JP6797889B2 - Curable composition, light-shielding film, solid-state image sensor, and color filter - Google Patents

Description

The present invention relates to curable compositions, light-shielding films, solid-state image sensors, and color filters.

Patent Document 1 describes a photosensitive resin curable composition for a black column spacer containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound having a specific structure, and a light-shielding agent.

Japanese Unexamined Patent Publication No. 2013-231935

Solid-state image sensors mounted on digital cameras, smartphones, etc. include CCDs (Charge-Coupled Devices) and CMOSs (Complementary Metal Oxide Semiconductors) behind them in addition to shooting lenses. It has a solid-state image sensor. This solid-state image sensor is provided with a light-shielding film for the purpose of light-shielding the back surface side, preventing noise generation due to light-shielding in the infrared region between pixels, and improving image quality.

The present inventors have defined the light reflectance of a film obtained by curing the photosensitive resin curable composition described in Patent Document 1 (light reflectance measured by a method described later, hereinafter simply "reflectance". As a result of examining (), it was found that the reflectance is high and the level of low reflectance required for a light-shielding film has not been reached recently.

Therefore, an object of the present invention is to provide a curable composition capable of producing a cured film having excellent low reflectivity. Another object of the present invention is to provide a light-shielding film obtained by curing the above-mentioned curable composition, a solid-state image sensor having the above-mentioned light-shielding film, and a color filter.

As a result of diligent studies to achieve the above problems, the present inventors have found that the above problems can be solved by a curable composition containing a specific component, and have completed the present invention.
That is, it was found that the above problem can be achieved by the following configuration.

(1) A curable composition containing a colorant, a photoradical polymerization initiator, a polymerizable compound, a base generator, and a dispersant.
(2) The curable composition according to (1), wherein the base generator contains a photobase generator.
(3) The curable composition according to (2), wherein the mass ratio of the photobase generator to the dispersant is 0.08 to 0.5.
(4) The curable composition according to any one of (2) and (3), wherein the photobase generator is represented by the general formula (PBG) described later.
(5) The curable composition according to any one of (2) to (4), wherein the base generated from the photobase generator is an amine compound, and the molecular weight of the amine compound is 150 or less.
(6) The curable composition according to any one of (1) to (5), wherein the photoradical polymerization initiator is an oxime-based initiator.
(7) The curable composition according to any one of (1) to (6), wherein the colorant is a light-shielding pigment.
(8) The curable composition according to (7), wherein the light-shielding pigment is a titanium compound.
(9) The curable composition according to any one of (1) to (8), which further contains a fluororesin.
(10) The curable composition according to any one of (1) to (9), which further contains two or more kinds of organic solvents.
(11) A light-shielding film obtained by curing the curable composition according to any one of (1) to (10).
(12) A solid-state image sensor having the light-shielding film according to (11).
(13) A color filter having the light-shielding film according to (12).

According to the present invention, it is possible to provide a curable composition capable of producing a cured film having excellent low reflectivity. Further, according to the present invention, it is possible to provide a light-shielding film obtained by curing the above-mentioned curable composition, a solid-state image sensor having the above-mentioned light-shielding film, and a color filter.

It is a perspective view which shows the solid-state image sensor of 1st Embodiment. It is an exploded perspective view of the solid-state image sensor of 1st Embodiment. It is sectional drawing which shows the solid-state image sensor of 1st Embodiment. It is sectional drawing which shows the solid-state image sensor of 2nd Embodiment. It is sectional drawing which shows the solid-state image sensor of 3rd Embodiment. It is sectional drawing which shows the solid-state image sensor of 4th Embodiment.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of groups (atomic groups) in the present specification, notations that do not describe substitutions and non-substitutions include those that do not have a substituent and those that have a substituent as long as the effects of the present invention are not impaired. It includes. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is synonymous with each compound.
Further, the term "radiation" in the present specification means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. Further, in the present specification, light means active light rays or radiation. Unless otherwise specified, the term "exposure" as used herein refers to not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, and EUV light, but also particle beams such as electron beams and ion beams. Drawing by is also included in the exposure.
Further, in the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either.
Further, in the present specification, "monomer" and "monomer" are synonymous. The monomer in the present specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less unless otherwise specified. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. A polymerizable functional group is a group involved in a polymerization reaction.
In addition, the term "preparation" in the present specification includes not only synthesizing or blending a specific material to prepare the material, but also procuring a predetermined material by purchasing the material.
Further, in the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

[Curable composition]
The curable composition of the present invention contains a colorant, a photoradical polymerization initiator, a polymerizable compound, a base generator, and a dispersant.

According to the curable composition of the present invention having such a structure, a cured film having excellent low reflectivity can be produced.
The mechanism by which this effect is obtained is not clear in detail, but the present inventors speculate as follows.

The curable composition of the present invention is applied onto a substrate by a method described later to form a coating film, and the coating film is cured to prepare a cured film (hereinafter, also simply referred to as "cured film"). be able to. Since the curable composition of the present invention contains a photoradical polymerization initiator and a base generator, when the above-mentioned coating film is irradiated with radiation of a predetermined wavelength, the polymerization reaction of the polymerizable compound by the photoradical polymerization initiator It is presumed that the reaction of generating radicals from the base generator and the reaction of generating radicals proceed competitively. This tendency is more remarkable when the base generator contains a photobase generator.
In the portion close to the surface on which the radiation is incident (a shallow portion in the coating film, that is, a region having a shallow depth from the coating film surface, hereinafter referred to as "upper region"), the above reaction proceeds and curing proceeds. At the same time, the base generator is decomposed to generate a base, and the base diffuses in the coating film. On the other hand, in a portion far from the incident surface of radiation (a deep portion in the coating film, that is, a region close to the surface of the base material, hereinafter referred to as "lower region"), the amount of radiation reached is higher than that in the upper region. Few. Therefore, as described above, in a system in which the reaction of the photoradical polymerization initiator (radical generation) and the base generation by the base generator proceed competitively, the polymerization of the polymerizable compound by the photoradical polymerization initiator in the lower region The progress rate of the reaction is presumed to be slower than that in the upper region. In particular, when the curable composition of the present invention contains a photobase generator, the radiation required for radical generation can also be used for base generation. Therefore, in the lower region where the amount of radiation reaching is relatively small, it is presumed that the progress rate of the polymerization reaction of the polymerizable compound by the photoradical polymerization initiator is slower than in the upper region. Further, since the base generated from the base generator diffuses from the upper region to the lower region, the progress of the polymerization reaction is further suppressed.
As described above, it is presumed that the rate and / or the degree of progress of the polymerization reaction differs between the upper region and the lower region. Therefore, in the cured film obtained by curing this coating film, the stress generated by the curing shrinkage differs between the upper region and the lower region, so that fine wrinkles occur in the upper region, which causes the cured film to have low reflectivity. It is presumed that it is contributing.

In the following, each component of the curable composition of the present invention will be described in detail.

[Colorant]
The curable composition of the present invention contains a colorant. As the colorant, a known colorant can be used, but it is preferable to contain a pigment. As the pigment, for example, when used for manufacturing a color filter, chromatic pigments (chromatic colors) such as R (red), G (green), and B (blue) that form the color pixels of the color filter. Pigments) can be used. When the cured film is used as a light-shielding film or a black matrix, the colorant preferably contains a light-shielding pigment because the cured film has excellent light-shielding properties.

As the light-shielding pigment, a known light-shielding pigment can be used, and carbon black, a titanium compound, iron oxide, manganese oxide, and graphite can be used from the viewpoint of achieving a high optical density (OD value) with a small amount. Etc. are preferable, and among them, it is more preferable to contain at least one selected from the group consisting of carbon black and titanium compounds, and titanium compounds are even more preferable. Specific examples of the light-shielding pigment include C.I. I. Examples thereof include organic pigments such as Pigment Black 1 and inorganic pigments such as Pigment Black 7.

As the titanium compound, known compounds can be used, and examples thereof include titanium oxide and titanium black. Of these, titanium black is preferable because it has a light-shielding property for a wide range of light rays of 400 to 1000 nm and has a high light transmittance in a wavelength range (less than 400 nm) that may be used for pattern formation of a light-shielding film. ..

Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide titanium nitride, titanium nitride and the like. The surface of the titanium black particles can be modified as needed for the purpose of improving dispersibility and suppressing cohesiveness. The surface of the titanium black particles can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, it is also possible to treat with a water-repellent substance as shown in Japanese Patent Application Laid-Open No. 2007-302836.
Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of the individual particles are small.
Specifically, the average primary particle size of titanium black is preferably in the range of 10 nm to 45 nm. The particle size in the present invention, that is, the particle diameter, is the diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles is obtained by measuring and averaging the areas of 300 particles obtained by photographing with an electron micrograph, and correcting the photographing magnification.

The specific surface area of titanium black is not particularly limited, but it is a value measured by the BET (Brunauer, Emmett, Teller) method because the water repellency after surface treatment of the titanium black with a water repellent agent has a predetermined performance. Is usually 5 m ² / g or more and 150 m ² / g or less, and particularly preferably 20 m ² / g or more and 120 m ² / g or less.
Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13RN, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilak ( Tilak) D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

Further, 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 curable composition, and the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is 0 in terms of mass. It is preferably 05 or more.
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).
If the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion in the present invention exceeds 0.5 (mass conversion), it is difficult to produce a curable composition using the dispersion. Therefore, the upper limit is preferably 0.5.
Further, when the light-shielding film using the disperse is patterned by optical lithography or the like, the residue is less likely to remain in the removed portion and the light-shielding ability is excellent. The Si / Ti of the disperse is 0.05 or more and 0. It is more preferably 5 or less, and further preferably 0.07 or more and 0.4 or less.
In order to change the Si / Ti of the dispersant (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.
Here, a specific embodiment for changing the Si / Ti of the dispersion to be dispersed will be described.
Titanium black in which Si / Ti is adjusted to, for example, 0.05 or more is prepared by, for example, the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of JP-A-2008-266045. Can be made.

In the present invention, the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms is adjusted to a suitable range (for example, 0.05 or more). When the light-shielding film is formed using the curable composition containing the dispersion, the residue derived from the curable composition outside the region where the light-shielding film is formed is reduced. The residue contains components derived from a curable composition such as titanium black particles and a resin component.
The reason why the residue is reduced is not yet clear, but the dispersant as described above tends to have a small particle size (for example, the particle size is 30 nm or less), and the Si atom of the dispersant tends to be small. It is speculated that the increase in the contained components reduces the adsorptivity of the entire film to the substrate, which contributes to the improvement of the developability of the uncured curable composition (particularly titanium black) in the formation of the light-shielding film. doing.
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 dispersant containing titanium black and Si atom (preferably Si / Ti is mass-converted). The light-shielding film formed by using (with a value of 0.05 or more) exhibits excellent light-shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is determined by, for example, the method (1-1) or method (1-2) described in paragraph 0033 of JP2013-249417A. ) Can be used for measurement.
Further, regarding the dispersion to be contained in the light-shielding film obtained by curing the curable composition, is the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion to be 0.05 or more? To determine whether or not, 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.
Further, in this dispersion, in addition to titanium black, for the purpose of adjusting dispersibility, colorability, etc., composite oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, and , Aniline black and the like may be used together as a dispersant by combining one type or two or more types.
In this case, it is preferable that the dispersed material made of titanium black accounts for 50% by mass or more of the total dispersed material.
Further, in this dispersion, for the purpose of adjusting the light-shielding property, other colorants (organic pigments, dyes, etc.) may be used in combination with titanium black as long as the effects of the present invention are not impaired. Good.
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 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 the silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
The curable composition of the present invention may contain one type of titanium black, or may contain two or more types.

Examples of the process for dispersing the pigment include a process using compression, squeezing, impact, shearing, cavitation and the like as the mechanical force used for dispersion. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and microfluidizers. In addition, "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and practical comprehensive data collection of industrial applications, Management Development Center Publishing Department The process and disperser described in "Published October 10, 1978" can be suitably used. Further, the pigment may be miniaturized by a salt milling step. As the materials, equipment, treatments, conditions and the like used in the salt milling step, for example, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used.
Of these, a sand mill (bead mill) is preferable. Further, in the dispersion treatment of the pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter or to treat under conditions in which the dispersion efficiency is increased by increasing the filling rate of the beads, and further filtering after the dispersion treatment. It is preferable to remove the elementary particles by centrifugation and / or centrifugation.

