (content of the polymerization inhibitor / content of the polymerizable compound (mass ratio)) is more than 0.0005. Preferably, 0.0006 to 0.02 is more preferable, and 0.0006 to 0.005 is even more preferable.

<Surfactant>
The curable composition may contain a surfactant. The surfactant contributes to the improvement of the coatability of the curable composition.
When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
As the surfactant, one type may be used alone or two or more types may be used in combination. When two or more surfactants are used in combination, the total amount is preferably within the above range.

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

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

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

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, F780, and F781 (above, DIC); Florard FC430, FC431, and FC171 (above, Sumitomo 3M); Surfron S-382, SC-101, SC. -103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by Asahi Glass); and PF636, Examples thereof include PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA).
A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090.

<UV absorber>
The curable composition may contain an ultraviolet absorber. As a result, the shape of the pattern of the cured film can be made into a better (fine) shape.
As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorber can be used. As specific examples thereof, the compounds of paragraphs 0137 to 0142 (corresponding US2012 / 0068292, paragraphs 0251 to 0254) of JP2012-066418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. ..
In addition, a diethylamino-phenylsulfonyl UV absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The content of the ultraviolet absorber is preferably 0.001 to 15% by mass with respect to the total solid content of the curable composition.

<Silane coupling agent>
The curable composition may contain a silane coupling agent.
The silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. A hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group is a substituent that is directly linked to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the number of carbon atoms thereof is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
When forming a cured film on a substrate, the silane coupling agent improves the adhesion between the substrate and the cured film, so that fluorine atoms and silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded). It is preferable not to contain a fluorine atom, a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and a linear alkyl group having 8 or more carbon atoms. It is desirable that the branched alkyl group having 3 or more carbon atoms is not contained.

The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass with respect to the total solid content in the curable composition.
The curable composition may contain one type of silane coupling agent alone, or may contain two or more types of the silane coupling agent. When the curable composition contains two or more kinds of silane coupling agents, the total may be within the above range.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. Examples thereof include vinyltrimethoxysilane and vinyltriethoxysilane.

<Solvent>
The curable composition preferably contains a solvent.
The solvent is not particularly limited, and a known solvent can be used.
The content of the solvent in the curable composition is not particularly limited, but is preferably adjusted so that the solid content of the curable composition is 10 to 90% by mass, and is preferably 15 to 50% by mass. It is more preferable to be adjusted. The solid content is intended to be a component other than the solvent.
One type of solvent may be used alone, or two or more types may be used in combination. When two or more kinds of solvents are used in combination, it is preferable that the total solid content of the curable composition is adjusted to be within the above range.

Examples of the solvent include water and an organic solvent.
Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and acetyl acetone. , Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, butyl acetate, methyl lactate, N -Methyl-2-pyrrolidone, ethyl lactate and the like can be mentioned, but the present invention is not limited thereto.

[Manufacturing method of curable composition]
As the curable composition, it is preferable to first produce a dispersion composition in which a black coloring material is dispersed, and then mix the obtained dispersion composition with other components to obtain a curable composition.
The dispersion composition is preferably prepared by mixing a black color material, a resin B, and a solvent. It is also preferable to include a polymerization inhibitor in the dispersion composition.

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

In preparing the curable composition, each component may be blended together, or each component may be dissolved or dispersed in a solvent and then sequentially blended. Further, the charging order and working conditions at the time of blending are not particularly limited.

The curable composition is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (containing high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP) can be mentioned. Be done. Among these materials, polypropylene (containing high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, further preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. Within this range, it becomes possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the pigment while suppressing the filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the pore diameters of the second and subsequent filters are the same or larger than the pore diameter of the first filtering. Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., and the like.
As the second filter, a filter made of the same material as the first filter described above can be used. The pore size of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and even more preferably 0.3 to 6.0 μm.
The curable composition preferably does not contain impurities such as metals, metal salts containing halogens, acids and alkalis. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, further preferably 100 pt or less, particularly preferably 10 pt or less, and substantially not contained (below the detection limit of the measuring device). That) is the most preferable.
The impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

[Procedure for manufacturing a cured film]
The curable composition layer (composition layer) formed by using the curable composition can be cured to obtain a patterned cured film.
The method for producing the cured film is not particularly limited, but it is preferable to include the following steps.
-Curable composition layer forming process-Exposure process-Development process Each process will be described below.

