WO2017141723A1 - Curable composition, light-shielding film, solid-state imaging device, and color filter - Google Patents

Curable composition, light-shielding film, solid-state imaging device, and color filter Download PDF

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WO2017141723A1
WO2017141723A1 PCT/JP2017/003898 JP2017003898W WO2017141723A1 WO 2017141723 A1 WO2017141723 A1 WO 2017141723A1 JP 2017003898 W JP2017003898 W JP 2017003898W WO 2017141723 A1 WO2017141723 A1 WO 2017141723A1
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group
curable composition
light
ring
dispersion
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PCT/JP2017/003898
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French (fr)
Japanese (ja)
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高桑　英希
恒光 留場
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富士フイルム株式会社
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Priority to JP2018500033A priority Critical patent/JP6797889B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to a curable composition, a light shielding film, a solid-state imaging device, and a color filter.
  • 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.
  • Solid-state imaging devices mounted on digital cameras and smartphones have a CCD (Charge-Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) behind the taking lens. It has a solid-state image sensor.
  • This solid-state imaging device is provided with a light shielding film for the purpose of light shielding on the back surface side, prevention of noise generation due to light shielding in the infrared region between pixels, and improvement of image quality.
  • the inventors of the present invention have disclosed a 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, it was found that the reflectance was high and the level of low reflectivity required for a light-shielding film has not been achieved.
  • 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-described curable composition, a solid-state imaging device having the above-described light-shielding film, and a color filter.
  • a curable composition containing a colorant, a radical photopolymerization 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 a 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.
  • PBG general formula
  • a curable composition capable of producing a cured film having excellent low reflectivity can be provided.
  • curing the above-mentioned curable composition, the solid-state imaging device which has the above-mentioned light shielding film, and a color filter can be provided.
  • FIG. 1 It is a perspective view which shows the solid-state imaging device of 1st Embodiment. It is a disassembled perspective view of the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 2nd Embodiment. It is sectional drawing which shows the solid-state imaging device of 3rd Embodiment. It is sectional drawing which shows the solid-state imaging device of 4th Embodiment.
  • the description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • the description that does not describe substitution and non-substitution includes 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 is included.
  • 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 also about each compound.
  • radiation in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • light means actinic rays or radiation.
  • exposure means not only exposure with deep ultraviolet rays, X-rays, EUV light, etc., typified by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in exposure.
  • (meth) acrylate represents both and / or acrylate and methacrylate
  • (meth) acryl represents both and / or acryl and methacryl
  • “monomer” and “monomer” are synonymous.
  • the monomer in the present specification is distinguished from an oligomer and a polymer, and means a compound having a weight average molecular weight of 2,000 or less unless otherwise specified.
  • the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer.
  • the polymerizable functional group refers to a group that participates in a polymerization reaction.
  • preparation in the present specification means that a specific material is synthesized or blended, and a predetermined item is procured by purchase or the like.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the curable composition of the present invention contains a colorant, a radical photopolymerization initiator, a polymerizable compound, a base generator, and a dispersant.
  • a 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 produce a cured film (hereinafter also simply referred to as “cured film”).
  • cured film a cured film
  • the curable composition of the present invention contains a radical photopolymerization initiator and a base generator, when the coating film is irradiated with radiation of a predetermined wavelength, the polymerization reaction of the polymerizable compound by the radical photopolymerization initiator. And the base generation reaction from the base generator are presumed to proceed competitively. This tendency is more remarkable when the base generator contains a photobase generator.
  • the above reaction proceeds and curing proceeds.
  • the base generator decomposes to generate a base, and the base diffuses in the coating film.
  • the amount of radiation that reaches is higher than that of the upper region.
  • the polymerization of the polymerizable compound by the radical photopolymerization initiator in the lower region is assumed to be slow compared to the upper region.
  • the radiation necessary for radical generation can also be used for base generation. Therefore, in the lower region where the amount of radiation that reaches 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 that in the upper region.
  • the base generated from the base generator diffuses from the upper region in the lower region, the progress of the polymerization reaction is further suppressed.
  • the speed and / or progress of the polymerization reaction are different between the upper region and the lower region.
  • the cured film obtained by curing this coating film has different wrinkles due to curing shrinkage between the upper region and the lower region, so that fine wrinkles are generated in the upper region, which reduces the low reflectivity of the cured film. Presumed to have contributed.
  • the curable composition of the present invention contains a colorant.
  • a known colorant can be used as the colorant, and among these, it is preferable to contain a pigment.
  • the pigment for example, when used in the production of a color filter, chromatic pigments (chromatic colors such as R (red), G (green), and B (blue)) that form color pixels of the color filter. Pigment).
  • a coloring agent when using a cured film as a light shielding film or a black matrix, it is preferable that a coloring agent contains a light shielding pigment at the point which the cured film has the outstanding light-shielding property.
  • the light-shielding pigment a known light-shielding pigment can be used. From the viewpoint of realizing a high optical density (Optical Density: OD value) in a small amount, carbon black, titanium compound, iron oxide, manganese oxide, and graphite. Among them, it is preferable to contain at least one selected from the group consisting of carbon black and a titanium compound, and a titanium compound is 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.
  • titanium compound For example, a titanium oxide, titanium black, etc. are mentioned. Of these, titanium black is preferable in that it has a light-shielding property for light in a wide range of 400 to 1000 nm, and has a high light transmittance in a wavelength region (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 oxynitride and titanium nitride.
  • the surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation.
  • 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, treatment with a water-repellent substance as disclosed in JP 2007-302836 A is also possible. Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small. Specifically, the average primary particle diameter of titanium black is preferably in the range of 10 nm to 45 nm.
  • the particle diameter that is, the particle diameter is a 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 the value measured by the BET (Brunauer, Emmett, Teller) method in order that the water repellency after surface treatment of such titanium black with a water repellent agent becomes a predetermined performance. Is usually about 5 m 2 / g or more and 150 m 2 / g or less, 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, 13R-N, 13M-T (trade names: above, manufactured by Mitsubishi Materials Corporation), Tilac ( Tilac) D (trade name: manufactured by Ako Kasei Co., Ltd.).
  • titanium black is contained as a dispersion in the curable composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.00 on a mass basis. It is preferable that it is 05 or more.
  • the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
  • the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion in the present invention exceeds 0.5 (in terms of mass), it is difficult to produce a curable composition using the dispersion.
  • the upper limit is preferably 0.5.
  • Si / Ti of the object to be dispersed is 0.05 or more and 0.0. It is more preferably 5 or less, and further preferably 0.07 or more and 0.4 or less.
  • 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 subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly formed.
  • a dispersed material containing Si and Ti as components can be obtained.
  • the specific aspect for changing Si / Ti of a to-be-dispersed body is demonstrated.
  • Titanium black in which Si / Ti is adjusted to 0.05 or more, for example, can be obtained by, for example, the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of JP-A-2008-266045. Can be produced.
  • the present invention by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), this coverage is achieved.
  • a suitable range for example, 0.05 or more
  • the residue derived from the curable composition outside the region where the light shielding film is formed is reduced.