The curable composition of the present invention may contain an extender pigment, if necessary, in addition to the colorant. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more. The amount of the extender pigment used is usually 0 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the colorant. In the present invention, colorants and extender pigments can be used by modifying their surfaces with a polymer, if necessary.

One type of colorant may be used alone, or two or more types may be used in combination. As the colorant, a colored organic pigment such as red, blue, yellow, green, and purple may be contained. When the light-shielding pigment and the colored organic pigment are used in combination, it is preferable to use 1 to 40% by mass of the colored organic pigment with respect to the light-shielding pigment. From the viewpoint of adjusting the color, it is preferable to use a red pigment and a light-shielding pigment in combination, and the red pigment is preferably Pigment Red 254, although it is not particularly limited. Further, from the viewpoint of enhancing the light-shielding property, it is preferable to use the yellow pigment and the light-shielding pigment in combination, and the yellow pigment is preferably Pigment Yellow 150, although it is not particularly limited.

The content of the colorant in the curable composition of the present invention is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and 35 to 60% by mass with respect to the total solid content in the curable composition. % Is more preferable.

[Photoradical polymerization initiator]
The curable composition of the present invention contains a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photoradical polymerization initiators. For example, those having photosensitivity in the ultraviolet region to the visible light region are preferable. Further, the photoradical polymerization initiator may be an activator that produces an active radical by causing some action with the photoexcited sensitizer. Further, the photoradical polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 in the range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).

The photoradical polymerization initiator is preferably a compound having at least an aromatic group, for example, (bis) acylphosphine oxide or an ester thereof, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether type. Compounds, Ketal derivative compounds, thioxanthone compounds, oxime ester compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, Ketal derivatives Examples thereof include compounds, onium salt compounds such as metallocene compounds, organic boron salt compounds, and disulfone compounds. From the viewpoint of sensitivity, an oxime ester compound, an acylphosphine oxide compound, an acetophenone compound, an α-aminoketone compound, a trihalomethyl compound, a hexaarylbiimidazole compound, or a thiol compound is preferable, and an oxime ester compound (oxime-based initiator, The form will be described later) is more preferable. When a black pigment is used as the colorant, excellent lithographic properties can be easily obtained by using the oxime ester compound as the photoradical polymerization initiator.

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

<Oxime-based initiator>
The photoradical polymerization initiator is more preferably an oxime-based initiator. In particular, an oxime-based initiator is preferable because it has high sensitivity, high polymerization efficiency, can be cured regardless of the concentration of the coloring material (coloring agent), and has a high concentration of the coloring material and is easy to design.
As specific examples of the oxime-based initiator, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166 can be used. Specific examples of the oxime-based initiator include, for example, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxyiminopentane. -3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, And 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one and the like.

As an oxime-based initiator, 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, the compounds described in JP-A-2000-80068, JP-A-2004-534977, and JP-A-2006-342166. Be done.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd. (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD)) 930 (manufactured by ADEKA Corporation) can also be used.

Further, as an oxime-based initiator other than the above, the compound described in JP-A-2009-5199004 in which an oxime is linked to the N-position of carbazole, and US Pat. No. 6,626,957 in which a hetero-substituent is introduced at the benzophenone moiety are described. Compounds, compounds described in Japanese Patent Application Laid-Open No. 2010-15025 in which a nitro group is introduced into a dye moiety, US Patent Publication No. 2009-292039, and ketooxime-based initiators and triazine skeletons described in International Publication Patent No. 2009-131189. The compound described in US Pat. No. 7,556,910, which contains the oxime skeleton in the same molecule, the compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source, and the like. You may use it. Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, the contents of which are incorporated herein by reference.

As the photoradical polymerization initiator, an oxime-based initiator having a fluorene ring can also be used. Specific examples of the oxime-based initiator having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein by reference.

An oxime-based initiator having a fluorine atom can also be used as the photoradical polymerization initiator. Specific examples of the oxime-based initiator having a fluorine atom include the compounds described in JP-A-2010-262028, the compounds 24 and 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Examples thereof include the described compound (C-3). This content is incorporated herein by reference.

As the photoradical polymerization initiator, an oxime-based initiator having a nitro group can be used. Specific examples of the oxime-based initiator having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466. ADEKA Arkuru's NCI-831 (manufactured by ADEKA) can be mentioned.

Specific examples of the oxime-based initiator are shown below, but the present invention is not limited thereto.

As the photoradical polymerization initiator, a compound having a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm is preferable, a compound having an absorption wavelength in the wavelength region of 360 nm to 480 nm is more preferable, and a compound having a high absorbance at 365 nm and 405 nm is particularly preferable. preferable.

From the viewpoint of sensitivity, the molar extinction coefficient of the photoradical polymerization initiator at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000. It is particularly preferably ~ 200,000. A known method can be used for measuring the molar extinction coefficient of the compound. Specifically, for example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) at a compound concentration of 0.01 g / L using an ethyl acetate solvent.
Two or more kinds of photoradical polymerization initiators may be used in combination, if necessary.

The content of the photoradical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass, based on the total solid content of the curable composition. %. In this range, better sensitivity and pattern formation can be obtained.

[Polymerizable compound]
The curable composition of the present invention contains a polymerizable compound. The polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure. The number of ethylenically unsaturated groups in the polymerizable compound is not particularly limited, but 2 or more is preferable, 4 or more is preferable, and 5 or more is more preferable in that the cured film has more excellent low reflectivity. The upper limit is not particularly limited, but 10 or less is preferable from the viewpoint of synthesis. Examples of the ethylenically unsaturated group include a (meth) acryloyl group, a (meth) acrylamide group, and a vinyl group.
Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxy. Monofunctional acrylates and methacrylates such as ethyl (meth) acrylates; polyethylene glycol di (meth) acrylates, trimethylol ethanetri (meth) acrylates, neopentyl glycol di (meth) acrylates, pentaerythritol tri (meth) acrylates, pentaerythritols. Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane, etc. Polyfunctional alcohol to which ethylene oxide or propylene oxide is added and then (meth) acrylated, pentaerythritol or dipentaerythritol poly (meth) acrylated, Tokukousho 48-41708, Tokukousho 50-6034 No., urethane acrylates described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-A-49-43191, JP-A-52-30490, In addition, polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth) acrylic acid, can be mentioned. Furthermore, the Journal of the Japan Adhesive Association Vol. Those introduced as photocurable monomers and oligomers on pages 20, No. 7, 300 to 308 can also be used.
Further, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol described as a general formula (1) and a general formula (2) together with specific examples in JP-A-10-62986 and then (meth) acrylated. Can also be used.
Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are linked to dipentaerythritol via ethylene glycol residues or propylene glycol residues. Is preferable. These oligomer types can also be used.
In addition, urethane acrylates as described in JP-A-48-41708, JP-A-51-37193, JP-F-2-32293, and JP-B-2-16765, and Urethane acrylates as described in JP-A-58- Urethane compounds having an ethylene oxide-based skeleton described in the publications of No. 49860, No. 56-17654, No. 62-39417, and No. 62-39418 are also suitable. Further, addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, are used. Thereby, a photopolymerizable curable composition having a very excellent photosensitive speed can be obtained. Commercially available products include urethane oligomer UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.). Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
Ethylene unsaturated compounds having an acid group are also suitable, and commercially available products include, for example, TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toa Synthetic Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. A certain TO-1382 and the like can be mentioned. As the polymerizable compound used in the present invention, a tetrafunctional or higher functional acrylate compound 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 combination mode can be appropriately set according to the physical properties required for the curable composition and the like. One of the preferred combinations of the polymerizable compounds includes, for example, combining two or more polymerizable compounds selected from the above-mentioned polyfunctional acrylate compounds, and one example thereof is dipentaerythritol hexaacrylate. And a combination of pentaerythritol triacrylate.
The content of the polymerizable compound in the curable composition of the present invention is preferably 3% by mass to 55% by mass, more preferably 10% by mass to 50% by mass, based on the total solid content in the curable composition.

[Base generator]
The curable composition of the present invention contains a base generator. Examples of the base generator include a thermal base generator and a photobase generator.

<Thermal base generator>
The type of the thermobase generator is not particularly limited, but for example, an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. At least one selected from.
The acidic compound (A1) and the ammonium salt (A2) generate a base when heated.
In the present specification, the acidic compound means that 1 g of the compound is collected in a container, 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added, and the compound is added at room temperature for 1 hour. Stir. It means a compound having a value of less than 7 measured at 20 ° C. using a pH meter for the solution.

The base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and even more preferably 165 ° C. or lower. The lower limit of the base generation temperature is preferably 130 ° C. or higher, more preferably 135 ° C. or higher.
For the base generation temperature, for example, using differential scanning calorimetry, the compound is heated to 250 ° C. in a pressure resistant capsule at 5 ° C./min, the peak temperature of the lowest exothermic peak is read, and the peak temperature is measured as the base generation temperature. can do.

The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. The boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, preferably 100 ° C. or higher, and most preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The value of the molecular weight is a theoretical value obtained from the structural formula.

The acidic compound (A1) preferably contains one or more selected from ammonium salts and compounds having cations represented by the general formula (TM1) described later.

The ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound excluding an acidic compound that generates a base when heated.
Hereinafter, the thermobase generator will be described in detail.

(Ammonium salt)
The ammonium salt means a salt of an ammonium cation represented by the following general formula (TM1) or general formula (TM2) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, may be present outside the molecule of the ammonium cation, but may be present outside the molecule of the ammonium cation. preferable. The fact that the anion is present outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the non-molecular anion of the cation part is also referred to as a counter anion.

In the general formula (TM1) and the general formula (TM2), R ^{1 to} R ⁶ independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ may be combined to form a ring, respectively.

The ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more.
The type of anion is preferably one selected from carboxylic acid anion, phenol anion, phosphate anion and sulfate anion, and more preferably carboxylic acid anion because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion.
In the present invention, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and is Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafliger, O.H., Hafliger, O. F.C .; Compilation: Braude, E.A., Nachod, F.C .; Academic Press, New
You can refer to the values described in York, 1955) and Data for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.

In the present invention, the carboxylic acid anion is preferably represented by the following general formula (X1).

In the above general formula (X1), EWG represents an electron-withdrawing group.

The electron-withdrawing group means that the substituent constant σm of Hammett shows a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-withdrawing group of the present invention is not limited to the substituents described in the above documents.
Examples of substituents in which σm shows a positive value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), and the like. CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0.34), _two H ₂ NCOCH groups (σm = 0.06) and the like can be mentioned. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

The EWG preferably represents a group represented by the following general formulas (EWG-1) to (EWG-6).

In the formula, R ^{x1 to} R ^x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic ring group.
The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The alkyl group may have a substituent or may be unsubstituted. Substituents that the alkyl group may have (hereinafter, also referred to as “substituent group A”) include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group and tert. -Alkyl groups such as butoxy groups; aryloxy groups such as phenoxy groups and p-tolyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups, butoxycarbonyl groups and phenoxycarbonyl groups; acetoxy groups, propionyloxy groups and benzoyloxy groups Acyloxy group; Acyl group such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; alkylsulfanyl group such as methylsulfanyl group and tert-butylsulfanyl group; phenylsulfanyl group and p-tolylsulfonyl group etc. Alkyl sulfanyl group; alkyl group such as methyl group, ethyl group, tert-butyl group and dodecyl group; alkyl halide such as alkyl fluoride; cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group; Aryl groups such as phenyl group, p-tolyl group, xsilyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxyl group; carboxyl group; formyl group; sulfonic acid group; cyano group; alkylaminocarbonyl group; arylamino Carbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; diarylamino group; thioxy group; or a combination thereof. Of these, a carboxyl group is preferable.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 10 carbon atoms. The alkenyl group may be linear, branched, or cyclic, preferably linear or branched, more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described as the above-mentioned Substituent Group A. As the substituent, a carboxyl group is preferable.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described as the above-mentioned Substituent Group A. As the substituent, a carboxyl group is preferable.
Specific examples of the aromatic ring group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, and phenanthrene ring. Anthracene ring, naphthalene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acrydin ring, phenanthrene ring , Thiantrene ring, chromene ring, xanthene ring, phenoxatiin ring, phenothiazine ring, and phenazine ring. Among them, from the viewpoint of storage stability and high sensitivity, a benzene ring, a naphthalene ring, an anthracene ring, a phenothiazine ring, or a carbazole ring is preferable, and a benzene ring or a naphthalene ring is most preferable.
Examples of the substituents that the aromatic ring group may have include those described as the above-mentioned Substituent Group A. As the substituent, a carboxyl group is preferable.