<Curable composition layer forming step>
The curable composition layer forming step is a step of forming a curable composition layer using the curable composition. Examples of the step of forming the curable composition layer using the curable composition include a step of applying the curable composition on a substrate to form the curable composition layer.
The type of the substrate is not particularly limited, but when used as a solid-state image sensor, for example, a silicon substrate may be mentioned, and when used as a color filter (containing a color filter for a solid-state image sensor), a glass substrate or the like may be mentioned. ..
As a method for applying the curable composition on the substrate, various coating methods such as spin coating, slit coating, inkjet method, spray coating, rotary coating, cast coating, roll coating, and screen printing method are applied. be able to.
The curable composition applied on the substrate is usually dried at 70 to 150 ° C. under the condition of about 1 to 4 minutes to form a curable composition layer.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed by irradiating it with active light or radiation to cure the light-irradiated curable composition layer.
The method of light irradiation is not particularly limited, but it is preferable to irradiate light through a photomask having a patterned opening.
By using the curable composition of the present invention, deterioration of the line width stability of the cured film caused by diffraction and / or scattering of the irradiated light can be suppressed. In particular, since the influence of diffracted light is likely to occur in proximity exposure, there is a great advantage in using the curable composition of the present invention.
The exposure is preferably performed by irradiation with radiation, and as the radiation that can be used for the exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferable, and a high-pressure mercury lamp is preferable as the light source. The irradiation intensity is preferably 5 to 1500 mJ / cm ² , more preferably 10 to 1000 mJ / cm ² .
When the curable composition contains a thermal polymerization initiator, the curable composition layer may be heated in the above exposure step. The heating temperature is not particularly limited, but is preferably 80 to 250 ° C. The heating time is not particularly limited, but is preferably 30 to 300 seconds.
When the curable composition layer is heated in the exposure step, it may also serve as a post-heating step described later. In other words, when the curable composition layer is heated in the exposure step, the method for producing the cured film does not have to include the post-heating step.

<Development process>
Following the exposure step, a development process (development step) is performed to elute the unirradiated portion of the light in the developing solution into the developer. As a result, only the photo-cured portion remains.
An alkaline developer may be used as the developer. In that case, it is preferable to use an organic alkaline developer. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkaline aqueous solution (alkali developing solution) include an inorganic alkali developing solution and an organic alkaline developing solution.
The inorganic alkaline developer contains alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, and sodium metasilicate in a concentration of 0.001 to 10% by mass (preferably). An alkaline aqueous solution dissolved so as to have a concentration of 0.005 to 0.5% by mass) can be mentioned.
Examples of the organic alkaline developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline. , Pyrol, piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass (preferably 0.005 to 0.5% by mass). %), An alkaline aqueous solution dissolved so as to be%) can be mentioned.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant may be added to the alkaline aqueous solution. When a developer composed of such an alkaline aqueous solution is used, the cured film is generally washed (rinsed) with pure water after development.

The method for producing the cured film may include other steps.
The other steps are not particularly limited and may be appropriately selected according to the purpose.
Examples of other steps include a surface treatment step of the base material, a preheating step (pre-baking step), a post-heating step (post-baking step), and the like.
As the method for producing the cured film, it is preferable to include a step (post-heating step) of heating the curable composition layer after exposure between the exposure step and the developing step.
The heating temperature in the pre-heating step and the post-heating step is preferably 80 to 250 ° C.
The upper limit is more preferably 200 ° C. or lower, further preferably 150 ° C. or lower. The lower limit is more preferably 90 ° C. or higher.
The heating time in the pre-heating step and the post-heating step is preferably 30 to 300 seconds. The upper limit is more preferably 240 seconds, still more preferably 180 seconds or less. The lower limit is more preferably 60 seconds or more.

[Physical characteristics of cured film and use of cured film]
<Physical characteristics of cured film>
The cured film obtained by using the curable composition of the present invention has an excellent light-shielding property, and has an optical density (OD: Optical Density) of 2 per 1.0 μm in a wavelength region of 400 to 1200 nm. .0 or more is preferable, and 3.0 or more is more preferable. The upper limit is not particularly limited, but is generally preferably 10 or less. The cured film can be preferably used as a light-shielding film.
Further, in the present specification, when the optical density per 1.0 μm film thickness in the wavelength region of 400 to 1200 nm is 3.0 or more, the optical density per 1.0 μm film thickness is defined in the entire wavelength range of 400 to 1200 nm. Intended to be 3.0 or higher.
In the present specification, as a method for measuring the optical density of a cured film, first, a cured film is formed on a glass substrate, and the measurement is performed using a transmission densitometer (X-rite 361T (visual) densitometer). The film thickness at each location is also measured, and the optical density per predetermined film thickness is calculated.