  • the residue includes 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 above-mentioned dispersed material tends to have a small particle size (for example, the particle size is 30 nm or less).
  • the adsorptivity of the entire film with the underlayer is reduced, which is assumed to contribute to the improvement in the development removability of the uncured curable composition (particularly titanium black) in the formation of the light shielding film. is doing.
  • titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is converted into mass)
  • the light-shielding film formed by using a material having a thickness 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, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
  • the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is 0.05 or more.
  • the method (2) described in paragraph 0035 of JP2013-249417A is used.
  • the above-described titanium black can be used.
  • complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, and A black pigment made of aniline black or the like may be used alone or in combination of two or more as a dispersion. In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black.
  • a Si-containing material such as silica may be used.
  • silica examples include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These can be selected and used as appropriate.
  • 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.
  • the fine particle type silica include 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 kind of titanium black or may contain two or more kinds.
  • 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 mill, sand mill, roll mill, ball mill, high speed impeller, sand grinder, flow jet mixer, high pressure wet atomization, ultrasonic dispersion, and microfluidizer.
  • Disperser described in “Issuance, October 10, 1978” can be preferably used.
  • materials, equipment, processing, conditions and the like used in the salt milling process for example, those described in JP-A-2015-194521, JP-A-2012-046629, etc. can be used.
  • a sand mill (bead mill) is preferable.
  • the curable composition of the present invention may contain extender pigments as necessary in addition to the colorant.
  • 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 extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the colorant.
  • the colorant and extender can be used with their surface modified with a polymer in some cases.
  • Coloring agents may be used alone or in combination of two or more.
  • a coloring agent you may contain colored organic pigments, such as red, blue, yellow, green, and purple.
  • the colored organic pigment is preferably used in an amount of 1 to 40% by mass with respect to the light-shielding pigment.
  • the red pigment is preferably Pigment Red 254, although not particularly limited.
  • Pigment Yellow 150 is preferable as the yellow pigment.
  • 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 more preferably 35 to 60% by mass with respect to the total solid content in the curable composition. % Is more preferable.
  • the curable composition of the present invention contains a radical photopolymerization initiator.
  • the radical photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known radical photopolymerization initiators. For example, those having photosensitivity from the ultraviolet region to the visible light region are preferable.
  • the photo radical polymerization initiator may be an activator that generates an active radical by generating some action with a photo-excited sensitizer.
  • the radical photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).
  • the radical photopolymerization initiator is preferably a compound having at least an aromatic group.
  • (bis) acylphosphine oxide or its esters, acetophenone compounds, ⁇ -aminoketone compounds, benzophenone compounds, benzoin ether compounds 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 onium salt compounds such as compounds, metallocene compounds, organoboron salt compounds, and disulfone compounds.
  • oxime ester compounds From the viewpoint of sensitivity, oxime ester compounds, acylphosphine oxide compounds, acetophenone compounds, ⁇ -aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, or thiol compounds are preferred, and oxime ester compounds (oxime initiators, The form is more preferable).
  • oxime ester compounds oxime initiators, The form is more preferable.
  • excellent lithographic properties can be easily obtained by using an oxime ester compound as a radical photopolymerization initiator.
  • hydroxyacetophenone compounds As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used.
  • acylphosphine-based initiator commercially available products IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • an oxime initiator is more preferable.
  • an oxime-based initiator is preferable because it has high sensitivity and high polymerization efficiency, can be cured regardless of the colorant (colorant) concentration, and can be easily designed with a high colorant concentration.
  • Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • oxime initiator examples include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane.
  • 3-benzoyloxyiminobutan-2-one 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane.
  • 2-acetoxyimino-1-phenylpropan-1-one 2-benzoyloxyimino-1-phenylpropan-1-one
  • 4--toluenesulfonyloxy iminobutan-2-one
  • 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one examples include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-
  • oxime initiators include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, and JP-A No. 2006-342166. It is done.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • TRONLY TR-PBG-304 TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcles NC 930 (manufactured by ADEKA) can also be used.
  • oxime initiators other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N-position, and those described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety
  • compounds compounds described in Japanese Patent Application Laid-Open No. 2010-15025, US Patent Publication No. 2009-292039, and ketoxime initiator and triazine skeleton described in International Patent Publication No. 2009-131189, in which a nitro group is introduced at the dye moiety
  • An oxime initiator having a fluorene ring can also be used as a photo radical polymerization initiator.
  • Specific examples of the oxime initiator having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.
  • an oxime initiator having a fluorine atom can also be used.
  • Specific examples of the oxime initiator having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. And the compound (C-3) described. This content is incorporated herein.
  • an oxime initiator having a nitro group can be used as the photo radical polymerization initiator.
  • Specific examples of the oxime initiator having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Adeka Arkles NCI-831 (manufactured by ADEKA) can be mentioned.
  • oxime initiator Specific examples of the oxime initiator are shown below, but the present invention is not limited thereto.
  • a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm is preferable, a compound having an absorption wavelength in a wavelength region of 360 nm to 480 nm is more preferable, and a compound having high absorbance at 365 nm and 405 nm is particularly preferable. preferable.
  • the molar extinction coefficient at 365 nm or 405 nm of the photo radical polymerization initiator is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, from the viewpoint of sensitivity, and 5,000. It is particularly preferred that it is ⁇ 200,000.
  • a known method can be used to measure 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) using an ethyl acetate solvent at a compound concentration of 0.01 g / L. Two or more kinds of radical photopolymerization initiators may be used in combination as necessary.
  • the content of the photo radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1 to 20% by mass with respect to the total solid content of the curable composition. %. Within this range, better sensitivity and pattern formability can be obtained.
  • 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 is preferably 2 or more, more preferably 4 or more, and more preferably 5 or more, in that the cured film has more excellent low reflectivity.
  • the upper limit is not particularly limited, but is preferably 10 or less from the viewpoint of synthesis.
  • Examples of the ethylenically unsaturated group include (meth) acryloyl group, (meth) acrylamide group, and vinyl group.
  • polyethylene glycol mono (meth) acrylate polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl)
  • a polyfunctional alcohol such as ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane, which is obtained by adding ethylene oxide or prop
  • dipentaerythritol penta (meth) acrylate dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are linked to dipentaerythritol via an ethylene glycol residue or a propylene glycol residue.
  • dipentaerythritol penta (meth) acrylate dipentaerythritol hexa (meth) acrylate
  • a structure in which these acryloyl groups are linked to dipentaerythritol via an ethylene glycol residue or a propylene glycol residue.
  • oligomer types can also be used.
  • urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58- Urethane compounds having an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used.
  • a photopolymerizable curable composition having an excellent photosensitive speed can be obtained.
  • Commercially available products include urethane oligomers UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name, Nippon Kasei) Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). Further, ethylenically unsaturated compounds having an acid group are also suitable.
  • Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.
  • the polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.
  • a polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the combination mode can be appropriately set according to physical properties required for the curable composition.