The carboxylic acid anion is preferably represented by the following general formula (X).

In the general formula ^{(X), L 10} represents a single bond or an alkylene group, an alkenylene group, an arylene group, -NR ^X - represents and divalent linking group selected from these combinations, ^{R X} is a hydrogen atom , Alkyl group, alkenyl group or aryl group.

The carbon number of the alkylene group represented by L ¹⁰ is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkylene group may be linear, branched, or cyclic, preferably straight or branched, more preferably straight. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described as the above-mentioned Substituent Group A.
The number of carbon atoms of the alkenylene group represented by L ¹⁰ is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The alkenylene group may be linear, branched, or cyclic, preferably linear or branched, more preferably linear. The alkenylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described as the above-mentioned Substituent Group A.
The carbon number of the arylene group represented by L ¹⁰ is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described as the above-mentioned Substituent Group A.

Number of carbon atoms of the alkyl group R ^X represents preferably 1 to 30, more preferably from 1 to 20, 1 to 10 is more preferable. The alkyl group may be linear, branched, or cyclic, preferably straight or branched, more preferably straight. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described as the above-mentioned Substituent Group A.
The number of carbon atoms of the alkenyl group R ^X represents preferably 2 to 30, more preferably from 2 to 20, more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic, preferably linear or branched, more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described as the above-mentioned Substituent Group A.
R ^X number of carbon atoms of the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, 6 to 12 is more preferable. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described as the above-mentioned Substituent Group A.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion. These can be preferably used.

The ammonium cation is preferably represented by any of the following general formulas (Y1-1) to (Y1-6).

In the above general formula, R ¹⁰¹ represents an n-valent organic group.
R ^{102 to} R ¹¹¹ independently represent a hydrogen atom or a hydrocarbon group, respectively.
R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group.
R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be coupled to each other to form a ring.
Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group.
n represents an integer of 1 or more
m represents an integer from 0 to 5.

R ¹⁰¹ represents an n-valent organic group. Examples of the monovalent organic group include an alkyl group, an alkylene group, and an aromatic ring group. Examples of the divalent or higher organic group include a monovalent organic group obtained by removing one or more hydrogen atoms to obtain an n-valent group.
R ¹⁰¹ is preferably an aromatic ring group. Specific examples of the aromatic ring group include those described in Ar ¹⁰ described later.

R ^{102 to} R ¹¹¹ independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group.
As the hydrocarbon group represented by R ^{102 to} R ¹¹¹ and R ¹⁵¹ , an alkyl group, an alkenyl group or an aryl group is preferable. The alkyl group, alkenyl group and aryl group may further have a substituent.
Examples of the hydrocarbon group represented by R ¹⁵⁰ include an alkylene group. The alkylene group may further have a substituent. Examples of the substituent include those described as the above-mentioned Substituent Group A.

The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, preferably straight or branched, more preferably straight. The alkyl group may have a substituent or may be unsubstituted.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 10 carbon atoms. The alkenyl group may be linear, branched, or cyclic, preferably linear or branched, more preferably linear. The alkenyl group may have a substituent or may be unsubstituted.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted.

Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted.

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be coupled to each other to form a ring. Examples of the ring include an alicyclic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocycle. The ring may be a single ring or a double ring. When the above groups are bonded to form a ring, the linking group comprises -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic ring group and a combination thereof. It can be linked with a divalent linking group selected from the group. Specific examples include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole ring, benzimidazole ring. , Pyrazine ring, quinoline ring, isoquinoline ring, quinoxalin ring, cinnoline ring, carbazole ring, and the like.

The ammonium cation preferably has a structure represented by the general formula (Y1-1) or (Y1-2), is represented by the general formula (Y1-1) or (Y1-2), and R ¹⁰¹ is an aromatic ring group. A certain structure is more preferable, and a structure represented by the general formula (Y1-1) in which R ¹⁰¹ is an aromatic ring group is particularly preferable.

The above thermal base generator may be used alone or in combination of two or more. When two or more kinds of thermobase generators are used in combination, the combination mode can be appropriately set according to the physical properties required for the curable composition, for example, the adhesion to the substrate. Further, it may be used in combination with a photobase generator described later.

The content of the thermobase generator in the curable composition of the present invention is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, based on the total solid content in the curable composition. It is more preferably ~ 7% by mass. When two or more kinds of base generators are used in combination, the total content of each is preferably within the above range.

<Photobase generator>
The curable composition of the present invention preferably contains a photobase generator in that it has more excellent effects of the present invention. The photobase generator is not particularly limited, and specific examples thereof include paragraphs 0207 to 0238 of JP2015-087612, paragraphs 0026 to 0039 of JP2008-247747, and International Publication No. The description of paragraphs 0009 to 0052 of 2010/064631 can be taken into consideration, the contents of which are incorporated herein by reference. Further, the description of paragraphs 0018 to 0105 of International Publication No. 2009/122664 and the description of paragraphs 0025 to 0072 of Japanese Patent No. 5223633 can be referred to, and the contents thereof are incorporated in the present specification. Further, the ionic photobase generator described in paragraphs 0053 to 0070 of JP-A-2015-28540 may be used, and the contents thereof are incorporated in the present specification.

As the photobase generator, a compound that emits amine by light is preferable because the cured film has excellent low reflectivity. For example, the photobase generator described in JP2013-80206 is preferable, and the contents thereof are incorporated in the present specification.

The commercially available photobase generator is not particularly limited, but Wako Pure Chemical Industries, Ltd.'s WPBG series "WPBG-082", "WPBG-167", "WPBG-168", "WPBG-018", "" WPBG-027 "," WPBG-140 "and the like can also be used. "WPBG-018" and "WPBG-027" can be preferably used because the cured film has excellent low reflectivity.

As the photobase generator, a photobase generator represented by the following general formula (PBG) is preferable because the cured film has excellent low reflectivity.

In the above general formula (PEG), ^Ra and R ^b independently represent hydrogen atoms or monovalent organic groups, respectively, and aromatic hydrocarbon groups and aliphatic groups in that the cured film has better low reflectivity. It is preferably a hydrocarbon group or a combination thereof, and examples thereof include an alkyl group and an aryl group. Among them, ^Ra and R ^b are preferably alkyl groups, more preferably linear or branched alkyl groups having 1 to 9 carbon atoms, and have more carbon atoms, in that the cured film has more excellent low reflectivity. 1 to 4 linear or branched alkyl groups are more preferable, methyl groups, ethyl groups and isopropyl groups are particularly preferable, and methyl groups are most preferable.
Further, ^Ra and R ^b may be combined with each other to form a ring. Examples of the cyclic amino group formed by bonding ^Ra and R ^b to each other include 1-aziridinyl group, 1-azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group and 1-. Heptamethylene imino group, 1-octamethylene imino group, 1-nonamethylene imino group, 1-1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolidinyl Examples include a group, a 1-piperazinyl group, a morpholino group and the like. Among them, a cyclic amino group having 2 to 9 carbon atoms having no unsaturated bond is preferable because the cured film has more excellent low reflectivity, and a 1-aziridinyl group, a 1-azetidinyl group, and a 1-pyrrolidinyl group are preferable. , Or a 1-piperidinyl group is more preferred, and a 1-pyrrolidinyl group is even more preferred.

In the above general formula (PBG), Ar ^a represents an aryl group or a heteroaryl group. The aryl group and the heteroaryl group may further have a monovalent organic group as a substituent. Among them, Ar ^a is preferably an aryl group or a heteroaryl group having ^a condensed ring structure in that the cured film has more excellent low reflectivity. The number of fused rings of Ar ^a is preferably 2 to 5, and more preferably 3 to 4, in that the cured film has more excellent low reflectivity. At this time, the condensed ring may contain a heterocycle, and each condensed ring may have one or more monovalent organic groups as substituents. Further, it is more preferable that the condensed ring structure described above is a π-conjugated system. When the condensed ring structure is a π-conjugated system, it has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm and reacts competitively with the photoradical polymerization initiator, so that a cured film having excellent low reflectivity can be obtained. Cheap. Specific embodiments of Preferable Ar ^a include the following general formulas (CR1) to (CR5), and the general formulas (CR1) to (CR4) are more preferable in that the cured film has better low reflectivity. Preferably, the general formulas (CR1) to (CR3) are more preferable. In the formula, * indicates a bond position, and each ring may have one or more monovalent organic groups as substituents.

When the photobase generator is irradiated with light having the above-mentioned predetermined wavelength, the photobase generator is decomposed to generate a base. The generated base is preferably an amine compound in that a cured film having better low reflectivity can be produced. Examples of the amine compound include a primary amine, a secondary amine, and a tertiary amine, and a primary amine or a secondary amine is preferable.
When a photobase generator represented by the general formula (PBG) is used as the photobase generator, a primary amine or a secondary amine represented by the following general formula (BA) is generated as a base. The molecular weight of the base generated from this photobase generator is preferably 150 or less, more preferably 100 or less, and more preferably 70 or less in that the cured film has better low reflectivity. More preferred. Although the mechanism is not clear, a base having a low molecular weight and easily diffusing is generated, and by diffusing in the coating film, the rate and / or the degree of progress of the polymerization reaction of the polymerizable compound in the upper region and the lower region is determined. There is a difference. Therefore, since the stress generated by the curing shrinkage differs between the upper region and the lower region, it is presumed that fine wrinkles are generated in the upper region, which contributes to the low reflectivity of the cured film.
In addition, in this specification, the molecular weight of a base means the molecular weight which can be calculated from the structural formula.

In the above general formula (BA), ^Ra and R ^b are the same as the definitions in the general formula (PBG).

The photobase generator may be used alone or in combination of two or more.
When two or more kinds of photobase generators are used in combination, the combination mode can be appropriately set according to the physical properties required for the curable composition, for example, the adhesion to the substrate.
The content of the photobase generator in the curable composition of the present invention is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, based on the total solid content in the curable composition. It is more preferably ~ 7% by mass. When two or more kinds of photobase generators are used in combination, the total content of each is preferably within the above range.

The content of the photobase generator is such that the mass ratio of the photobase generator to the dispersant (mass of the photobase generator / mass of the dispersant) is 0.05 to 0 in relation to the content of the dispersant described later. In many cases, it is 0.7, and it is preferably 0.08 to 0.5 in that the cured film has better low reflectivity.

[Dispersant]
The curable composition of the present invention contains a dispersant. The dispersant contributes to improving the dispersibility of the colorant and the photobase generator (hereinafter, referred to as “dispersed body”).

As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Dispersants include polymer dispersants [for example, polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylics. Copolymer, naphthalene sulfonic acid formarin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, pigment derivative and the like can be mentioned.
Polymer compounds can be further classified into linear polymers, terminally modified polymers, graft-type polymers, and block-type polymers based on their structures.

The polymer compound has an interaction with a dispersion to be dispersed and an extender pigment or the like to be used in combination if desired. Therefore, the polymer compound is adsorbed on the surface of the dispersion to be dispersed and acts to prevent reaggregation. Therefore, a terminal-modified polymer having an anchor site on the surface of the colorant, a graft polymer, and a block polymer can be mentioned as preferable structures. The anchor site on the surface of the colorant is preferably an acid group or a hydroxyl group, more preferably an acid group, good dispersion stability of the colorant, good development, and excellent pattern formation, and a carboxyl group is particularly preferable.
On the other hand, by modifying the surface of titanium black or the above-mentioned titanium black and the dispersion to be dispersed containing Si atoms, the adsorptivity of the polymer compound to these can be promoted.