Further, it is also preferable that the cured film has a surface uneven structure. By doing so, the reflectance of the cured film can be reduced when the cured film is a light-shielding film. The surface of the cured film itself may have a concavo-convex structure, or another layer may be provided on the cured film to impart the concavo-convex structure. The shape of the surface uneven structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm or more and 1.5 μm or less.
The reflectance of the cured film is preferably less than 7%, more preferably less than 5%, still more preferably less than 3%.
The method for producing the surface uneven structure is not particularly limited. For example, as described above, even if the number of ethylenically unsaturated groups contained in the polymerizable compound in the curable composition is adjusted to a predetermined range, the surface of the cured film is appropriately roughened and the surface is uneven. You can get the structure.
In addition, a method of containing an organic filler and / or an inorganic filler in the cured film or other layer, a lithography method using exposure development, or a cured film or other by an etching method, a sputtering method, a nanoimprint method, or the like. It may be a method of roughening the surface of the layer.
In addition to the above, as a method for reducing the reflectance of the cured film, a method of providing a low refractive index layer on the cured film, a method of providing a plurality of layers having different refractive indexes (for example, a high refractive index layer), and a method of providing a plurality of layers having different refractive indexes. , A method for forming a low optical density layer and a high optical density layer, which is described in JP-A-2015-1654.

Further, the cured film is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, and a digital camera; an OA (Office Automation) device such as a printer compound machine and a scanner; a surveillance camera, a bar code reader, and cash. Industrial equipment such as automated depository machines (ATMs: automated teller machines), high-speed cameras, and equipment with personal identification functions using face image authentication; in-vehicle camera equipment; endoscopes, capsule endoscopes, And medical camera equipment such as catheters; and biosensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, meteorological and oceanographic observation cameras, land resource exploration cameras, and space astronomical and deep space targets. It is suitable for light-shielding members and light-shielding films of optical filters and modules used in space equipment such as exploration cameras; and also antireflection members and antireflection films.

The cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The cured film is suitable for optical filters and optical films used for micro LEDs and micro OLEDs, as well as members for imparting a light shielding function or an antireflection function.
Examples of the micro LED and the micro OLED include those described in the special table 2015-500562 and the special table 2014-533890.

The cured film is also suitable as an optical filter and an optical film used in a quantum dot sensor and a quantum dot solid-state image sensor. Further, it is suitable as a member for imparting a light shielding function and an antireflection function. Examples of the quantum dot sensor and the quantum dot solid-state image sensor include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313.
It is also preferable to use the cured film as a light-shielding member and / or a light-shielding film of a headlight unit used for a headlight for a vehicle such as an automobile. It is also preferable to use it for an antireflection member, an antireflection film and the like.

<Light-shielding film, optical element, solid-state image sensor and solid-state image sensor>
The cured film obtained by using the curable composition of the present invention is also preferably used as a so-called light-shielding film. It is also preferable to use such a light-shielding film for a solid-state image sensor.
The light-shielding film is one of the preferred forms of the cured film obtained by using the curable composition of the present invention. That is, it is also preferable that the cured film of the present invention is a light-shielding film.
The method for producing a cured film, which is a light-shielding film, can be similarly performed by the method described as the above-mentioned method for producing a cured film. Specifically, a curable composition can be applied to a substrate to form a curable composition layer, which can be exposed and developed to produce a light-shielding film.

The present invention also includes the invention of an optical element. The optical element of the present invention is an optical element having the above-mentioned cured film (light-shielding film). Examples of the optical element include an optical element used in an optical device such as a camera, binoculars, a microscope, and a semiconductor exposure apparatus.
Above all, the optical element is preferably a solid-state image sensor mounted on, for example, a camera or the like.
As described above, the solid-state image pickup device of the present invention contains the above-mentioned cured film (light-shielding film). The form in which the solid-state image sensor contains a cured film (light-shielding film) is not particularly limited, and for example, a plurality of photodiodes constituting a light-receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a substrate. And those having a light receiving element made of polysilicon or the like and having a cured film on the light receiving element forming surface side of the support (for example, a portion other than the light receiving portion and / or a pixel for color adjustment) or on the opposite side of the forming surface. Can be mentioned.
The solid-state image sensor contains the solid-state image sensor.

Configuration examples of the solid-state image pickup device and the solid-state image pickup device will be described with reference to FIGS. 1 and 2. In addition, in FIGS. 1 and 2, in order to clarify each part, the ratio of the mutual thickness and / or the width is ignored and a part is exaggerated.
As shown in FIG. 1, the solid-state image sensor 100 includes a rectangular solid-state image sensor 101 and a transparent cover glass 103 that is held above the solid-state image sensor 101 and seals the solid-state image sensor 101. There is. Further, a lens layer 111 is provided on the cover glass 103 so as to be overlapped with the spacer 104. The lens layer 111 is composed of a support 113 and a lens material 112. The lens layer 111 may be configured such that the support 113 and the lens material 112 are integrally molded. When stray light is incident on the peripheral region of the lens layer 111, the effect of condensing light on the lens material 112 is weakened by the diffusion of light, and the light reaching the image pickup unit 102 is reduced. In addition, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 111 is provided with a light-shielding film 114 to block light. The cured film obtained by using the curable composition of the present invention can also be used as the light-shielding film 114.

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

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

An image pickup unit 102 is provided at the center of the surface of the chip substrate 106. Further, when stray light is incident on the peripheral region of the imaging unit 102, dark current (noise) is generated from the circuit in the peripheral region, so that the peripheral region is shielded by a light-shielding film 115. The cured film obtained by using the curable composition is preferably used as the light-shielding film 115.