  • a suitable combination aspect of a polymeric compound the aspect which combines 2 or more types of polymeric compounds selected from the polyfunctional acrylate compound mentioned above is mentioned, for example, As an example, dipentaerythritol hexaacrylate is mentioned. 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 and more preferably 10% by mass to 50% by mass with respect to the total solid content in the curable composition.
  • the curable composition of the present invention contains a base generator.
  • the base generator include a thermal base generator and a photobase generator.
  • the type of the thermal base generator is not particularly limited.
  • an acidic compound (A1) that generates a base when heated to 40 ° C. or higher and an ammonium salt (A2) having an anion having an pKa1 of 0 to 4 and an ammonium cation And at least one selected from.
  • the acidic compound (A1) and the ammonium salt (A2) generate a base when heated.
  • the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, and 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 further preferably 165 ° C. or lower.
  • the lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher.
  • the base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
  • the base generated by the hot base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine.
  • the base generated by the thermal base generator preferably has a boiling point of 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 molecular weight value 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 a cation 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.
  • the thermal base generator will be described in detail.
  • 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, and may be outside the molecule of the ammonium cation, but may be outside the molecule of the ammonium cation. preferable.
  • numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple
  • the anion outside the molecule of the cation moiety is also referred to as a counter anion.
  • R 1 to R 6 each independently represents a hydrogen atom or a hydrocarbon group
  • R 7 represents a hydrocarbon group.
  • R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 5 and R 7 may be bonded to form a ring.
  • the ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation.
  • the upper limit of the anion pKa1 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 kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate 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.
  • the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and the determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafrigerch, O., Hafliger, O., Hafliger, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafliger, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch., Hafrigerch., Hafrigerch., Hafrigerch., Hafrigerch., Hafrigerch., Hafrigerch., Hafrigerch., Hafrigerch., Hafrigerch., Hafrigerch., Haf
  • the carboxylate anion is preferably represented by the following general formula (X1).
  • EWG represents an electron-withdrawing group.
  • the electron-withdrawing group means a group having a positive Hammett's substituent constant ⁇ m.
  • ⁇ m is a review by Yugo Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) P.I. 631-642.
  • the electron-withdrawing group of the present invention is not limited to the substituents described in the above documents.
  • Me represents a methyl group
  • Ac represents an acetyl group
  • Ph represents a phenyl group.
  • EWG preferably represents a group represented by the following general formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group
  • Ar represents an aromatic ring group.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted.
  • substituent group A examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group and tert group -Alkoxy groups such as butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acetoxy group, propionyloxy group and benzoyloxy group 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;
  • the alkenyl group has preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 10 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkenyl group may have a substituent or may be unsubstituted.
  • a substituent what was demonstrated as the above-mentioned substituent group A is mentioned.
  • a carboxyl group is preferable.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the aryl group may have a substituent or may be unsubstituted.
  • a substituent what was demonstrated as the above-mentioned substituent group A is mentioned.
  • a carboxyl group is preferable.
  • Specific examples of the aromatic ring group include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, Anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyr
  • 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.
  • the substituent which the aromatic ring group may have what was demonstrated as the above-mentioned substituent group A is mentioned.
  • a carboxyl group is preferable.
  • the carboxylate anion is preferably represented by the following general formula (X).
  • L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR X —, and a combination thereof
  • R X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.
  • the alkylene group represented by L 10 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkylene group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
  • the number of carbon atoms of the alkenylene group represented by L 10 is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10.
  • the alkenylene group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkenylene group may have a substituent or may be unsubstituted.
  • substituent group A As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
  • the number of carbon atoms of the arylene group represented by L 10 is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.
  • the arylene group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
  • the number of carbon atoms of the alkyl group represented by R X is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
  • the alkenyl group represented by R X preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkenyl group may have a substituent or may be unsubstituted.
  • substituent group A what was demonstrated as the above-mentioned substituent group A is mentioned.
  • the number of carbon atoms of the aryl group represented by R X is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.
  • the aryl group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
  • carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
  • ammonium cation is preferably represented by any one of the following general formulas (Y1-1) to (Y1-6).
  • R 101 represents an n-valent organic group
  • R 102 to R 111 each independently represents a hydrogen atom or a hydrocarbon group
  • 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 bonded 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 of 0 to 5.
  • R 101 represents an n-valent organic group.
  • the monovalent organic group include an alkyl group, an alkylene group, and an aromatic ring group.
  • the divalent or higher valent organic group include those obtained by removing one or more hydrogen atoms from a monovalent organic group to form 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 each independently represent a hydrogen atom or a hydrocarbon group
  • R 150 and R 151 each independently represent a hydrocarbon group.
  • the hydrocarbon group represented by R 102 to R 111 and R 151 is preferably an alkyl group, an alkenyl group or an aryl group.
  • 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.
  • a substituent what was demonstrated as the above-mentioned substituent group A is mentioned.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted.
  • the alkenyl group has preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 10 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, preferably linear or branched, and 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 still more preferably 6 to 12 carbon atoms.
  • the aryl group may have a substituent or may be
  • 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 still 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 bonded to each other to form a ring.
  • the ring include an alicyclic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring.
  • the ring may be monocyclic or multicyclic.
  • the linking group is composed of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic ring group, and combinations thereof. They can be linked by a divalent linking group selected from the group.
  • 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.
  • the ammonium cation preferably has a structure represented by the general formula (Y1-1) or (Y1-2), 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 thermal base generator may be used alone or in combination of two or more.
  • the combination mode can be appropriately set according to physical properties required for the curable composition, for example, adhesion to the substrate. Moreover, you may use in combination with the photobase generator mentioned later.
  • the content of the thermal base 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. More preferably, it is 7% by mass. In addition, when using in combination of 2 or more types of base generators, it is preferable that the sum total of each content exists in the said range.
  • the curable composition of the present invention preferably contains a photobase generator from the viewpoint of having more excellent effects of the present invention.
  • the photobase generator is not particularly limited, and specific examples thereof include, for example, paragraphs 0207 to 0238 of JP-A-2015-087612, paragraphs 0026 to 0039 of JP-A-2008-247747, and International Publication No.
  • the description of paragraphs 0009 to 0052 of 2010/064631 can be referred to, the contents of which are incorporated herein.
  • 5223633 can be referred to, and the contents thereof are incorporated in the present specification. Further, it may be an ionic photobase generator described in paragraphs 0053 to 0070 of JP-A-2015-28540, the contents of which are incorporated herein.
  • the photobase generator a compound that releases an amine by light is preferable in that the cured film has excellent low reflectivity.
  • a photobase generator described in JP2013-80206 is preferable, and the contents thereof are incorporated in the present specification.
  • a commercial product of the photobase generator is not particularly limited.
  • WPBG series “WPBG-082”, “WPBG-167”, “WPBG-168”, “WPBG-018”, “WPBG-018”, “Wako Pure Chemical Industries, Ltd.”
  • WPBG-027 ",” WPBG-140 ", etc.
  • WPBG-018” and “WPBG-027” can be preferably used in that the cured film has excellent low reflectivity.
  • a photobase generator represented by the following general formula (PBG) is preferable in that the cured film has excellent low reflectivity.