The polymer compound preferably has a structural unit having a graft chain. In addition, in this specification, "structural unit" is synonymous with "repeating unit".
A polymer compound having a structural unit having such a graft chain has an affinity with a solvent due to the graft chain, and therefore has excellent dispersibility of the dispersant and dispersion stability after aging. Further, in the curable composition, the presence of the graft chain has an affinity with a polymerizable compound or other resin that can be used in combination, so that a residue is less likely to be generated by alkaline development.
When the graft chain is long, the steric repulsion effect is high and the dispersibility is improved, while when the graft chain is too long, the adsorption force to the disperse is lowered and the dispersibility tends to be lowered. Therefore, the graft chain preferably has an atomic number in the range of 40 to 10,000 excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and atoms excluding hydrogen atoms. Those having a number of 60 to 500 are more preferable.
Here, the graft chain indicates from the root of the main chain of the copolymer (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 has a polymer structure, and such polymer structures include, for example, a polyacrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and the like. A polyether structure and the like can be mentioned.
In order to improve the interoperability between the graft chain and the solvent, thereby increasing the dispersibility of the colorant, the graft chain shall be at least one selected from the group consisting of polyester structure, polyether structure and polyacrylate structure. It is preferably a graft chain having, and more preferably a graft chain having at least one of a polyester structure and a polyether structure.

The macromonomer having such a polymer structure as a graft chain is not particularly limited, but preferably a macromonomer having a reactive double bond group can be preferably used.

Commercially available macromonomers that correspond to the structural unit having the graft chain of the polymer compound and are preferably used for the synthesis of the polymer compound include AA-6 (trade name, Toa Synthesis Co., Ltd.) and AA-10 (AA-10). Product name, Toa Synthetic Co., Ltd.), AB-6 (Product name, Toa Synthetic Co., Ltd.), AS-6 (Product name, Toa Synthetic Co., Ltd.), AN-6 (Product name, Toa Synthetic Co., Ltd.) (Manufactured by Toa Synthetic Co., Ltd.), AW-6 (trade name, manufactured by Toa Synthetic Co., Ltd.), AA-714 (trade name, manufactured by Toa Synthetic Co., Ltd.), AY-707 (trade name, manufactured by Toa Synthetic Co., Ltd.), AY-714 (trade 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 (product name) Name, Toa Synthetic Co., Ltd., Blemmer PP-100 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PP-500 (trade name, manufactured by Nichiyu Co., Ltd.), Brenmer PP-800 (trade name, manufactured by Nichiyu Co., Ltd.) Nichiyu Co., Ltd.), Blemmer PP-1000 (trade name, Nissui Co., Ltd.), Blemmer 55-PET-800 (trade name, Nissui Co., Ltd.), Brenmer PME-4000 (trade name, manufactured by Nichiyu Co., Ltd.) Blemmer PSE-400 (trade name, manufactured by Nissui Co., Ltd.), Blemmer PSE-1300 (trade name, manufactured by Nissui Co., Ltd.), and Blemmer 43PAPE-600B (trade name, manufactured by Nichiyu Co., Ltd.) Nichiyu Co., Ltd.) is used. Of these, preferably AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.). , AS-6 (trade name, Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), and Blemmer PME-4000 (trade name, manufactured by Nichiyu Co., Ltd.), etc. Be done.

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

In the above general formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ independently represent an oxygen atom or NH, respectively. W ¹ , W ² , W ³ and W ⁴ are preferably oxygen atoms.
In the general 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. From the viewpoint of synthetic constraints, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are preferably hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, respectively, and are independent of each other. In addition, a hydrogen atom or a methyl group is more preferable, and a methyl group is further preferable.

In the general 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 group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following linking groups (Y-1) to (Y-21). .. In the structure shown below, A and B mean the bonding positions with the left terminal group and the right terminal group in the general 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 general formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The organic group is not particularly limited, and specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Be done. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are preferable from the viewpoint of improving dispersibility, and each of them has 5 to 24 carbon atoms independently. Of these, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms are particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

In the general formulas (1) to (4), n, m, p, and q are each independently an integer from 1 to 500.
Further, in the general formulas (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the general formula (1) and the general formula (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoint of dispersion stability and developability.

In the general formula (3), R ³ represents a branched 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, R ³ existing in plural numbers may be different from one another the same.
In the general formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly structurally limited. Preferred as R ^4, a hydrogen atom, an alkyl group, an aryl group, and heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. 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 general formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

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

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

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

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

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

The polymer compound more preferably has a structural unit represented by the general formula (1A) as a structural unit having a graft chain.

In the polymer compound, the structural unit having a graft chain (for example, the structural unit represented by the above general formulas (1) to (4)) is 2 to 90 with respect to the total mass of the polymer compound in terms of mass. It is preferably contained in the range of%, and more preferably contained in the range of 5 to 30%. When the structural unit having a graft chain is included in this range, the dispersible substance (particularly, titanium black particles) has high dispersibility, and the developability when forming a light-shielding film is good.

Moreover, it is preferable that the polymer compound has a hydrophobic structural unit different from the structural unit having a graft chain (that is, it does not correspond to the structural unit having a graft chain). However, in the present invention, the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxyl 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 more preferably derived from a compound having a ClogP value of 1.2 to 8. It is a structural unit. Thereby, the effect of the present invention can be more reliably exhibited.

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 literature below). The fragment approach is based on the chemical structure of a compound, and the logP value of the compound is estimated by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. Leo, Comprehensive Medical Chemistry, Vol. 4, C.I. Hansch, P.M. G. Sammenens, J. Mol. B. Taylor and C.I. 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 has one or more structural units selected from structural units derived from the monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units. ..

In the general formulas (i) to (iii), R ¹ , R ² , and R ³ independently have a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or a carbon number of 1. Represents an alkyl group of ~ 6 (eg, methyl group, ethyl group, 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, and a substituted alkynylene group), and a divalent aromatic group (for example, a substituted alkynylene group). arylene group, a substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, where Examples of R ³¹ 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. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups.

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. Moreover, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups and heterocyclic groups.

The divalent heterocyclic group preferably has 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. Moreover, 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 fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups, and heterocyclic groups.

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−, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Examples of Z include an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (for example, an arylene group and a substituted arylene group), a heterocyclic group, and the like. oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} represents an aliphatic group, an aromatic group or a heterocyclic group) , A carbonyl group (-CO-), and combinations thereof.

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 -Includes cyclohexylphenyl groups and the like. As the crosslinked cyclic hydrocarbon ring, for example, 2 such as pinan, bornan, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane rings. , Tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodecane and tetracyclic 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, perhydroacenaphthene, 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. In addition, 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. Moreover, 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 has 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. Moreover, 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 fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups. However, the heterocyclic group does not have an acid group as a substituent.

In the general formula ^(iii), R 4, ^{R 5,} and ^{R 6} are each independently a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine), an alkyl group having 1 to 6 carbon atoms (e.g. , Methyl group, ethyl group, propyl group, etc.), Z, or LZ. Here, L and Z are synonymous with those in the above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the above general formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, and L is a single bond or an alkylene group or an oxyalkylene structure. A compound 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 as a divalent linking group containing.
Further, as the monomer represented by the above general 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. Is preferred. Further, as the monomer represented by the above general 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. Certain compounds are preferred.

Examples of typical compounds represented by the general 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 general formulas (i) to (iii), the compounds described in paragraphs 089 to 093 of JP2013-249417A can be referred to, and the contents thereof are described. Incorporated herein.

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.

The polymer compound can introduce a functional group capable of forming an interaction with the dispersion (particularly titanium black). Here, it is preferable that the polymer compound further has a structural unit having a functional group capable of forming an interaction with the dispersion.
Examples of the functional group capable of forming an interaction with the dispersant include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound has an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit having an acid group, a structural unit having a basic group, and a coordinating group, respectively. It is preferable to have a structural unit having the above, or a structural unit having reactivity.
In particular, when the polymer compound further has an alkali-soluble group such as a carboxyl group as an acid group, the polymer compound can be imparted with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, in the curable composition of the present invention, the polymer compound as a dispersant that contributes to the dispersion of the dispersoid 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, since the polymer compound has a structural unit having an acid group, the polymer compound tends to be easily compatible with the solvent and the coatability tends to be improved.
This is because the acid group in the structural unit having an acid group easily interacts with the object to be dispersed, the polymer compound stably disperses the object to be dispersed, and the viscosity of the polymer compound that disperses the object to be dispersed is low. It is presumed that this is because the polymer compound itself is likely to be stably dispersed.

However, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the structural unit having a graft chain described above or a different structural unit, but an alkali-soluble group as an acid group The structural unit having 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 the dispersant include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group and the like, and preferably a carboxyl group and a sulfonic acid group. , And at least one of the phosphoric acid groups, more preferably a carboxyl group, in that it has good adsorption to the colorant and high dispersibility of the colorant.
That is, the polymer compound preferably further has a structural unit having at least one of a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or more structural units having an acid group.
The polymer compound may or may not contain a structural unit having an acid group, but when it is contained, the content of the structural unit having an acid group is based on the total mass of the polymer compound in terms of mass. It is preferably 5 to 80%, and more preferably 10 to 60% 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 the dispersant include a primary amino group, a secondary amino group, a tertiary amino group, a heterocycle containing an N atom, and an amide. There are groups and the like, and more preferable ones are tertiary amino groups in that they have good adsorption power to the colorant and high dispersibility of the colorant. The polymer compound can have one or more of these basic groups.
The polymer compound may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is the total mass of the polymer compound in terms of mass. On the other hand, it is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppressing developmental inhibition.

Coordinating groups, which are functional groups capable of forming an interaction with the dispersant, and reactive functional groups include, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and a acid compound. And so on. A more preferable one is an acetylacetoxy group in that it has a good adsorptivity to a colorant and has a high dispersibility of the colorant. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, but when it is contained, the content of these structural units is determined. In terms of mass, it is preferably 10% or more and 80% or less with respect to the total mass of the polymer compound, and more preferably 20% or more and 60% or less from the viewpoint of suppressing developmental inhibition.

When the polymer compound in the present invention has a functional group capable of forming an interaction with the dispersion to be dispersed in addition to the graft chain, it contains a functional group capable of forming an interaction with various black pigments as described above. You just have to. How these functional groups are introduced is not particularly limited, but the polymer compound is selected from structural units derived from monomers represented by the following general formulas (iv) to (vi). It is preferable to have one or more structural units.

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

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

Further, L ₁ in the general formula (iv) to the general formula (v) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), and divalent aromatic group (eg, substituted alkynylene group). , an arylene group, and a substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), substituted imino bond ^{(-NR 31} '- , wherein ^{R 31} 'represents an aliphatic group, an aromatic group or a heterocyclic group), carbonyl bond (-CO-), and, combinations thereof and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups and heterocyclic groups.

The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. Moreover, the aromatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aliphatic groups, aromatic groups and heterocyclic groups.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocycle. One or more of other heterocycles, aliphatic rings or aromatic rings may be condensed on the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups.

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 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 general formula (iv) to the general formula (vi), Z ₁ represents a functional group capable of forming an interaction with a colorant other than the graft chain, and is preferably a carboxyl group or a tertiary amino group, preferably a carboxyl group. More preferably it is a group.

In the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms, halogen atoms (for example, fluorine, chlorine, bromine, etc.) and alkyl groups having 1 to 6 carbon atoms (for example, for example). methyl group, ethyl group, propyl group, etc.), - represents a _{Z 1} or _L 1 -Z _1,. Here, L ₁ and Z ₁ are synonymous with L ₁ and Z ₁ described above, and so are preferred examples. As R ¹⁴ , R ¹⁵ and R ¹⁶ , each independently has a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom is more preferable.