A plurality of electrode pads 108 are provided on the surface edge of the chip substrate 106. The electrode pad 108 is electrically connected to the image pickup unit 102 via a signal line (may be a bonding wire) provided on the surface of the chip substrate 106 (which may be a bonding wire).

On the back surface of the circuit board 107, external connection terminals 109 are provided at positions substantially below each electrode pad 108. Each external connection terminal 109 is connected to the electrode pad 108 via a through electrode 110 that vertically penetrates the laminated substrate 105. Further, each external connection terminal 109 is connected to a control circuit that controls the drive of the solid-state image sensor 101, an image processing circuit that performs image processing on the image pickup signal output from the solid-state image sensor 101, and the like via wiring (not shown). Has been done.

As shown in FIG. 2, the image pickup unit 102 is composed of each unit provided on a substrate 204 such as a light receiving element 201, a color filter 202, and a microlens 203. The color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The cured film obtained by using the curable composition of the present invention can also be used as a black matrix 205 bm.

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

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

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

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

<Black Matrix>
The cured film obtained by using the curable composition of the present invention is also preferably contained in a black matrix. The black matrix may be contained in an image display device such as a color filter, a solid-state image sensor, and a liquid crystal display device.
The black matrix has already been described above; a black edge provided on the peripheral edge of an image display device such as a liquid crystal display device; a grid pattern and / or a stripe between red, blue, and green pixels. A black portion having a shape; a dot-shaped and / or a linear black pattern for light-shielding a TFT (thin film transistor); and the like can be mentioned. For the definition of this black matrix, see, for example, Taihei Kanno, "Dictionary of Terminology for Liquid Crystal Display Manufacturing Equipment", 2nd Edition, Nikkan Kogyo Shimbun, 1996, p. There is a description in 64.
The black matrix has high light-shielding properties (with optical density OD) in order to improve the display contrast and, in the case of an active matrix-driven liquid crystal display device using a thin film transistor (TFT), to prevent image quality deterioration due to light current leakage. 3 or more) is preferable.

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

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

<Color filter>
The cured film obtained by using the curable composition of the present invention is also preferably contained in a color filter.
The form in which the color filter contains a cured film is not particularly limited, and examples thereof include a color filter including a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the opening of the black matrix formed on the substrate can be exemplified.

A color filter containing a black matrix (cured film) can be produced, for example, by the following method.
First, a coating film (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a substrate. The resin composition for each color is not particularly limited, and a known resin composition can be used. However, in the curable composition described in the present specification, the black pigment is replaced with a colorant corresponding to each pixel. You may use the one.
Next, the resin composition layer is exposed through a photomask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed portion by a developing process, colored pixels can be formed in the opening of the black matrix by baking. By performing a series of operations using, for example, a resin composition for each color containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be produced.

It is also preferable that the color filter as described above is used in, for example, a liquid crystal display device.
In addition, there is no limitation on the use of the cured film (light-shielding film) obtained by using the curable composition of the present invention, and it may be used for, for example, an infrared sensor.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the invention should not be construed as limiting by the examples shown below.

[Preparation of curable composition]
A curable composition was prepared using the components shown below.

<Dispersion composition and black dye solution>
The following dispersion composition (dispersion liquid) and black dye solution were prepared and used for the preparation of the curable composition.

(A-1: Titanium Black Dispersion Liquid (A-1))
A titanium black dispersion (A-1) was obtained using the raw materials shown below.
-Titanium black (a-1) (details will be described later)
-Resin (X-1) (equivalent to resin B)
・ PGMEA (Propylene Glycol Monomethyl Ether Acetate)

The structure of the resin (X-1) is as follows. The acid value was 58 and the weight average molecular weight was 32000. The numbers attached to each repeating unit indicate the molar ratio of each unit.

Resin (X-1) (5.5 parts by mass) was added to titanium black (a-1) (20 parts by mass), and PGMEA was further added so that the solid content concentration was 35% by mass.
The obtained dispersion was sufficiently stirred with a stirrer and premixed. The obtained dispersion was subjected to a dispersion treatment under the following dispersion conditions using an NPM Pilot manufactured by Symmal Enterprises to obtain a titanium black dispersion liquid (A-1).