  • R a and R b each independently represent a hydrogen atom or a monovalent organic group, and an aromatic hydrocarbon group or aliphatic group in that the cured film has more excellent 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, R a and R b are preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 9 carbon atoms, and more preferably a carbon number, in that the cured film has more excellent low reflectivity.
  • R a and R b may be bonded to each other to form a ring.
  • Examples of the cyclic amino group formed by combining R a and R b with each other include, for example, 1-aziridinyl group, 1-azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group, 1- Heptamethyleneimino group, 1-octamethyleneimino group, 1-nonamethyleneimino group, 1-1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolidinyl Group, 1-piperazinyl group, morpholino group and the like.
  • a cyclic amino group having 2 to 9 carbon atoms that does not have an unsaturated bond is preferable in that the cured film has excellent low reflectivity, and includes a 1-aziridinyl group, 1-azetidinyl group, and 1-pyrrolidinyl group.
  • a 1-piperidinyl group is more preferable, and a 1-pyrrolidinyl group is more preferable.
  • Ar a represents an aryl group or a heteroaryl group.
  • the aryl group and heteroaryl group may further have a monovalent organic group as a substituent.
  • 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. Cured film in that it has a more excellent low reflectivity is, the number of condensed rings in Ar a is preferably 2-5, 3-4 is more preferable.
  • the condensed ring may include a heterocycle, and each condensed ring may have one or more monovalent organic groups as a substituent.
  • the condensed ring structure described above is more preferably a ⁇ -conjugated system.
  • the condensed ring structure When the condensed ring structure is a ⁇ -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 examples 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.
  • the general formulas (CR1) to (CR3) are more preferable.
  • * represents a bonding position, and each ring may have one or more monovalent organic groups as a substituent.
  • the photobase generator When the photobase generator is irradiated with light having the 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.
  • an amine compound a primary amine, a secondary amine, and a tertiary amine are mentioned, It is preferable that it is a primary amine or a secondary amine.
  • PBG general formula
  • BA general formula
  • the molecular weight of the base generated from the 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. Further preferred. Although this mechanism is not clear, a base having a low molecular weight and easy to diffuse is generated and diffuses in the coating film, so that the rate and / or progress of the polymerization reaction of the polymerizable compound in the upper region and the lower region can be increased. There is a difference. For this reason, since the stress generated by the curing shrinkage is different between the upper region and the lower region, fine wrinkles are generated in the upper region, which is presumed to contribute to the low reflectivity of the cured film.
  • the molecular weight of the base means a molecular weight that can be calculated from the structural formula.
  • R a and R b are the same as defined in the general formula (PBG).
  • a photobase generator may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the combination mode can be appropriately set according to physical properties required for the curable composition, for example, 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. More preferably, it is 7% by mass.
  • the content of the photobase generator is related to the content of the dispersant described later, and the mass ratio of the photobase generator to the dispersant (the mass of the photobase generator / the mass of the dispersant) is 0.05 to 0. .7 in many cases, and 0.08 to 0.5 is preferable in that the cured film has more excellent low reflectivity.
  • 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 “to-be-dispersed”).
  • the dispersant for example, a known pigment dispersant can be appropriately selected and used.
  • polymer compounds are preferable.
  • the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
  • the polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
  • the polymer compound has an interaction property with the object to be dispersed and, if desired, an extender used together. Therefore, the high molecular compound is adsorbed on the surface of the dispersion and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the colorant surface can be cited as preferred structures.
  • the anchor site to the surface of the colorant is preferably an acid group or a hydroxyl group, more preferably an acid group, and a carboxyl group is particularly preferred from the viewpoint of good dispersion stability of the colorant, good development, and excellent pattern formability.
  • the adsorptivity of the polymer compound to these can be promoted.
  • the polymer compound preferably has a structural unit having a graft chain.
  • structural unit is synonymous with “repeating unit”.
  • Such a polymer compound having a structural unit having a graft chain has an affinity for a solvent due to the graft chain, and thus has excellent dispersibility of the dispersion and dispersion stability after aging.
  • the curable composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development. When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved.
  • the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
  • the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a 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 examples of such a polymer structure include a polyacrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and Examples thereof include a polyether structure.
  • the graft chain is made of at least one selected from the group consisting of a polyester structure, a polyether structure and a polyacrylate structure.
  • the graft chain is preferably a graft chain, 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 a macromonomer having a reactive double bond group can be preferably used.
  • AA-6 trade name, Toa Gosei Co., Ltd.
  • AA-10 Product name, manufactured by Toa Gosei Co., Ltd.
  • AB-6 trade name, manufactured by Toa Gosei Co., Ltd.
  • AS-6 trade name, produced by Toa Gosei Co., Ltd.
  • AN-6 trade name, manufactured by Toa Gosei Co., Ltd.
  • Co., Ltd. AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.
  • AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PME-4000 (trade name, manufactured by NOF Corporation), etc. It is done.
  • the polymer compound preferably includes a structural unit represented by any one of the following general formulas (1) to (4) as a structural unit having a graft chain. It is more preferable that the structural unit represented by any one of (2A), general formula (3A), general formula (3B), and general formula (4) is included.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, from the viewpoint of synthesis constraints.
  • a hydrogen atom or a methyl group is more preferable, and a methyl group is more preferable.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups.
  • a and B mean the bonding positions with the left end group and the right end group in the general formulas (1) to (4), respectively.
  • (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
  • 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 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. It is done.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
  • 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 is particularly preferable.
  • the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
  • n, m, p, and q are each independently an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the general formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
  • R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
  • R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or 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 more preferable.
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, in the molecule of the polymer compound, structural units represented by the general formulas (1) to (4) having different structures may be included. In the general formulas (1) to (4), when n, m, p, and q each represent an integer of 2 or more, in the general formula (1) and the general formula (2), j and k may include different structures. In the general formula (3) and the general formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
  • the structural unit represented by the general formula (1) is more preferably a structural unit represented by the following general formula (1A) from the viewpoint of dispersion stability and developability.
  • the structural unit represented by the general formula (2) is more preferably a structural unit represented by the following general formula (2A) from the viewpoint of dispersion stability and developability.
  • 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. .
  • 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 preferably has a structural unit represented by the general formula (1A) as a structural unit having a graft chain.
  • the structural unit having a graft chain (for example, the structural unit represented by the general formula (1) to the general formula (4)) is 2 to 90 relative to the total mass of the polymer compound in terms of mass. % Is preferably included, and more preferably in the range of 5 to 30%.
  • the dispersoid particularly, titanium black particles
  • the structural unit having a graft chain is contained within this range, the dispersoid (particularly, titanium black particles) has high dispersibility and good developability when a light-shielding film is formed.
  • the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding to the structural unit having a graft chain).
  • the hydrophobic structural unit is a structural unit having no acid group (for example, carboxyl group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
  • ClogP values are available from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
  • log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines 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 represented by the following formula.
  • logP log (Coil / Cwater)
  • Coil represents the molar concentration of the compound in the oil phase
  • Cwater represents the molar concentration of the compound in the aqueous phase.