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

Hereinafter, typical examples of the monomers (compounds) represented by the general formulas (iv) to the general formulas (vi) are shown.
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. , A reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule and phthalic acid anhydride, and a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic acid anhydride. , A reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule and pyromellitic acid anhydride, Examples thereof include acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenylmethacrylate.

The content of the structural unit having a functional group capable of forming an interaction with the dispersion is the total mass of the polymer compound from the viewpoint of interaction with the dispersion, dispersion stability, and permeability to a developer. With respect to this, 0.05% by mass to 90% by mass is preferable, 1.0% by mass to 80% by mass is more preferable, and 10% by mass to 70% by mass is further preferable.

Further, for the purpose of improving various performances such as image intensity, the polymer compound forms an interaction with a structural unit having a graft chain, a hydrophobic structural unit, and a colorant as long as the effects of the present invention are not impaired. It further has other structural units having various functions (for example, structural units having functional groups having an affinity with the dispersion medium used for the dispersion), which are different from the structural units having possible functional groups. You may.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles.
The polymer compound can use one or more of these other structural units, and its content is preferably 0% or more and 80% or less with respect to the total mass of the polymer compound in terms of mass. It is particularly preferable that it is 10% or more and 60% or less. Sufficient pattern formation is maintained when the content is in the above range.

The acid value of the polymer compound is preferably in the range of 0 mgKOH / g or more and 250 mgKOH / g or less, more preferably in the range of 0 mgKOH / g or more and 160 mgKOH / g or less, and further preferably 10 mgKOH / g or more and 140 mgKOH / g. The range is g or less, and particularly preferably 20 mgKOH / g or more and 120 mgKOH / g or less.
When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a light-shielding film can be more effectively suppressed. 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, the precipitation of the dispersion to be dispersed can be further suppressed, the number of coarse particles can be further reduced, and the stability over time of the curable composition can be further improved. ..

In the present invention, the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer 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 polymer compound.

The weight average molecular weight of the polymer compound in the present invention is a polystyrene-equivalent value obtained by the GPC (Gel Permeation Chromatography) method from the viewpoint of suppressing pattern peeling during development and developability when forming a light-shielding film. , 4,000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, 10,000 or more and 50 or less. It is particularly preferable that it is 000 or less.
In the GPC method, HLC-8020GPC (manufactured by Tosoh Corporation) is used, TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) are used as columns, and THF (tetrahydrofuran, manufactured by Tosoh Corporation) is used as an eluent. ) Is used.

The polymer compound can be synthesized based on a known method, and examples of the solvent used in synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, Examples thereof include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound that can be used in the present invention include "Disperbyk-161, 162, 163, 164, 165, 166, 170, 190 (trade name, polymer copolymer)" manufactured by BYK Chemie, EFKA. Examples thereof include "EFKA4047, 4050, 4010, 4165 (trade name, polyurethane type), EFKA4330, 4340 (trade name, block copolymer)" and the like.
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 dispersant, in addition to the above-mentioned polymer compound, the graft copolymers of paragraphs 0037 to 0115 of JP-A-2010-106268 (paragraphs 0075 to 0133 of the corresponding US2011 / 0124824) can be used. The contents of are hereby incorporated into this specification.
In addition to the above, it has a side chain structure in which the acidic groups of paragraphs 0028 to 0084 of JP2011-153283 (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group. High molecular weight compounds containing the constituents can be used, the contents of which can be incorporated and incorporated herein by reference.

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

[Other ingredients]
<Fluororesin>
The curable composition of the present invention may further contain a fluororesin from the viewpoint of obtaining a cured film having better low reflectivity. In the present specification, the fluororesin refers to an oligomer or polymer having a fluorine atom. The fluororesin is not included in the above-mentioned dispersant and the below-mentioned binder polymer. Examples of the fluororesin include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, and F482. , F554, F780, F781F (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Ltd.), Surflon S-382, SC-101, SC -103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.) and the like.
One type of fluororesin may be used, or two or more types may be combined.
The amount of the fluororesin added is preferably 0.01 to 3% by mass, preferably 0.5 to 1.5% by mass, based on the total mass of the curable composition, in that the cured film has better low reflectivity. More preferably by mass.

A fluoropolymer having an ethylenically unsaturated group in the side chain can also be used as the fluororesin. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation. Can be mentioned.
When a fluoropolymer having an ethylenically unsaturated group in the side chain and a fluororesin are used in combination, it is preferable that the total amount of the fluoropolymer added is within the above-mentioned preferable range.

<Binder polymer>
The curable composition of the present invention may contain a binder polymer.
As the binder polymer, it is preferable to use a linear organic polymer. As such a linear organic polymer, known ones can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to allow water or weak alkaline water development. Among them, as the binder polymer, an alkali-soluble resin (a resin having a group that promotes alkali solubility) is particularly preferable.
The binder polymer is a linear organic polymer and is an alkali having at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from the soluble resins. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, or acrylic / acrylamide copolymer resin is preferable, and from the viewpoint of developability control, acrylic resin, An acrylamide resin or an acrylic / acrylamide copolymer resin is preferable.
Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like, and these acid groups may be one kind. There may be two or more types.

Examples of the binder polymer include radical polymers having a carboxyl group in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Application Laid-Open No. 54-34327, Japanese Patent Application Laid-Open No. 58-125777, Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Application Laid-Open No. Those described in JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins having a monomer having a carboxyl group alone or copolymerized, and a monomer having an acid anhydride. Examples thereof include a resin obtained by hydrolyzing, half-esterifying or half-amidizing an acid anhydride unit by itself or copolymerizing the above, and an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like, and examples of the monomer having an acid anhydride include Maleic anhydride and the like can be mentioned. Similarly, an acidic cellulose derivative having a carboxyl group in the side chain is also mentioned as an example. In addition to this, a polymer having a hydroxyl group to which a cyclic acid anhydride is added is useful.
Further, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in each of the publications such as European Patent No. 9993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318436 has an excellent balance between film strength and developability. It is suitable.
Further, as the water-soluble linear organic polymer, polyvinylpyrrolidone, polyethylene oxide and the like are useful. Further, in order to increase the strength of the cured film, alcohol-soluble nylon, a polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer if necessary] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / necessary Other Additive Polymeric Vinyl Monopolymers] Copolymers are suitable because they have an excellent balance of film strength, sensitivity, and developability.
Examples of commercially available products include Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai Co., Ltd.), and Cyclomer P (ACA) 230AA manufactured by Daicel Ornex Co., Ltd. Can be mentioned.
The binder polymer may contain the structural unit having the above-mentioned graft chain (the structural unit represented by any of the above general formulas (1) to (4)).

For the production of the binder polymer, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent when producing an alkali-soluble resin by a radical polymerization method can be easily set by those skilled in the art and are experimental conditions. It is also possible to determine.

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

<Solvent>
The curable composition of the present invention may contain a solvent.
Examples of the solvent include water and organic solvents.
Examples of organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate , Methyl Lactate, Ethyl Lactate, and the like, but are not limited thereto.

The solvent may be used alone, but it is preferable to use two or more kinds of organic solvents in combination because the cured product has more excellent low reflectivity. It is considered that the solubility of the base generator is improved by using two or more kinds of organic solvents in combination, and the low reflectivity of the cured product is improved.
When two or more kinds of organic solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate are particularly preferable. , 2-Heptanone, cyclohexanone, cyclopentanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
The amount of the solvent contained in the curable composition is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, based on the total mass of the curable composition.

<Others>
The curable composition of the present invention may contain an ultraviolet absorber. As a result, the shape of the pattern can be made more excellent (fine).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples thereof, compounds of paragraphs 0137 to 0142 of JP2012-068418A (corresponding paragraphs 027 to 0254 of US2012 / 0068292) can be used, and these contents 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.
When the curable composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass, preferably 0.01 to 10% by mass, based on the total solid content of the curable composition. More preferably, 0.1 to 5% by mass is further preferable.

The curable composition may contain various surfactants from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. In particular, the curable composition of the present invention further improves the liquid characteristics (particularly, fluidity) by containing a fluorine-based surfactant, and thus further improves the uniformity of coating thickness and liquid saving property. be able to.
In the curable composition of the present invention, the above-mentioned fluororesin may have a function as a surfactant. The fluorine-based surfactant that can be suitably used for the curable composition of the present invention is the same as that exemplified as the above-mentioned fluororesin.
One type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the curable composition.

<Polymerization inhibitor>
It is desirable that the curable composition of the present invention contains a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, and 4,4'-thiobis (3-methyl-6-). tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine first cerium salt and the like. When the composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the curable composition. One type of polymerization inhibitor may be used, or two or more types may be combined. When two or more types are included, the total amount is preferably in the above range.

In addition to the above components, the curable composition of the present invention may contain the following components. Examples thereof include sensitizers, co-sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and fat sensitizers. Furthermore, adhesion promoters and other auxiliaries on the surface of the substrate (eg, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, etc. Known additives such as (chain transfer agent, etc.) may be included in the curable composition, if necessary.
These components are, for example, paragraph Nos. 0183 to 0228 of JP2012-003225A ([0237] to [0309] of the corresponding US Patent Application Publication No. 2013/0034812), JP-A-2008-250074. The description of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP2013-195480 can be referred to, and the contents thereof are described in the present specification. Be incorporated.

[Method for preparing curable composition]
The curable composition of the present invention can be prepared by mixing the above-mentioned various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
The method of mixing the various components is not particularly limited, but for the purpose of improving the dispersibility of the colorant, the colorant is previously dispersed in another component (for example, resin or solvent) and then mixed with the other component. It is also preferable to disperse the colorant in the dispersant in advance and then mix it with other components in terms of further improving the dispersibility.
The curable composition of the present invention is preferably filtered through a filter for the purpose of removing foreign substances and reducing defects. The filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, a polyolefin resin such as polyethylene and polypropylene (PP) (including high density and ultrahigh molecular weight) and the like can be mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and further preferably about 0.3 to 0. It is 7 μm. Within this range, it is possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the pigment-containing colorant while suppressing filtration clogging of the pigment-containing colorant.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed 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., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd. ..
As the second filter, one formed of the same material as the first filter described above can be used. The pore size of the second filter is preferably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.
The curable composition of the present invention 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.

[Shading film]
The cured film obtained by curing the curable composition of the present invention can be used as a light-shielding film having excellent low reflectivity when a light-shielding pigment is used as a colorant.
The film thickness of the light-shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 to 50 μm, more preferably 0.5 to 30 μm, and 0. 7 to 25 μm is more preferable, and 1.0 to 10 μm is particularly preferable.
The above-mentioned thickness is an average thickness, which is a value obtained by measuring the thicknesses of any five or more points of the light-shielding film and arithmetically averaging them.

[Manufacturing method of light-shielding film]
The method for producing the light-shielding film is not particularly limited, and examples thereof include a method in which the above-mentioned curable composition is applied onto a substrate to form a coating film, and the coating film is cured to produce a light-shielding film. ..
The method of the curing treatment is not particularly limited, but a photocuring treatment is usually selected.
The type of substrate used is not particularly limited, and various members in the solid-state image sensor (for example, an infrared light cut filter, an outer peripheral portion of the solid-state image sensor, a wafer level lens outer peripheral portion, a back surface of the solid-state image sensor, etc.) ) Etc. are preferably mentioned.

A preferred embodiment in the case of producing a patterned light-shielding film is a step of applying the curable composition of the present invention on a substrate to form a curable composition layer (hereinafter, appropriately "curable composition layer formation"). The process is abbreviated as "step"), the step of exposing the curable composition layer through a mask (hereinafter, appropriately abbreviated as "exposure step"), and the process of developing the curable composition layer after exposure to block light. Examples thereof include a step of forming a film (patterned light-shielding film) (hereinafter, appropriately abbreviated as “development step”).
Specifically, the curable composition of the present invention is applied directly or via another layer onto a substrate to form a curable composition layer (curable composition layer forming step), and a predetermined mask is formed. A patterned light-shielding film can be produced by exposing through a pattern, curing only the light-irradiated curable composition layer portion (exposure step), and developing with a developing solution (development step).
Hereinafter, each step in the above embodiment will be described.