(Dispersion condition)
・ Bead diameter: φ0.05mm
-Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 11m / s
・ Amount of mixed liquid to be dispersed: 15.0 g
・ Circulation flow rate (pump supply amount): 60 kg / hour
-Treatment liquid temperature: 20 to 25 ° C
・ Cooling water: Tap water 5 ℃
・ Bead mill ring passage internal volume: 2.2L
・ Number of passes: 84 passes

Preparation of Titanium Black (a-1) Titanium oxide MT-150A (trade name, manufactured by Teika) (100 g) with an average particle size of 15 nm, silica particles with a BET surface area of 300 m ² / g AEROSIL® 300/30 (Ebonic) (25 g) and dispersant DISPERBYK-190 (trade name, manufactured by BYK) (100 g), weighed, added ion electric exchange water (71 g), and rotated around using KURABO MAZERSTAR KK-400W. A uniform aqueous mixture was obtained by treating for 20 minutes at a rotation speed of 1360 rpm and a rotation speed of 1047 rpm. This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), the atmosphere is replaced with nitrogen, and ammonia gas is added at 100 mL / min at the same temperature for 5 hours. Nitriding reduction treatment was carried out by flowing. After completion, the recovered powder was pulverized in a mortar to obtain a powdery titanium black (a-1) having a specific surface area of 73 m ² / g containing Si atoms.

(A-2: Carbon black dispersion (A-2))
A carbon black dispersion (A-2) was obtained using the raw materials shown below.
・ Coated carbon black (details will be described later)
-Resin (X-1) (corresponding to resin B, same as that used for preparing the titanium black dispersion (A-1))
・ Solsperse 12000 (pigment derivative, manufactured by Lubrizol)
・ PGMEA (Propylene Glycol Monomethyl Ether Acetate)

Resin (X-1) (4.5 parts by mass) and Solsparse 12000 (1 part by mass) are added to the coated carbon black (20 parts by mass) so that the solid content concentration becomes 35% by mass. PGMEA was added.
The obtained mixed solution was sufficiently stirred with a stirrer and premixed. Further, the dispersion was subjected to a dispersion treatment under the following dispersion conditions using an Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. to obtain a dispersion composition. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a carbon black dispersion (A-2).

(Dispersion condition)
・ Bead diameter: φ0.05mm
-Bead filling rate: 75% by volume
・ Mill peripheral speed: 8m / sec
-Amount of mixed liquid to be dispersed: 500 g
・ Circulation flow rate (pump supply amount): 13 kg / hour
-Treatment liquid temperature: 25 to 30 ° C
・ Cooling water: Tap water ・ Bead mill ring passage internal volume: 0.15L
・ Number of passes: 90 passes

-Manufacturing of coated carbon black Carbon black was manufactured by the usual oil furnace method. However, as the raw material oil, ethylene bottom oil having a small Na content, Ca content, and S content was used, and combustion was performed using gas fuel. Further, as the reaction stop water, pure water treated with an ion exchange resin was used.
Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. This slurry was transferred to a container with a screw type stirrer, and toluene (600 g) in which the epoxy resin "Epicoat 828" (manufactured by Japan Epoxy Resin) (60 g) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, all of the carbon black dispersed in water moved to the toluene side and became particles of about 1 mm.
Next, after draining with a 60-mesh wire mesh, the separated particles were placed in a vacuum dryer and dried at 70 ° C. for 7 hours to remove toluene and water. The resin coating amount of the obtained coated carbon black was 10% by mass with respect to the total amount of the carbon black and the resin.

(A-3: Black dye solution (A-3))
A black dye solution (A-3) was obtained using the raw materials shown below.
・ VALUESTAR BLACK 3804 (black dye, manufactured by Orient Chemical Industry Co., Ltd.)
・ PGMEA (Propylene Glycol Monomethyl Ether Acetate)

PGMEA (73.2 parts by mass) was added to VALIFAST BLACK 3804 (manufactured by Orient Chemical Industry Co., Ltd.) (26.8 parts by mass) and dissolved to prepare a black dye solution (A-3).

<Resin (resin solution)>
Resin solutions (B-1) to (B-9) containing the resin represented by the following structure 1 or structure 2 were used for preparing the curable composition.
In the structural formula, the numbers attached to each repeating unit (X and Y are also numbers) are intended to be the content (molar ratio) of each repeating unit in the resin.
In the resin of structure 1, the ratio of X and Y was appropriately changed so that the acid value of each resin became the value shown in Table 1.

The structure of the resin contained in the resin solutions (B-1) to (B-9), and the molecular weight and acid value thereof are shown in the table below.
The ratio (mass ratio) of the content of the resin and the solvent (PGMEA) contained in the resin solution is also shown in the table below.
The resin contained in the resin solutions (B-1) to (B-5) corresponds to the resin A.

<Photopolymerization initiator>
The following photopolymerization initiators were used in the preparation of the curable composition.
・ C-1: IRGACURE OXE-03 (manufactured by BASF)
・ C-2: IRGACURE OXE-02 (manufactured by BASF)
・ C-3: IRGACURE 369 (manufactured by BASF)
Among the above photopolymerizable compounds, C-1 and C-2 are oxime ester-based polymerization initiators.
Further, C-1 has the following structure.