  • the polymer compound preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units. .
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or a carbon number of 1 Represents an alkyl group of ⁇ 6 (for example, methyl group, ethyl group, propyl group, etc.).
  • R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are more preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • 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
  • a divalent aromatic group for example, Arylene group, substituted arylene group
  • divalent heterocyclic group oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • the heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 represents a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group.
  • L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z includes an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (for example, an arylene group, a substituted arylene group), a heterocyclic group, Oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 is an aliphatic group, aromatic group or heterocyclic group) , A carbonyl group (—CO—), and combinations thereof.
  • 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, a substituted arylene group
  • a heterocyclic group Oxygen atom (—O—), sulfur atom (—S—), imino group (—
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included.
  • bridged cyclic hydrocarbon ring examples include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring and bicyclo [3.2.1] octane ring).
  • Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, 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 .
  • the bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
  • a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10.
  • the aromatic group may have a substituent.
  • the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the aromatic group does not have an acid group as a substituent.
  • the heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • the heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • the heterocyclic group does not have an acid group as a substituent.
  • R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, , Methyl group, ethyl group, propyl group, etc.), Z, or LZ.
  • L and Z are as defined above.
  • R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, 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.
  • R 1 is a hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. 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.
  • Examples of typical compounds represented by the general formula (i) to the general formula (iii) the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are as follows. Incorporated herein.
  • the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
  • the polymer compound a functional group capable of forming an interaction with a dispersion target (particularly titanium black) can be introduced.
  • the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with the dispersion.
  • the functional group capable of forming an interaction with the object to be dispersed include an acid group, a basic group, a coordination group, and a reactive functional group.
  • the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group
  • the structural unit having an acid group, the structural unit having a basic group, or a coordinating group respectively. It is preferable to have a structural unit having or a reactive structural unit.
  • the polymer compound since the polymer compound further has an alkali-soluble group such as a carboxyl group as an acid group, the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of the dispersion is alkali-soluble in the curable composition of the present invention.
  • the curable composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • a high molecular compound has a structural unit which has an acid group
  • the acid group in the structural unit having an acid group easily interacts with the dispersion, the polymer compound stably disperses the dispersion, and the viscosity of the polymer compound that disperses the dispersion is low. This is presumably because the polymer compound itself is easily dispersed stably.
  • the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. Is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
  • the acid group which is a functional group capable of forming an interaction with the dispersion target include a carboxyl group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably a carboxyl group or a sulfonic acid group.
  • at least one of phosphoric acid groups, and more preferable is a carboxyl group in that the adsorbing power to the colorant is good and the dispersibility of the colorant is high.
  • 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.
  • the content of the structural unit having an acid group is based on the total mass of the polymer compound in terms of mass. Preferably, it is 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
  • Examples of the basic group that is a functional group capable of forming an interaction with the dispersion target include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide Among them, a tertiary amino group is more preferable because it has a good adsorptive power to the colorant and a 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 calculated by mass conversion to the total mass of the polymer compound. 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 suppression of developability inhibition.
  • Examples of the coordinating group which is a functional group capable of forming an interaction with the dispersion, and the reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, acid chloride Etc. More preferred is an acetylacetoxy group in that the adsorbing power to the colorant is good and the dispersibility of the colorant is high.
  • 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: In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of inhibition of developability inhibition with respect to the total mass of the polymer compound.
  • the polymer compound in the present invention has a functional group capable of forming an interaction with the object 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. It only has to be.
  • the polymer compound is selected from structural units derived from monomers represented by the following general formula (iv) to general formula (vi) It is preferable to have one or more structural units.
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
  • R 11 , R 12 , and R 13 are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably Each independently represents a hydrogen atom or a methyl group.
  • R 12 and R 13 are each particularly preferably a hydrogen atom.
  • X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the general formula (v) represents a methine group or a nitrogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group include 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), a divalent aromatic group (for example, , Arylene groups, and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ —
  • R 31 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 1 represents a functional group capable of interacting with the colorant in addition to the graft chain, and is preferably a carboxyl group or a tertiary amino group, More preferably, it is a group.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), - represents a Z 1 or L 1 -Z 1,.
  • L 1 and Z 1 has the same meaning as L 1 and Z 1 in the above, are the preferable examples.
  • R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure.
  • a compound in which X is an oxygen atom or an imino group and Z is a carboxyl group is preferable.
  • R 11 is a hydrogen atom or a methyl group
  • L 1 is an alkylene group
  • Z 1 is a carboxyl group
  • Y is a methine group. Is preferred.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z A compound in which is a carboxyl group is preferred.
  • monomers represented by general formula (iv) to general formula (vi).
  • 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 a phthalic anhydride a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic 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 anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and - such as hydroxyphenyl methacrylamide.
  • the content of the structural unit having a functional group capable of forming an interaction with the dispersion is determined based on the total mass of the polymer compound from the viewpoint of the interaction with the dispersion, the dispersion stability, and the permeability to the developer. Is preferably 0.05% to 90% by weight, more preferably 1.0% to 80% by weight, and still more preferably 10% to 70% by weight.
  • the polymer compound interacts 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.
  • structural units having various functions for example, structural units having functional groups having affinity with the dispersion medium used in the dispersion).
  • Such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles.
  • the polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 250 mgKOH / g, more preferably in the range of 0 mgKOH / g to 160 mgKOH / g, and still more preferably 10 mgKOH / g to 140 mgKOH / g.
  • the range is not more than g, and particularly preferably not less than 20 mgKOH / g and not more than 120 mgKOH / g. If the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming the light-shielding film can be more effectively suppressed.
  • the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable.
  • the acid value of the polymer compound is 20 mgKOH / g or more, sedimentation of the dispersion can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the curable composition can be further improved.
  • the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound.
  • the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
  • the weight average molecular weight of the polymer compound in the present invention is a polystyrene conversion value by GPC (Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition and developability at the time of developing a light-shielding film.
  • GPC Gel Permeation Chromatography
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the polymer compound can be synthesized based on a known method, and examples of the solvent used when 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, dimethyl sulfoxide, toluene,
  • Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
  • polymer compound As specific examples 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.
  • graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 corresponding to paragraphs 0075 to 0133 in US2011 / 0124824.
  • it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 (corresponding to columns 0075 to 0133 of US 2011/0279759) of JP 2011-153283 A are bonded via a linking group.
  • Polymeric compounds containing constituents can be used, the contents of which can be incorporated and incorporated herein.
  • the content of the dispersant in the curable composition of the present invention is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, based on the total solid content of the curable composition.
  • the curable composition of the present invention may further contain a fluorine-containing resin from the viewpoint of obtaining a cured film having more excellent low reflectivity.
  • the fluorine-containing resin refers to an oligomer or polymer having a fluorine atom.
  • a fluorine-containing resin shall not be contained in the above-mentioned dispersing agent and the below-mentioned binder polymer.
  • the fluororesin include, for example, MegaFuck F171, F172, F173, F176, F177, F141, F142, F143, F143, F144, R30, F437, F475, F479, and F482.