<Curable composition layer forming step>
In the curable composition layer forming step, the curable composition of the present invention is applied onto a substrate to form a curable composition layer.
Examples of the substrate include various members in the solid-state image sensor (for example, an infrared light cut filter, an outer peripheral portion of the solid-state image sensor, a wafer-level lens outer peripheral portion, a back surface of the solid-state image sensor, and the like).
As a method for applying the curable composition of the present invention onto a substrate, various coating methods such as slit coating, inkjet method, rotary coating, cast coating, roll coating, and screen printing can be applied. ..
The curable composition applied on the substrate is usually dried at 70 ° C. or higher and 110 ° C. or lower under the conditions of about 2 minutes or more and 4 minutes or less, and a curable composition layer is formed.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed through a mask, and only the light-irradiated curable composition layer portion is cured.
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 preferably used, and a high-pressure mercury lamp is preferred as the light source. The irradiation intensity is preferably 5 mJ / cm ² or more 1500 mJ / cm ² or less, 10 mJ / cm ² or more 1000 mJ / cm ² or less being more preferred.

<Development process>
Following the exposure step, a development process (development step) is performed to elute the unirradiated portion of the light in the exposure step into a developer (for example, an alkaline aqueous solution).
As the developing solution, an organic alkaline developing solution is desirable. The developing temperature is usually preferably 20 ° C. or higher and 30 ° C. or lower, and the developing time is preferably 20 seconds or longer and 90 seconds or lower.
As the alkaline aqueous solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, and sodium metasilicate are used as the inorganic developing solution in a concentration of 0.001 to 10% by mass, preferably 0.001 to 10% by mass. An alkaline aqueous solution dissolved so as to have a concentration of 0.005 to 0.5% by mass can be mentioned. Organic developing solutions include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, and pyrrole. , Piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene and the like so that the concentration is 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass. An alkaline aqueous solution dissolved in is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the alkaline aqueous solution. When a developer composed of such an alkaline aqueous solution is used, it is generally preferable to wash (rinse) it with pure water or the like after development.

After performing the curable composition layer forming step, the exposure step, and the developing step, if necessary, a curing step of curing the formed patterned light-shielding film by heating and / or exposure may be performed.

[Infrared light cut filter with light-shielding film, solid-state image sensor]
When a light-shielding pigment is used as the colorant, the cured film described above can be suitably applied as a so-called light-shielding film. Further, such a light-shielding film can be suitably applied to a solid-state image sensor.
In the following, first, the first embodiment of the solid-state image sensor having the light-shielding film of the present invention will be described in detail.
As shown in FIGS. 1 and 2, the solid-state image pickup device 2 includes a CMOS sensor 3 as a solid-state image pickup element, a circuit board 4 on which the CMOS sensor 3 is mounted, and a ceramic ceramic substrate 5 that holds the circuit board 4. And have. Further, the solid-state image sensor 2 is held on a ceramic substrate 5, an IR cut filter 6 that cuts infrared light (IR) directed toward the CMOS sensor 3, a photographing lens 7, and a lens holder 8 that holds the photographing lens 7. And a holding cylinder 9 for movably holding the lens holder 8. Further, a CCD sensor or an organic CMOS sensor may be provided instead of the CMOS sensor 3.
The ceramic substrate 5 has an opening 5a into which the CMOS sensor 3 is inserted and has a frame shape, and surrounds the side surface of the CMOS sensor 3. In this state, the circuit board 4 on which the CMOS sensor 3 is mounted is fixed to the ceramic substrate 5 with an adhesive (for example, an epoxy adhesive, the same applies hereinafter). Various circuit patterns are formed on the circuit board 4.

In the IR cut filter 6, a reflective film that reflects infrared light is formed on a plate-shaped glass or blue glass, and the surface on which the reflective film is formed becomes an incident surface 6a. The IR cut filter 6 is formed in a size one size larger than the opening 5a, and is fixed to the ceramic substrate 5 with an adhesive so as to cover the opening 5a.
A CMOS sensor 3 is arranged behind the photographing lens 7 (lower in FIGS. 2 and 3), and an IR cut filter 6 is arranged between the photographing lens 7 and the CMOS sensor 3. The subject light enters the light receiving surface of the CMOS sensor 3 through the photographing lens 7 and the IR cut filter 6. At this time, the infrared light is cut by the IR cut filter 6.
The circuit board 4 is connected to a control unit provided in an electronic device (for example, a digital camera) on which the solid-state image sensor 2 is mounted, and power is supplied from the electronic device to the solid-state image sensor 2. In the CMOS sensor 3, a large number of color pixels are two-dimensionally arranged on a light receiving surface, and each color pixel photoelectrically converts incident light and accumulates the generated signal charge.

As shown in FIGS. 2 and 3, the above-mentioned light-shielding film (light-shielding layer) 11 is arranged over the entire circumference of the incident surface 6a of the IR cut filter 6, and infrared light with a light-shielding film is provided. A cut filter is formed. When the reflected light R1 emitted from the photographing lens 7 and reflected on the front surface of the ceramic substrate 5 (upper surface in FIGS. 2 and 3) is repeatedly reflected and refracted in the apparatus and then enters the CMOS sensor 3, and the image is taken. When the reflected light R2 reflected from the inner wall surface of the lens holder 8 emitted from the lens 7 is incident on the CMOS sensor 3, it causes flare in the captured image. The light-shielding film 11 blocks harmful light such as reflected light R1 and R2 directed toward the CMOS sensor 3. The light-shielding film 11 is applied by, for example, a spin coating method or a spray coating method. In addition, in FIG. 2 and FIG. 3, the thickness of the light-shielding film 11 is exaggerated.

FIG. 4 shows the solid-state image sensor 20 of the second embodiment. The same components as those of the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.
The solid-state image sensor 20 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The above-mentioned light-shielding film (light-shielding layer) 21 is formed on the side end surface of the IR cut filter 6 over the entire circumference. If the reflected light R3 emitted from the photographing lens 7 and reflected on the front surface of the ceramic substrate 5 enters the CMOS sensor 3 after repeated reflection and refraction in the apparatus, it causes flare in the photographed image. .. The light-shielding film 21 blocks harmful light such as reflected light R3 directed toward the CMOS sensor 3.

FIG. 5 shows the solid-state image sensor 30 of the third embodiment. The same components as those of the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.
The solid-state image sensor 30 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The above-mentioned light-shielding film (light-shielding layer) 31 is formed on the end and side end faces of the incident surface 6a of the IR cut filter 6 over the entire circumference. That is, it is a combination of the first and second embodiments. In this embodiment, the light-shielding performance is higher than that in the first and second embodiments, so that the occurrence of flare is surely suppressed.

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

[Image display device, color filter]
The cured film obtained by curing the curable composition of the present invention can be used in an image display device such as a liquid crystal display device and an organic electroluminescence display device. Further, the cured film can be used as a color filter.
Further, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
In this case, the partition wall preferably has a low refractive index for each color pixel.

For details on the definition of display devices and the details of each display device, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", "Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd.)" (Issued in the first year) ”etc. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".

The color filter in the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. A color TFT liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Publishing Co., Ltd. in 1996)". Further, the present invention is a liquid crystal display device having an enlarged viewing angle such as a transverse electric field drive method such as IPS (In Plane Switching) and a pixel division method such as MVA (Multi-domine Vertical Alginment), STN (Super-Twisted Nematic). , TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optical Protect) can also be applied.
Further, the color filter in the present invention can also be used in a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter are required for the interlayer insulating film, that is, low dielectric constant and resistance to the stripping liquid, in addition to the usual required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA type liquid crystal display device having high resolution and excellent long-term durability. In order to satisfy the required characteristics of low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD Display-Latest Trends in Technology and Market- (Toray Research Center Research Division, 2001)". Further, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478 and JP-A-2014-179757.

In addition to the color filter of the present invention, the liquid crystal display device of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these materials, for example, "'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima Co., Ltd., published in 1994)", "2003 Liquid Crystal Related Market Current Status and Future Prospects (Vol. 2)" Fuji Chimera Research Institute, Inc., published in 2003) ”.
Regarding the backlight, see SID meeting Digest 1380 (2005) (A.Konno et.al), Monthly Display December 2005 issue, pages 18-24 (Yasuhiro Shima), and pages 25-30 (Takaaki Yagi). Have been described.

In addition, the cured film obtained by curing the curable composition is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, or a digital camera; an OA (Office Automation) device such as a printer compound machine or a scanner; a surveillance camera. , Bar code readers, automatic cash deposit machines (ATMs), high-speed cameras, personal authentication using facial image authentication, and other industrial equipment; in-vehicle camera equipment; medical care such as endoscopes, capsule endoscopes, and catheters. Camera equipment; used for space equipment such as biosensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, meteorological and ocean observation cameras, land resource exploration cameras, exploration cameras for space astronomical and deep space targets, etc. It can be used as a light-shielding member or a light-shielding layer of an optical filter or module, and further as an antireflection member or an antireflection layer.

Further, the cured film obtained by curing the curable composition can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). Although not particularly limited, it is preferably used for optical filters and optical films used for micro LEDs and micro OLEDs, as well as members for imparting a light shielding function and an antireflection function.
Examples of the micro LED and the micro OLED include those of the special table 2015-500562 and the special table 2014-533890.

Further, the cured film obtained by curing the curable composition can also be used for applications such as quantum dot displays. Although not particularly limited, it is suitably used for an optical filter and an optical film used in a quantum dot display, as well as a member imparting a light shielding function and an antireflection function.
Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. Things can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, "parts" and "%" are based on mass.

[Production of Titanium Black A-1]
100 g of titanium oxide MT-150A (trade name: manufactured by TAYCA Corporation) having an average particle diameter of 15 nm, 25 g of silica particles AEROSIL 300 (registered trademark) 300/30 (manufactured by Ebonic) having a BET specific surface area of 300 m ² / g, and , Silica190 (trade name: manufactured by Big Chemie) was weighed and added to 71 g of ion electroexchanged water to obtain a mixture. Then, using MAZERSTAR KK-400W manufactured by KURABO, the mixture was treated at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm for 30 minutes to obtain a uniform aqueous mixture solution. The aqueous mixture solution was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Then, the atmosphere was replaced with nitrogen in the small rotary kiln, and the nitriding reduction treatment was carried out by flowing ammonia gas at 100 mL / min at the same temperature for 5 hours. After completion, the recovered powder was pulverized in a mortar to obtain a powdery titanium black [titanium black particles and a dispersion containing Si atoms] having a specific surface area of 73 m ² / g containing Si atoms (hereinafter, "titanium"). It is described as "black". However, it is described as "colorant 1" in Table 1).

[Preparation of Titanium Black Dispersion (TB Dispersion Solution 1)]
The components shown in composition 1 below were mixed for 15 minutes using a stirrer (Eurostar manufactured by IKA) to obtain a dispersion a.
The pigment dispersion resin (corresponding to the dispersant) described below was synthesized with reference to the description in JP2013-249417A. The weight average molecular weight of the pigment-dispersed resin was 30,000, the acid value was 60 mgKOH / g, and the number of atoms in the graft chain (excluding hydrogen atoms) was 117.

<Composition 1>
-Titanium black obtained as described above: 25.0 parts by mass-Propylene glycol monomethyl ether acetate 20% by mass solution of pigment dispersion resin
... 37.5 parts by mass-Propylene glycol monomethyl ether acetate (PGMEA) (solvent)
・ ・ ・ 10.5 parts by mass ・ Butyl acetate (solvent) ・ ・ ・ 27.0 parts by mass

The structure of the pigment-dispersed resin described above is as follows.