<Polymerizable compound>
The following polymerizable compounds were used to prepare the curable composition.
-D-1: A compound represented by "C- (CH ₂ OOC-CH = CH ₂ ) ₄ ". (4 functional, double bond equivalent 11.3 mmol / g)
D-2: The following compound (5 to 6 functional, double bond equivalent 10.1 mmol / g)
D-3: The following compound (tetrafunctional, double bond equivalent 7.6 mmol / g)
The above-mentioned "functional" value indicates the number of ethylenically unsaturated groups contained in one molecule of the polymerizable compound.
In D-2, a pentafunctional polymerizable compound and a hexafunctional polymerizable compound are mixed, and the mixing ratio thereof is a pentafunctional polymerizable compound / a hexafunctional polymerizable compound = 30/70 (). (Mass ratio). The double bond equivalent of D-2 as a whole (the weighted average value of the double bond equivalents of the hexafunctional polymerizable compound and the pentafunctional polymerizable compound) is 10.1 mmol / g.

<Surfactant>
The following surfactants were used in the preparation of the curable composition.
E-1: Surfactant represented by the following structural formula The numbers attached to each repeating unit in the following structural formula indicate the molar ratio of each repeating unit. Further, in the structural formula, m ₁ = 17, m ₂ = 17, l ₁ + n ₁ = 14, l ₂ + n ₂ = 14. The weight average molecular weight is 15,000.

<Polymerization inhibitor>
The following polymerization inhibitors were used to prepare the curable composition.
・ P-Methoxyphenol

<Solvent>
The following solvents were used to prepare the curable composition.
・ Cyclohexanone

The above components were mixed to prepare a curable composition for use in each Example or Comparative Example.

〔test〕
<Measurement of line width (line width stability)>
The curable composition immediately after preparation was applied onto a glass substrate by a spin coating method to form a coating film having a film thickness of 1.7 μm after exposure. After prebaking at 100 ° C. for 120 seconds, a high-pressure mercury lamp (lamp power 50 mW / cm) was used for the obtained curable composition layer using UX-1000SM-EH04 (manufactured by Ushio, Inc.). In ² ), exposure by the proximity method (proximity exposure) was performed through a mask of a line-and-space pattern having an opening line width of 50 μm.
At this time, the exposure amount was adjusted so that the average value (average value of 100 points) of the width (line width) of the line portion of the pattern obtained after development was 50 μm.
After the exposure, development was carried out by the paddle method for 15 seconds with a developer (CD-2060, manufactured by Fujifilm Electronics Materials Co., Ltd.) using a developing device (AD-1200, manufactured by Mikasa). Further, it was washed with pure water for 30 seconds using a shower nozzle to form a patterned cured film (also simply referred to as “pattern”) on the substrate.
The line width of the pattern was measured using an optical microscope (100 points), and the variation in line width (3σ) was evaluated from the following viewpoints.

A: Line width variation is 4 μm or less B: Line width variation is more than 4 μm 8 μm or less C: Line width variation is more than 8 μm

<Measurement of undercut width (undercut suppression)>
A pattern was formed on the substrate in the same manner as in the line width measurement test.
A cross-sectional SEM image of the pattern was observed using a scanning electron microscope (SEM, S-4800 (Hitachi High-Technologies Corporation)), the undercut width was measured, and the evaluation was made from the following viewpoints.

A: No problem when the undercut width is less than 1.2 μm B: Practical problem when the undercut width is 1.2 μm or more and less than 1.8 μm C: Practical use when the undercut width is 1.8 μm or more Problematic level

<Measurement of peeling (peeling inhibitory property)>
A pattern was formed on the substrate in the same manner as in the line width measurement test.
A microscope image of the surface of the pattern was observed using an optical microscope, and the presence or absence of pattern peeling was evaluated from the following viewpoints.

A: No problem with peeling in the entire pattern B: Peeling is seen in some patterns but no problem in practical use C: Most of the pattern is peeled off and there is a problem in practical use

<Measurement of residue (residue inhibitory property)>
A pattern was formed on the substrate in the same manner as in the line width measurement test.
Using a scanning electron microscope (S-4800 (Hitachi High-Technologies Corporation)), the portion of the substrate from which the curable composition layer was removed in the developing step was observed and evaluated from the following viewpoints.

A: No problem with no residue B: Some residue is seen but no problem in practical use C: A lot of residue is seen and there is no problem in practical use

<Evaluation of reflectance>
A cured film-forming substrate having a cured film on the substrate was produced in the same manner as in the line width measurement test, except that light was irradiated without using a mask during exposure.
Measured by injecting light with a wavelength of 500 nm at an incident angle of 5 ° using a spectroscope manufactured by Nippon Spectrometer Co., Ltd. (product name: V7200, combined with an absolute reflectance measuring unit) on the produced cured film-forming substrate. The reflectance was evaluated from the following viewpoints. The reflectance is preferably small.