  • F554, F780, F781F (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC -103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).
  • One type of fluorine-containing resin may be used, or two or more types may be combined.
  • the addition amount of the fluorine-containing resin is preferably 0.01 to 3% by mass with respect to the total mass of the curable composition in that the cured film has more excellent low reflectivity, and preferably 0.5 to 1.5%. The mass% is more preferable.
  • a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-containing resin.
  • Specific examples thereof include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, such as MegaFac RS-101, RS-102, and RS-718K manufactured by DIC. Can be mentioned.
  • the addition amount makes both become the above-mentioned suitable range.
  • the curable composition of the present invention may contain a binder polymer.
  • a binder polymer a linear organic polymer is preferably used.
  • a linear organic polymer a well-known thing can be used arbitrarily.
  • a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development.
  • an alkali-soluble resin a resin having a group that promotes alkali-solubility
  • the binder polymer is a linear organic polymer, and an alkali having at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or styrene copolymer as a main chain). It can select suitably from soluble resin. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin is preferable, and from the viewpoint of developing property control, an acrylic resin, Acrylamide resins or acrylic / acrylamide copolymer resins are preferred.
  • these acid groups include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like. Two or more types may be used.
  • binder polymer examples include radical polymers having a carboxyl group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Those described in JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins having a carboxyl group alone or copolymerized, monomers having an acid anhydride And a copolymer obtained by hydrolyzing, half-esterifying, or half-amidating an acid anhydride unit, and an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride.
  • radical polymers having a carboxyl group in the side chain such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Those described in JP-A-54
  • Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxyl styrene.
  • Examples of monomers having an acid anhydride include And maleic anhydride.
  • acidic cellulose derivatives having a carboxyl group in the side chain are also exemplified.
  • those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
  • the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent Nos. 993966, 120204000, and 2001-318463 has an excellent balance between film strength and developability. It is preferable.
  • polyvinyl pyrrolidone and polyethylene oxide are useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
  • the other addition polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity, and developability.
  • Commercially available products include, for example, Acrybase FF-187, FF-426 (Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai Co., Ltd.), Daicel Ornex Co., Ltd. Cyclomer P (ACA) 230AA, etc. Is mentioned.
  • the binder polymer may contain a structural unit having a graft chain as described above (a structural unit represented by any one of the general formulas (1) to (4)).
  • 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 radical polymerization can be easily set by those skilled in the art, and 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, and preferably 0.3 to 25% by mass with respect to the total solid content of the curable composition. Is more preferable.
  • the curable composition of the present invention may contain a solvent.
  • the solvent include water and organic solvents.
  • 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 Nomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, acetic acid Examples include, but are not limited to, ethyl, butyl acetate, methyl lactate, and ethyl lactate.
  • a solvent may be used individually by 1 type, it is preferable to use combining 2 or more types of organic solvents at the point which hardened
  • a solvent may be used individually by 1 type, it is preferable to use combining 2 or more types of organic solvents at the point which hardened
  • the amount of the solvent contained in the curable composition is preferably 10 to 90% by mass and more preferably 20 to 85% by mass with respect to the total mass of the curable composition.
  • the curable composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of a pattern can be made more excellent (fine).
  • an ultraviolet absorber salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
  • compounds of paragraphs 0137 to 0142 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
  • a diethylamino-phenylsulfonyl ultraviolet absorber (trade name: UV-503, manufactured by Daito Chemical Co., Ltd.) is also preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
  • the content of the ultraviolet absorber is preferably 0.001 to 15% by mass, and 0.01 to 10% by mass with respect to the total solid content of the curable composition. More preferred is 0.1 to 5% by mass.
  • Various surfactants may be contained in the curable composition from the viewpoint of further improving applicability.
  • 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.
  • the curable composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) are further improved, so that the uniformity of coating thickness and the liquid-saving property are further improved. be able to.
  • the above-mentioned fluororesin may have a function as a surfactant.
  • the fluorine-based surfactant that can be suitably used in the curable composition of the present invention is the same as those exemplified as the above-mentioned fluorine-containing resin.
  • 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 mass%, more preferably 0.005 to 1.0 mass%, based on the total solid content of the curable composition.
  • a polymerization inhibitor is desirably contained in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition.
  • the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the curable composition.
  • a polymerization inhibitor may use 1 type and may combine 2 or more types. When two or more types are included, the total amount is preferably within the above range.
  • the curable composition of the present invention may contain the following components.
  • examples thereof include a sensitizer, a co-sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, a diluent, and a fat sensitizer.
  • adhesion promoters to the substrate surface and other auxiliaries for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers,
  • a known additive such as a chain transfer agent may be contained in the curable composition as necessary.
  • paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No. 2013/0034812 [0237] to [0309]), JP2008-250074A.
  • paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP 2013-195480 A can be taken into account, and the contents thereof are described in the present specification. Incorporated.
  • 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).
  • a known mixing method for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser.
  • the mixing method of 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. In view of further improving the dispersibility, it is preferable to disperse the colorant in the dispersant in advance and then mix it with other components.
  • the curable composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
  • a filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given.
  • PTFE polytetrafluoroethylene
  • polyamide resin such as nylon
  • polyolefin resin including high density and ultra high molecular weight
  • polyethylene and polypropylene (PP) polypropylene
  • nylon are preferable.
  • the pore size of the filter is suitably about 0.1 to 7.0 ⁇ m, preferably about 0.2 to 2.5 ⁇ m, more preferably about 0.2 to 1.5 ⁇ m, and still more preferably 0.3 to 0.0 ⁇ m. 7 ⁇ m. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the colorant containing the pigment while suppressing filtration clogging of the colorant containing the pigment.
  • different filters may be combined. At that time, the filtering by the first filter may be performed once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • 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 Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
  • the second filter a filter formed of the same material as the first filter described above can be used.
  • the pore size of the second filter is suitably about 0.2 to 10.0 ⁇ m, preferably about 0.2 to 7.0 ⁇ m, more preferably about 0.3 to 6.0 ⁇ m.
  • the curable composition of the present invention does not contain impurities such as metals, metal salts containing halogen, acids and alkalis.
  • the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
  • 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 thickness of the light-shielding film is not particularly limited, but is preferably 0.2 to 50 ⁇ m, more preferably 0.5 to 30 ⁇ m in terms of the film thickness after drying in terms of more excellent reflection characteristics of the light-shielding film. It is more preferably 7 to 25 ⁇ m, particularly preferably 1.0 to 10 ⁇ m.
  • the above thickness is an average thickness, and is a value obtained by measuring the thicknesses of any five or more points of the light shielding film and arithmetically averaging them.
  • a preferred embodiment in the case of producing a patterned light-shielding film is a step of forming a curable composition layer by applying the curable composition of the present invention on a substrate (hereinafter referred to as “curable composition layer formation” as appropriate).
  • step a step of exposing the curable composition layer through a mask (hereinafter abbreviated as “exposure step” where appropriate), and a curable composition layer after exposure is developed to block light.
  • exposure step a step of forming a film (patterned light-shielding film)
  • development step as appropriate.