The obtained dispersion a was subjected to a dispersion treatment using NPM-Pilot manufactured by Symmul Enterprises Co., Ltd. under the following conditions, and a titanium black dispersion (hereinafter referred to as TB dispersion 1). Got

<Dispersion condition>
-Bead diameter: φ0.05 mm, made of zirconia-Bead filling rate: 65% by volume
・ Mill peripheral speed: 10 m / sec
・ Separator peripheral speed: 11 m / s
・ Amount of mixed liquid to be dispersed: 15 kg
・ Circulation flow rate (pump supply amount): 60 kg / hour
-Treatment liquid temperature: 19 to 21 ° C
・ Cooling water: Water ・ Number of passes: 90 passes

[Preparation of Titanium Black Dispersion (TB Dispersion Liquid 2)]
The TB dispersion liquid 2 was obtained in the same manner as the TB dispersion liquid 1 except that the dispersant a described below was used instead of the pigment dispersion resin. The dispersant a was synthesized with reference to the description in JP-A-2014-177614, where n represents 15 and * represents a connecting portion with the Z portion in the left structural formula.

[Preparation of Titanium Black Dispersion (TB Dispersion 3)]
The TB dispersion liquid 3 was obtained in the same manner as the TB dispersion liquid 1 except that the dispersant b described below was used instead of the pigment dispersion resin. The dispersant b was synthesized with reference to the description in JP-A-2010-6932, and * in the formula represents a connecting portion.

[Preparation of carbon black dispersion (CB dispersion)]
In the preparation of the above TB dispersion liquid 1, instead of titanium black, carbon black (trade name "Color Black S170", manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m ² / g, produced by gas black method). The dispersion b was prepared by the same method except that the carbon black was used, which is referred to as “colorant 2” in Table 1), and the carbon black dispersion (hereinafter referred to as CB dispersion) was prepared. .) Was obtained.

[Preparation of titanium black and carbon black dispersion (TB / CB dispersion)]
In the preparation of the TB dispersion liquid 1, the dispersion c was prepared by the same method except that 35 parts of titanium black and 10 parts of carbon black were used instead of titanium black, and titanium black was prepared. And a carbon black dispersion (hereinafter referred to as TB / CB dispersion) were obtained.

[Preparation of titanium black and pigment yellow (TB / PY dispersion)]
In the preparation of the above TB dispersion 1, instead of 45 parts of titanium black, 40 parts of titanium black and 150 parts of Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 pigment yellow 5GN, in Table 1 Dispersion d was prepared by the same method except that a mixture with 5 parts was used, and titanium black and pigment yellow dispersion (hereinafter referred to as TB / PY dispersion) were prepared. .) Was obtained.

[Synthesis of photobase generator]
For the photobase generators represented by the following general formulas (PBG1) to (PBG13), refer to JP-A-2015-087612, JP-A-2008-247747, and International Publication No. 2010/064631. Synthesized. PBG1 is also available as "WPBG-018" (product name) of Wako Pure Chemical Industries, Ltd.

[Example 1: Preparation of curable composition 1]
The curable composition 1 was obtained by mixing the following compositions. The titanium black described below is prepared by the above method, and a TB dispersion liquid 1 in which titanium black is dispersed using a pigment dispersion resin is prepared by the above method, and then the TB dispersion liquid 1 and other materials are mixed. did. Further, the curable composition 1 was diluted with propylene glycol monomethyl ether acetate (corresponding to an organic solvent) so as to have a solid content of 30%.

-Dipentaerythritol hexaacrylate 20.49 parts by mass (KAYARAD DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd.) Corresponds to a polymerizable compound. In Table 1, it is referred to as "polymerizable compound 1". )
OXE-02 5.90 parts by mass (corresponds to an oxime-based initiator manufactured by BASF. In Table 1, it is referred to as "photoradical polymerization initiator 1").
-PBG1 2.95 parts by mass (corresponds to a photobase generator)
Fluororesin 1: 0.07 parts by mass (mixture represented by the following chemical formula (weight average molecular weight (Mw) = 14000))

-Megafuck RS-72-K 1.00 parts by mass (manufactured by DIC, solid content 30%, solvent: propylene glycol monomethyl ether acetate, corresponding to fluororesin. In Table 1, "fluororesin 2" write.)
-0.01 parts by mass of p-methoxyphenol (manufactured by Kanto Chemical Co., Inc., polymerization inhibitor)
Binder polymer 11.5 parts by mass (benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer, ratio of each structural unit 60/20/20 wt%, weight average molecular weight: 14,000, corresponds to alkali-soluble resin .)
13.46 parts by mass of pigment dispersion resin (corresponding to the above-mentioned pigment dispersion resin and dispersant)
-Titanium black 45.00 parts by mass (corresponding to the above-mentioned titanium black and colorant)

[Examples 2-12: Preparation of curable compositions 2-12]
Curable compositions 2 to 12 were obtained by the same method except that PBGs 2 to 12 (both correspond to photobase generators) were used instead of PBG1 of Example 1.

[Example 13: Preparation of curable composition 13]
The same applies except that IRGACURE379 (manufactured by BASF, which corresponds to a photoradical polymerization initiator. In Table 1, it is referred to as “photoradical polymerization initiator 2”) is used instead of OXE-02 of Example 1. The curable composition 13 was obtained by the method of.

[Example 14: Preparation of curable composition 14]
The curable composition 14 was obtained by the same method as in Example 1 except that the amount of PBG1 used was 1.09 parts by mass and the amount of binder polymer used was 13.01 parts by mass.

[Example 15: Preparation of curable composition 15]
The curable composition 15 was obtained by the same method as in Example 1 except that the amount of PBG1 used was 1.07 parts by mass and the amount of binder polymer used was 13.03 parts by mass.

[Example 16: Preparation of curable composition 16]
The curable composition 16 was obtained by the same method as in Example 1 except that the amount of PBG1 used was 6.60 parts by mass and the amount of binder polymer used was 7.50 parts by mass.

[Example 17: Preparation of curable composition 17]
A curable composition 17 was obtained by the same method as in Example 1 except that the amount of PBG1 used was 6.85 parts by mass and the amount of binder polymer used was 7.25 parts by mass.

[Example 18: Preparation of curable composition 18]
The curable composition 18 was obtained by the same method as in Example 1 except that the amount of the fluororesin 1 used was 0.07 parts by mass and the amount of Megafuck RS-72-K used was 0.93 parts by mass. It was.

[Example 19: Preparation of curable composition 19]
Example 1 except that the amount of the fluororesin 1 used was 0.07 parts by mass, the amount of Megafuck RS-72-K used was 0.90 parts by mass, and the amount of the binder polymer used was 11.25 parts by mass. A curable composition 19 was obtained by the same method.

[Example 20: Preparation of curable composition 20]
By the same method as in Example 1 except that the amount of the fluororesin 1 used was 0 parts by mass, the amount of Megafuck RS-72-K used was 0 parts by mass, and the amount of the binder polymer used was 12.22 parts by mass. , A curable composition 20 was obtained.

[Example 21: Preparation of curable composition 21]
The curable composition 21 was obtained by the same method as in Example 1 except that the amount of p-methoxyphenol used was 0 parts by mass and the amount of binder polymer used was 11.16 parts by mass.

[Example 22: Preparation of curable composition 22]
The curable composition 22 was obtained by the same method as in Example 1 except that the amount of dipentaerythritol hexaacrylate used was 31.64 parts by mass and the amount of binder polymer used was 0 parts by mass.

[Example 23: Preparation of curable composition 23]
The curable composition 23 was obtained by the same method as in Example 1 except that the CB dispersion prepared by the above method was used instead of the TB dispersion 1.

[Example 24: Preparation of curable composition 24]
The curable composition 24 was obtained by the same method as in Example 1 except that the TB / CB dispersion prepared by the above method was used instead of the TB dispersion 1.

[Example 25: Preparation of curable composition 25]
The curable composition 25 was obtained by the same method as in Example 1 except that the TB / PY dispersion prepared by the above method was used instead of the TB dispersion 1.

[Example 26: Preparation of curable composition 26]
Propylene glycol monomethyl ether acetate and cyclopentanone were used as the organic solvent, and the mixture was diluted so that the content of cyclopentanone in the curable composition was 10% by mass and the solid content of the curable composition was 30%. The curable composition 26 was obtained by the same method as in Example 1 except for the above.

[Example 27: Preparation of curable composition 27]
The curable composition 27 was obtained by the same method as in Example 1 except that the TB dispersion 2 prepared by the above method was used instead of the TB dispersion 1.

[Example 28: Preparation of curable composition 28]
The curable composition 28 was obtained by the same method as in Example 1 except that the TB dispersion 3 prepared by the above method was used instead of the TB dispersion 1.

[Example 29: Preparation of curable composition 29]
By the same method as in Example 1 except that pentaerythritol tetraacrylate (corresponding to a polymerizable compound; referred to as “polymerizable compound 2” in Table 1) was used instead of dipentaerythritol hexaacrylate. , A curable composition 29 was obtained.

[Example 30: Preparation of curable composition 30]
The curable composition 30 was obtained by the same method as in Example 1 except that 10.00 parts by mass of dipentaerythritol hexaacrylate and 10.49 parts by mass of pentaerythritol tetraacrylate were used instead of dipentaerythritol hexaacrylate. It was.

[Example 31: Preparation of curable composition 31]
Example 1 except that OXE-01 (manufactured by BASF, which corresponds to an oxime-based initiator. In Table 1, it is referred to as "photoradical polymerization initiator 3") was used instead of OXE-02. The curable composition 31 was obtained by the same method.

[Example 32: Preparation of curable composition 32]
Except for the use of a compound represented by the following formula (I-1) (corresponding to an oxime-based initiator. In Table 1, it is referred to as "photoradical initiator 4") instead of OXE-02. The curable composition 33 was obtained by the same method as in Example 1. The following formula (I-1) was synthesized with reference to the methods described in paragraphs 0344 to 0345 of Japanese Patent Application Laid-Open No. 2014-500852.

[Example 33: Preparation of curable composition 33]
A curable composition 34 was obtained by the same method as in Example 1 except that PEG13 was used instead of PBG1.

[Comparative Example 1]
A comparatively curable composition was obtained by the same method as in Example 1 except that a binder polymer was used instead of PEG1 (14.10 parts by mass in total of the binder polymer).

〔Evaluation method〕
<Preparation of cured film>
Each curable composition was applied by a spin coating method on a glass plate (Corning 1737, manufactured by Corning Inc.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm so that the dry film thickness was 2.0 μm. Then, the glass plate coated with the curable composition was heat-treated (prebaked) for 120 seconds using a hot plate at 100 ° C. to form a coating film. Next, the entire surface of the coating film was exposed to an exposure amount of 1000 mJ / cm ^{2 with} a high-pressure mercury lamp. Then, a glass plate having a coating film exposed on the entire surface was heated on a hot plate at 200 ° C. for 300 seconds to obtain a cured film.

<Measurement of reflectance>
Light was incident on the cured film on the glass plate formed by the above method at an incident angle of 5 °, and specular reflection measurement was performed. The measurement was carried out using a spectrophotometer U-4100 manufactured by Hitachi High-Technology, and the wavelength of the incident light was changed in the range of 400 to 1100 nm to confirm the maximum reflectance.

The measurement results of the reflectance and the composition of each curable composition are summarized in Table 1 below. The numerical values in each component column in Table 1 represent parts by mass. Further, in Table 1, the "molecular weight of the generated base" means the molecular weight of the base (primary amine or secondary amine) generated by the decomposition of the photobase generator, calculated from the structural formula. Further, the "quantity ratio" means the mass ratio of the photobase generator and the dispersant (mass of the photobase generator / mass of the dispersant).

As shown in Table 1, the cured film formed by the curable composition containing a predetermined component had excellent low reflectivity. It was also found that each cured film has an excellent light-shielding property and can be used as a light-shielding film.
On the other hand, the cured film formed by the curable composition of Comparative Example 1 containing no predetermined photobase generator did not have the desired effect.

Examples 14 to 17 and Examples in which the mass ratio of the photobase generator to the dispersant (mass of the photobase generator / mass of the dispersant) was changed to 0.081, 0.079, 0.49, 0.51. Comparing with No. 1, it was found that the light-shielding film formed by the curable composition having a mass ratio of 0.08 to 0.5 had better low reflectivity.