A: No problem if the reflectance is less than 3% B: No problem in practical use if the reflectance is 3% or more and less than 5% C: No problem in practical use if the reflectance is 5% or more and less than 7% Level D: No problem in practical use Is 7% or more, which is a practically problematic level

<Evaluation of change rate of reflectance (stability of reflectance over time)>
The prepared curable composition was stored at 23 ° C. for 10 days and then at 7 ° C. for 90 days. Except for the fact that the curable composition after such storage treatment was used, the reflectance was evaluated in the same manner as described above, and the rate of change in reflectance was calculated from the obtained results according to the following formula. The temporal stability of reflectance was evaluated as a standard. The rate of change in reflectance is preferably small.
(Equation) (Reflectance rate of change) = (((Reflectance of the cured film formed using the curable composition after the storage treatment))-(Formed using the curable composition before the storage treatment) (Reflectance of cured film)) / (Reflectance of cured film formed using the curable composition before storage treatment)) x 100 (%)

A: There is no problem if the rate of change in reflectance is less than 5%.
B: A problematic level when the rate of change in reflectance is 5% or more.

<Evaluation of rate of change in line width (stability of line width over time)>
The prepared curable composition was stored at 23 ° C. for 10 days and then at 7 ° C. for 90 days.
The curable composition after such a preservation treatment was used to form a pattern as in the line width measurement test. However, here, the exposure amount was the same as the exposure amount when the pattern having the line width of 50 μm was formed by using the curable composition before the storage treatment.
The average value obtained by measuring the line width of the obtained pattern at 100 points was taken as the line width of the pattern formed by using the curable composition after the storage treatment.
From the obtained results, the rate of change of the line width was calculated according to the following formula, and the stability of the line width over time was evaluated according to the following criteria. The rate of change in line width is preferably small.
(Formula) (Rate of change in line width) = (((Line width of pattern formed using curable composition after storage treatment))-(Pattern formed using curable composition before storage treatment) Line width)) / (Line width of line pattern formed using the curable composition before storage treatment)) x 100 (%)

A: There is no problem if the rate of change in line width is less than 5%.
B: A problematic level when the rate of change in line width is 5% or more.

〔result〕
The table below shows the formulations of the curable compositions used in each Example and Comparative Example, as well as the test results.
No pattern could be formed in the compounds of Comparative Examples 1 and 4.
In the table, the column of "content" indicates the content (mass%) of each component in each curable composition. The description of "remaining" as the content of the solvent indicates that the required amount of solvent was added so that the total content of each component shown in the table would be 100.
For example, the curable composition of Example 1 shows that it contains 63% by mass of the titanium black dispersion (A-1).
The column of "acid value of resin" indicates the acid value of the resin contained in the resin solution used in the curable composition.
The column of "Molecular weight of resin" indicates the weight average molecular weight of the resin contained in the resin solution used in the curable composition.
The column of "resin B" indicates whether or not the curable composition contains resin B. The case where the above requirements were satisfied was designated as A, and the case where the above requirements were not met was designated as B.
The column of "Oxime-based photopolymerization initiator" indicates whether or not the photopolymerization initiator contained in the curable composition is an oxime ester-based polymerization initiator. The case where the above requirements were satisfied was designated as A, and the case where the above requirements were not met was designated as B.
The column of "Specified photopolymerization initiator" indicates whether or not the photopolymerization initiator contained in the curable composition is a specific polymerization initiator. The case where the above requirements were satisfied was designated as A, and the case where the above requirements were not met was designated as B.
The column of "Type of black color material" indicates the type of black color material contained in the curable composition. TB is intended for titanium black (titanium nitride), CB is intended for carbon black, and black dye is intended for black dye.
The column of "Number of functional groups of the polymerizable compound" indicates the number of ethylenically unsaturated groups contained in the polymerizable compound contained in the curable composition.

It was confirmed that by using the curable composition of the present invention, a cured film (containing a patterned cured film) having excellent line width stability can be formed.
Further, in the curable composition of Comparative Example 5 containing no polymerization inhibitor, there was no problem in the temporal stability of the line width of the obtained cured film, but there was a problem in the temporal stability of the reflectance. On the other hand, the curable composition of the present invention containing a polymerization inhibitor also had good temporal stability of the reflectance of the obtained cured film.
It was confirmed that when the curable composition contained the resin B, the reflectance of the cured film was more excellent (comparison between Examples 5 and 6).
When a black pigment is used as the black color material, the reflectance of the cured film is better (compared with Examples 5 and 6), and when the black pigment is titanium black (titanium nitride), the cured film is peeled off. It was confirmed that the inhibitory property was more excellent (comparison between Examples 1 and 5).
It was confirmed that when the acid value of the resin A satisfying the requirement 1 is 170 to 300 mgKOH / g, the line width stability of the cured film, the undercut inhibitory property, and the reflectance are more excellent (as in Example 1). Comparison with 8).
When the weight average molecular weight of the resin A satisfying the requirement 2 is 6500 or less, the residue suppressing property of the cured film is more excellent (compared with Examples 9 and 10), and when it is 3000 to 5000, the line width of the cured film is obtained. It was confirmed that the stability, the undercut inhibitory property, and the reflectance were better (comparison between Examples 1 and 9).
When the photopolymerizable compound is an oxime-based photopolymerization initiator, the cured film has better linear width stability and undercut inhibitory properties (compared with Examples 3 and 12), and is a specific photopolymerization initiator. It was confirmed that the peeling inhibitory property of the cured film was more excellent (comparison between Examples 1 and 3).
When the number of ethylenically unsaturated groups contained in the polymerizable compound is 4, the reflectance of the cured film is higher (comparison between Example 7 and other examples), and further, the double bond of the polymerizable compound is obtained. When the equivalent was 11.0 mmol / g or more, it was confirmed that the line width stability, undercut inhibitory property, peeling inhibitory property, and reflectance of the cured film were more excellent (comparison between Examples 1 and 11). ).