  • the curable composition of the present invention is applied directly or via another layer to a substrate to form a curable composition layer (curable composition layer forming step), and a predetermined mask.
  • a pattern-shaped light-shielding film can be produced by exposing only through the pattern, curing only the curable composition layer portion irradiated with light (exposure process), and developing with a developer (development process).
  • exposure process curing only the curable composition layer portion irradiated with light
  • development process developing with a developer
  • the curable composition of the present invention is applied on the substrate to form a curable composition layer.
  • the substrate include various members in the solid-state imaging device (for example, an infrared light cut filter, an outer peripheral portion of the solid-state imaging device, an outer peripheral portion of a wafer level lens, a back surface of the solid-state imaging device, etc.).
  • a coating method of the curable composition of the present invention on the substrate various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be applied.
  • the curable composition applied on the substrate is usually preferably dried at 70 ° C. or more and 110 ° C. or less for 2 minutes or more and 4 minutes or less, and a curable composition layer is formed.
  • the curable composition layer formed in the curable composition layer forming step is exposed through a mask, and only the curable composition layer portion irradiated with light is cured.
  • the exposure is preferably performed by irradiation with radiation.
  • radiation that can be used for exposure ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is preferred as a 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.
  • a development process (development process) is performed, and the light non-irradiated part in the exposure process is eluted in a developer (for example, an alkaline aqueous solution).
  • a developer for example, an alkaline aqueous solution.
  • an organic alkali developer is desirable.
  • the development temperature is usually preferably 20 ° C. or higher and 30 ° C. or lower, and the development time is preferably 20 seconds or longer and 90 seconds or shorter.
  • alkaline aqueous solution for example, as the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate having a concentration of 0.001 to 10% by mass, preferably An alkaline aqueous solution dissolved so as to be 0.005 to 0.5 mass% can be mentioned.
  • Organic developers include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole , Piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene such that the concentration is 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass.
  • An aqueous alkali solution dissolved in 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.
  • a water-soluble organic solvent such as methanol or ethanol and / or a surfactant
  • the solid-state imaging device 2 includes a CMOS sensor 3 as a solid-state imaging device, a circuit board 4 on which the CMOS sensor 3 is mounted, and a ceramic substrate 5 made of ceramic that holds the circuit board 4. And.
  • the solid-state image pickup device 2 is held on a ceramic substrate 5, an IR cut filter 6 that cuts infrared light (IR) 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 that holds the lens holder 8 movably.
  • a CCD sensor or an organic CMOS sensor may be provided instead of the CMOS sensor 3.
  • the ceramic substrate 5 has an opening 5 a into which the CMOS sensor 3 is inserted, has a frame shape, and surrounds the side surface of the CMOS sensor 3.
  • 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).
  • an adhesive for example, an epoxy adhesive, the same applies hereinafter.
  • Various circuit patterns are formed on the circuit board 4.
  • a reflection film that reflects infrared light is formed on a plate-like glass or blue glass, and the surface on which the reflection film is formed becomes the incident surface 6a.
  • the IR cut filter 6 is formed in a size slightly 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 disposed behind the photographing lens 7 (downward in FIGS. 2 and 3), and an IR cut filter 6 is disposed 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 imaging device 2 is mounted, and power is supplied from the electronic device to the solid-state imaging device 2.
  • an electronic device for example, a digital camera
  • CMOS sensor 3 a large number of color pixels are two-dimensionally arranged on the light receiving surface, and each color pixel photoelectrically converts incident light and accumulates generated signal charges.
  • the light shielding film (light shielding layer) 11 described above is disposed over the entire circumference at the end of the incident surface 6 a of the IR cut filter 6, and infrared light with a light shielding film is provided.
  • a cut filter is formed.
  • the reflected light R1 emitted from the photographing lens 7 and reflected by the front surface (the upper surface in FIGS. 2 and 3) of the ceramic substrate 5 is incident on the CMOS sensor 3 after being repeatedly reflected and refracted in the apparatus, and when photographing.
  • the reflected light R ⁇ b> 2 reflected from the inner wall surface of the lens holder 8 emitted from the lens 7 enters the CMOS sensor 3, flare occurs in the captured image.
  • the light shielding film 11 shields harmful light such as reflected light R ⁇ b> 1 and R ⁇ b> 2 toward the CMOS sensor 3.
  • the light shielding film 11 is applied by, for example, spin coating or spray coating. 2 and 3, the thickness of the light shielding film 11 is exaggerated.
  • FIG. 4 shows a solid-state imaging device 20 according to the second embodiment.
  • the solid-state imaging device 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-described light shielding film (light shielding layer) 21 is formed on the side end face of the IR cut filter 6 over the entire circumference.
  • the light shielding film 21 shields harmful light such as reflected light R ⁇ b> 3 directed toward the CMOS sensor 3.
  • FIG. 5 shows a solid-state imaging device 30 according to the third embodiment.
  • the solid-state imaging device 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 light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference. That is, the first and second embodiments are combined. In this embodiment, since the light shielding performance is higher than in the first and second embodiments, the occurrence of flare is reliably suppressed.
  • FIG. 6 shows a solid-state imaging device 40 of the fourth embodiment.
  • the solid-state imaging device 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 light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference.
  • a light shielding film (light shielding layer) 41 is formed on the inner wall surface of the ceramic substrate 5.
  • the cured film obtained by curing the curable composition of the present invention can be used in image display devices such as liquid crystal display devices and organic electroluminescence display devices.
  • the cured film can be used for a color filter.
  • the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
  • the partition in this case preferably has a low refractive index for each color pixel.
  • display devices For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Sangyo Tosho) Issued in the first year).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the color filter in the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device.
  • the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
  • the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and a super-twist neutral (STN).
  • IPS In Plane Switching
  • MVA Multi-domain Vertical Alignment
  • STN super-twist neutral
  • the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system.
  • COA Color-filter On Array
  • the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling liquid, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided.
  • a resin film may be provided on the color filter layer.
  • image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)".
  • the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
  • the partition in this case preferably has a low refractive index for each color pixel.
  • Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.
  • the liquid crystal display device of the present invention includes 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.
  • these components for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
  • backlighting SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.
  • 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 multifunction device or a scanner; , Barcode readers, automated teller machines (ATMs), high-speed cameras, industrial devices such as personal authentication using facial image authentication; in-vehicle camera devices; medical treatment such as endoscopes, capsule endoscopes, and catheters Camera equipment: Used in space equipment such as biosensors, biosensors, military reconnaissance cameras, 3D map cameras, weather and ocean observation cameras, land resource exploration cameras, space astronomy and deep space target exploration cameras Optical filters and light shielding members and light shielding layers of modules, It can be used for antireflection member and an anti-reflection layer.
  • curing a curable composition can be used also for uses, such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode).
  • micro LED Light Emitting Diode
  • micro OLED Organic Light Emitting Diode
  • the optical filter and optical film which are used for micro LED and micro OLED it uses suitably with respect to the member which provides a light-shielding function and an antireflection function.