Comparing Examples 1 and 9 to 12 with respect to Examples 6 to 8, when the molecular weights of the generated secondary amines are the same, Ar ^a in the general formula (PBG) has ^a condensed ring structure. It was found that the light-shielding film formed by the curable composition containing the photobase generator having a photobase generator has better low reflectivity.

Comparing Examples 1 to 5 in which the Ar ^a group in the general formula (PBG) of the photobase generator is the formula (CR1), it is formed by a curable composition containing a photobase generator having a small molecular weight of the generated base. It was found that the light-shielding film to be used had better low reflectivity.
Further, comparing Examples 1 and 33, in the general formula (PBG), the light-shielding film formed by the curable composition containing a photobase generator in which ^Ra and R ^b are alkyl groups is better. It was found to have better low reflectivity.

Comparing Example 1 and Example 20, it was found that the light-shielding film formed of the curable composition containing a fluororesin had better low reflectivity.

Comparing Example 1, Example 13, Example 31, and Example 32, the light-shielding film formed by the curable composition containing an oxime-based initiator as a radical initiator is more excellent and lower. It was found to have reflectivity.

Comparing Example 1 and Example 26, it was found that the light-shielding film formed of the curable composition containing two or more kinds of organic solvents had a better low reflectance. ..

Comparing Example 1 and Example 23, it was found that the light-shielding film formed of the curable composition containing a titanium compound (titanium black) had better low reflectance. ..
Comparing Example 1, Example 27, and Example 28, a light-shielding film formed of a curable composition containing a polymer compound having a structural unit represented by the general formula (1) as a dispersant. It was found that the one had better low reflectance.
Comparing Example 1 and Example 29, the light-shielding film formed of the curable composition containing a polymerizable compound having 5 or more ethylenically unsaturated groups has a better low reflectance. I found out that I was doing it.

[Manufacturing and evaluation of light-shielding film for wafer level lens]
A lens film was formed by the following operations.

<Formation of lens film>
A 5 × 5 cm glass substrate (thickness) containing 2 mL of a lens film forming composition obtained by adding 1% by mass of an aryl sulfonium salt derivative (SP-172 manufactured by ADEKA) to an alicyclic epoxy resin (EHPE-3150 manufactured by Daicel Chemical Co., Ltd.). It was applied on 1 mm, BK7) manufactured by Schott, and the coating film was heated at 200 ° C. for 1 minute to be cured to form a lens film having a thickness of 80 μm.

<Curable composition layer forming step>
The curable composition of Example 1 is applied onto the lens film of a glass substrate (hereinafter referred to as “support”) on which the lens film is formed, and the curable composition 1 is applied by a hot plate having a surface temperature of 120 ° C. The support was heated for 120 seconds. In this way, a coating film having a film thickness of 2.0 μm (corresponding to the curable composition layer) was obtained.

<Exposure process>
Next, the obtained curable composition layer was exposed with an exposure amount of 500 mJ / cm ² using a high-pressure mercury lamp through a photomask having a hole pattern of 10 mm.

<Development process>
The curable composition layer after the exposure was paddle-developed at a temperature of 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide as a developing solution. Then, the developed curable composition layer was rinsed by a spin shower, and the rinsed composition layer was washed with pure water to obtain a patterned light-shielding film. ..

<Manufacturing of solid-state image sensor>
A coating film was formed on the patterned light-shielding film produced by the above-mentioned method by using the above-mentioned lens film-forming composition. Then, the shape was transferred with a quartz mold having a lens shape, and the coating film was cured with an exposure amount of 400 mJ / cm ² with a high-pressure mercury lamp to prepare a wafer level lens array having a plurality of wafer level lenses.
After cutting the produced wafer level lens array and producing a lens module using the obtained wafer level lens, an image sensor and a sensor substrate were attached to produce an image pickup unit (corresponding to a solid-state image pickup device).

<Evaluation>
The obtained wafer level lens had good transparency with no residue in the lens opening. Further, the light-shielding layer had low reflection, high uniformity of the coated surface, and high light-shielding property.

[Manufacturing and evaluation of color filters having a black matrix]
A color filter having a black matrix was produced by the following operation.

<Formation of black matrix>
The curable composition of Example 1 is applied to a glass wafer by a spin coating method, and then the glass wafer coated with the curable composition is heated at 120 ° C. for 2 minutes on a hot plate to obtain a coating film (cured). (Corresponding to the sex composition layer) was obtained. The film thickness of the obtained coating film was 2.0 μm.
The curable composition layer was then exposed using an i-line stepper through a photomask having an Island pattern with a pattern of 0.1 mm at an exposure of 500 mJ / cm ² .
The curable composition layer after the exposure was paddle-developed at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide as a developing solution. After that, the developed curable composition layer is rinsed by a spin shower, and the rinsed curable composition layer is washed with pure water to obtain a patterned light-shielding film (black). Matrix) was obtained.

<Preparation of chromatic color curable composition>
In the curable composition of Example 1, titanium black was replaced with the following chromatic pigment, and the same was true for the red (R) color curable composition R-1 and the green (G) color curable composition, respectively. A sex composition G-1 and a color curable composition B-1 for blue (B) were prepared.
~ RGB chromatic pigments for forming colored pixels of each color ~
-Red (R) pigment C. I. Pigment Red 254
-Pigment for green (G) C. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 and 30/70 [mass ratio] mixture, blue (B) pigment C.I. I. Pigment Blue 15: 6 and C.I. I. 30/70 [mass ratio] mixture with Pigment Violet 23

<Making color filters>
In the black matrix produced above, the coloring curable composition R-1 for red (R) is used to color 80 × 80 μm red (R) in the same manner as in the method for producing the black matrix produced above. Formed a pattern. Further, similarly, a green (G) coloring curable composition G-1 is used to obtain a green (G) chromatic coloring pattern, and a blue (B) coloring curable composition B-1 is used to obtain a blue color. The chromatic coloring pattern of (B) was sequentially formed to prepare a color filter having a black matrix for a liquid crystal display device.

<Evaluation>
It was found that the liquid crystal display device equipped with the obtained color filter obtained a clear image with high contrast and was extremely excellent in visibility even under external light.
The light-shielding layer has a high optical density and can realize sufficient light-shielding property to prevent the light from the backlight from passing through, so that not only a high-contrast and clear image can be obtained, but also the low reflectance makes it possible to obtain a clear image even under external light. It is presumed that the visibility is extremely excellent.

2,20,30,40 Solid-state image sensor 3 CMOS sensor 4 Circuit board 5 Ceramic board 5a Aperture 5b Inner wall surface 6 IR cut filter 6a Incident surface 7 Shooting lens 8 Lens holder 9 Holding cylinder 10,11,21,31,41 Shading Film (light-shielding layer)

Claims (17)

A curable composition containing a colorant, a photoradical polymerization initiator, a polymerizable compound, a base generator, a dispersant, and two or more kinds of organic solvents.
The photoradical polymerization initiator is an oxime-based initiator.
Weight ratio before Kishio radical generator to said dispersing agent, Ri 0.08 to 0.5 der,
The colorant is, you containing a titanium compound, a curable composition. A curable composition containing a colorant, a photoradical polymerization initiator, a polymerizable compound, a base generator, a dispersant, and two or more kinds of organic solvents.
The photoradical polymerization initiator is an oxime-based initiator having a fluorine atom.
A curable composition in which the mass ratio of the base generator to the dispersant is 0.08 to 0.5.
However, the curable composition does not contain the compound represented by the following formula (1).

In equation (1), R ¹ And R ² Independently indicate a hydrogen atom or an organic group. However, R ¹ And R ² At least one of them represents an organic group. R ¹ And R ² They may be bonded to form a cyclic structure or may contain a heteroatom bond. R ³ Indicates a single bond or an organic group. R ⁴ And R ⁵ Are independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato. Indicates a group or an organic group. R ⁶ , R ⁷ , R ⁸ , And R ⁹ Are independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato. Indicates a group, amino group, ammonio group, or organic group. However, R6 and R7 do not become hydroxyl groups. R ⁶ , R ⁷ , R ⁸ , And R ⁹ May form a cyclic structure in which two or more of them are bonded to each other, and may contain a heteroatom bond. R ¹⁰ Indicates a hydrogen atom or an organic group. A curable composition containing a colorant, a photoradical polymerization initiator, a polymerizable compound, a base generator, a dispersant, and two or more kinds of organic solvents.
The photoradical polymerization initiator is an oxime-based initiator.
The mass ratio of the base generator to the dispersant is 0.08 to 0.5.
A curable composition in which the colorant contains a yellow pigment and a light-shielding pigment.
However, the curable composition does not contain the compound represented by the following formula (1).

In equation (1), R ¹ And R ² Independently indicate a hydrogen atom or an organic group. However, R ¹ And R ² At least one of them represents an organic group. R ¹ And R ² They may be bonded to form a cyclic structure or may contain a heteroatom bond. R ³ Indicates a single bond or an organic group. R ⁴ And R ⁵ Are independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato. Indicates a group or an organic group. R ⁶ , R ⁷ , R ⁸ , And R ⁹ Are independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato. Indicates a group, amino group, ammonio group, or organic group. However, R6 and R7 do not become hydroxyl groups. R ⁶ , R ⁷ , R ⁸ , And R ⁹ May form a cyclic structure in which two or more of them are bonded to each other, and may contain a heteroatom bond. R ¹⁰ Indicates a hydrogen atom or an organic group. A curable composition containing a colorant, a photoradical polymerization initiator, a polymerizable compound, a base generator, a dispersant, two or more kinds of organic solvents, and a fluororesin.
The photoradical polymerization initiator is an oxime-based initiator.
A curable composition in which the mass ratio of the base generator to the dispersant is 0.08 to 0.5.
However, the curable composition does not contain the compound represented by the following formula (1).

In equation (1), R ¹ And R ² Independently indicate a hydrogen atom or an organic group. However, R ¹ And R ² At least one of them represents an organic group. R ¹ And R ² They may be bonded to form a cyclic structure or may contain a heteroatom bond. R ³ Indicates a single bond or an organic group. R ⁴ And R ⁵ Are independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato. Indicates a group or an organic group. R ⁶ , R ⁷ , R ⁸ , And R ⁹ Are independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato. Indicates a group, amino group, ammonio group, or organic group. However, R6 and R7 do not become hydroxyl groups. R ⁶ , R ⁷ , R ⁸ , And R ⁹ May form a cyclic structure in which two or more of them are bonded to each other, and may contain a heteroatom bond. R ¹⁰ Indicates a hydrogen atom or an organic group. The curable composition according to any one of claims 1 , 3 and 4 , wherein the oxime-based initiator is an oxime-based initiator having a fluorine atom. The curable composition according to any one of claims 1 to 5 , wherein the oxime-based initiator is a compound represented by the following formula (I-1).
The curable composition according to claim 2 or 4 , wherein the colorant is a light-shielding pigment. The curable composition according to any one of claims 2, 4 and 7 , wherein the colorant contains a yellow pigment and a light-shielding pigment. The curable composition according to any one of claims 3, 7 and 8 , wherein the light-shielding pigment is a titanium compound. The curable composition according to any one of claims 1 to 3 , further comprising a fluororesin. The curable composition according to any one of claims 1 to 10 , wherein the base generator contains a photobase generator. The curable composition according to claim 11 , wherein the photobase generator is represented by the following general formula (PBG).

In the general formula (PBG), ^Ra and R ^b independently represent a hydrogen atom or a monovalent organic group, ^Ra and R ^b may be bonded to each other to form a ring, and Ar ^a may be an aryl group. Or represents a heteroaryl group. The curing according to claim 12 , wherein in the general formula (PBG), ^Ra and R ^b each independently represent a hydrogen atom or an alkyl group, and ^Ra and R ^b may be bonded to each other to form a ring. Sex composition. The curable composition according to any one of claims 11 to 13 , wherein the base generated from the photobase generator is an amine compound, and the molecular weight of the amine compound is 150 or less. A light-shielding film obtained by curing the curable composition according to any one of claims 1 to 14 . A solid-state image sensor having the light-shielding film according to claim 15 . A color filter having the light-shielding film according to claim 15 .