100 ... Solid-state image sensor 101 ... Solid-state image sensor 102 ... Image pickup unit 103 ... Cover glass 104 ... Spacer 105 ... Laminated substrate 106 ... Chip substrate 107 ... Circuit substrate 108 ... Electrode pad 109 ... External connection terminal 110 ... Through electrode 111 ... Lens layer 112 ... Lens material 113 ... Support 114, 115 ... Hardened film 201 ... Light receiving element 202 ... Color filter 201 ... Light receiving element 202 ... Color filter 203 ... Micro lens 204 ... Substrate 205b ... Blue pixel 205r ... Red pixel 205g ... Green pixel 205bm ...・ Black matrix 206 ・ ・ ・ p-well layer 207 ・ ・ ・ Read gate part 208 ・ ・ ・ Vertical transfer path 209 ・ ・ ・ Element separation region 210 ・ ・ ・ Gate insulating film 211 ・ ・ ・ Vertical transfer electrode 212 ・ ・ ・ Curing Films 213, 214 ... Insulation film 215 ... Flattening film

Claims (18)

Contains a black colorant, a polymerizable compound, a resin A, a photopolymerization initiator, and a polymerization inhibitor.
The resin A is a curable composition that satisfies either the requirement of having an acid value of 120 to 350 mgKOH / g and having a weight average molecular weight of 3000 to 7500.
A curable composition having a double bond equivalent of the polymerizable compound of 11.0 mmol / g or more. However, when the curable composition contains a plurality of types of the polymerizable compound and their double bond equivalents are not the same, the mass ratio of each polymerizable compound in the total polymerizable compound and each polymerizable compound. The sum of the products of the compounds with the double bond equivalents is taken as the double bond equivalent. The curable composition according to claim 1 , wherein the acid value of the resin A is 170 to 300 mgKOH / g. The curable composition according to claim 1 or 2 , wherein the photopolymerization initiator is an oxime ester-based polymerization initiator. Contains a black colorant, a polymerizable compound, a resin A, a photopolymerization initiator, and a polymerization inhibitor.
The resin A is a curable composition having an acid value of 170 to 300 mgKOH / g.
A curable composition in which the photopolymerization initiator is an oxime ester-based polymerization initiator. The curable composition according to any one of claims 1 to 4, wherein the mass ratio of the content of the polymerization inhibitor to the content of the polymerizable compound is more than 0.0005. Contains a black colorant, a polymerizable compound, a resin A, a photopolymerization initiator, and a polymerization inhibitor.
The resin A is a curable composition having an acid value of 170 to 300 mgKOH / g.
A curable composition in which the mass ratio of the content of the polymerization inhibitor to the content of the polymerizable compound is more than 0.0005. Further, claim 1 to 6, wherein the resin B is different from the resin A and has one or more groups selected from the group consisting of an oxyalkylene group and an oxyalkylene carbonyl group. The curable composition according to any one item. The curable composition according to any one of claims 1 to 7 , wherein the polymerizable compound has four ethylenically unsaturated groups. The curable composition according to any one of claims 1 to 8 , wherein the resin A has a weight average molecular weight of 3000 to 5000. The curable composition according to any one of claims 1 to 9, wherein the content of the repeating unit derived from the (meth) acrylic monomer is 50 mol% or more in all the repeating units of the resin A. The curable composition according to any one of claims 1 to 10, wherein the resin A is a copolymer of benzyl (meth) acrylate and (meth) acrylic acid. The curable composition according to any one of claims 1 to 11, wherein the photopolymerization initiator is a compound represented by the following general formula (A).

The curable composition according to any one of claims 1 to 12, wherein the black color material is a black pigment. A cured film formed by using the curable composition according to any one of claims 1 to 13. The cured film according to claim 14, which is a light-shielding film. An optical element having the cured film according to claim 14 or 15. A solid-state image sensor having the cured film according to claim 14 or 15. A color filter having the cured film according to claim 14 or 15.

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