  • the micro LED and the micro OLED include those in JP-T-2015-500562 and JP-T-2014-533890.
  • curing a curable composition can be used also for uses, such as a quantum dot display.
  • a quantum dot display In addition to the optical filter and optical film which are used for a quantum dot display, it uses suitably with respect to the member which provides a light-shielding function and an antireflection function.
  • quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960. Things.
  • Titanium Black A-1 100 g of titanium oxide MT-150A having an average particle size of 15 nm (trade name: manufactured by Teika Co., Ltd.), 25 g of silica particles AEROSIL300 (registered trademark) 300/30 (manufactured by Evonik) having a BET specific surface area of 300 m 2 / g, and Disperbyk190 (trade name: manufactured by Big Chemie) was weighed 100 g, and these were added to 71 g of ion-electroexchanged water to obtain a mixture.
  • AEROSIL300 registered trademark
  • Disperbyk190 trade name: manufactured by Big Chemie
  • the mixture was treated for 30 minutes at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm using a MAZARSTAR KK-400W manufactured by KURABO to obtain a uniform aqueous mixture solution.
  • This aqueous mixture 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.). Thereafter, the atmosphere in the small rotary kiln was replaced with nitrogen, and nitriding reduction treatment was performed by flowing ammonia gas at 100 mL / min for 5 hours at the same temperature.
  • titanium black a dispersion containing titanium black particles and Si atoms
  • Si atoms containing Si atoms and having a powder specific surface area of 73 m 2 / g (hereinafter referred to as “titanium”).
  • titanium black a dispersion containing titanium black particles and Si atoms
  • titanium a powder specific surface area of 73 m 2 / g
  • TB dispersion 1 Preparation of titanium black dispersion (TB dispersion 1)
  • the component shown in the following composition 1 was mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain dispersion a.
  • the pigment dispersion resin described below (corresponding to a dispersant) was synthesized with reference to the description in JP-A-2013-249417.
  • the weight average molecular weight of the pigment-dispersed resin was 30000, the acid value was 60 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.
  • the obtained dispersion a was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. to obtain a titanium black dispersion (hereinafter referred to as TB dispersion 1).
  • TB dispersion 1 a titanium black dispersion
  • TB Dispersion 2 Preparation of Titanium Black Dispersion (TB Dispersion 2)
  • a TB dispersion 2 was obtained in the same manner as the TB dispersion 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 No. 2014-177614.
  • n represents 15 and * represents a connecting portion with the Z portion in the left structural formula.
  • TB dispersion 3 was obtained in the same manner as the TB dispersion 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, where * represents a linking moiety.
  • CB dispersion Preparation of carbon black dispersion (CB dispersion)
  • carbon black trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, manufactured by gas black method instead of titanium black.
  • the dispersion b was prepared in the same manner except that the carbon black thus obtained was expressed as “Colorant 2” in Table 1, and a carbon black dispersion (hereinafter referred to as CB dispersion) was prepared. .)
  • TB / CB dispersion Preparation of titanium black and carbon black dispersion (TB / CB dispersion)
  • dispersion c was prepared in the same manner except that instead of titanium black, a mixed part of 35 parts of titanium black and 10 parts of carbon black was used, And a carbon black dispersion (hereinafter referred to as TB / CB dispersion).
  • PBG1 Synthesis of photobase generator
  • PBG13 The photobase generators represented by the following general formulas (PBG1) to (PBG13) are described in 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 composition.
  • the following titanium black is prepared by the above method, and after preparing the TB dispersion 1 in which the titanium black is dispersed using the pigment dispersion resin by the above method, the TB dispersion 1 is mixed with other materials. did. Further, the curable composition 1 was diluted with propylene glycol monomethyl ether acetate (corresponding to an organic solvent) so that the solid content was 30%.
  • Example 13 Preparation of curable composition 13
  • IRGACURE 379 corresponding to a radical photopolymerization initiator manufactured by BASF Corp. is represented as “photoradical polymerization initiator 2” in Table 1
  • the curable composition 13 was obtained by the method.
  • Example 14 Preparation of curable composition 14
  • a curable composition 14 was obtained in the same manner as in Example 1 except that the amount of PBG1 used was 1.09 parts by mass and the amount of the binder polymer used was 13.01 parts by mass.
  • Example 15 Preparation of curable composition 15
  • a curable composition 15 was obtained in the same manner as in Example 1 except that the amount of PBG1 used was 1.07 parts by mass and the amount of the binder polymer used was 13.03 parts by mass.
  • Example 16 Preparation of curable composition 16
  • a curable composition 16 was obtained in the same manner as in Example 1 except that the amount of PBG1 used was 6.60 parts by mass and the amount of the binder polymer used was 7.50 parts by mass.
  • Example 17 Preparation of curable composition 17
  • a curable composition 17 was obtained in the same manner as in Example 1, except that the amount of PBG1 used was 6.85 parts by mass and the amount of the binder polymer used was 7.25 parts by mass.
  • Example 18 Preparation of curable composition 18
  • a curable composition 18 was obtained in the same manner as in Example 1, except that the amount of fluororesin 1 used was 0.07 parts by mass, and the amount of MegaFac RS-72-K was 0.93 parts by mass. It was.
  • Example 19 Preparation of curable composition 19
  • Example 1 except that the amount of fluorine-containing resin 1 used was 0.07 parts by mass, the amount of megafac RS-72-K used was 0.90 parts by mass, and the amount of binder polymer used was 11.25 parts by mass.
  • the curable composition 19 was obtained by the same method.
  • Example 20 Preparation of curable composition 20
  • the curable composition 20 was obtained.
  • Example 21 Preparation of curable composition 21
  • a curable composition 21 was obtained in the same manner as in Example 1 except that the amount of p-methoxyphenol used was 0 parts by mass and the amount of the binder polymer used was 11.16 parts by mass.
  • Example 22 Preparation of curable composition 22
  • a curable composition 22 was obtained in the same manner as in Example 1 except that the amount of dipentaerythritol hexaacrylate used was 31.64 parts by mass and the amount of the binder polymer used was 0 parts by mass.
  • Example 23 Preparation of curable composition 23
  • a curable composition 23 was obtained in the same manner as in Example 1 except that the CB dispersion prepared by the above-described method was used in place of the TB dispersion 1.
  • Example 24 Preparation of curable composition 24
  • a 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.
  • Example 25 Preparation of curable composition 25
  • a 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.
  • Example 26 Preparation of curable composition 26
  • an organic solvent propylene glycol monomethyl ether acetate and cyclopentanone were used and 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%. Except for the above, a curable composition 26 was obtained in the same manner as in Example 1.
  • Example 27 Preparation of curable composition 27
  • a curable composition 27 was obtained in the same manner as in Example 1 except that the TB dispersion 2 produced by the above-described method was used in place of the TB dispersion 1.
  • Example 28 Preparation of curable composition 28
  • a curable composition 28 was obtained in the same manner as in Example 1 except that the TB dispersion 3 produced by the above-described method was used in place of the TB dispersion 1.
  • Example 29 Preparation of curable composition 29
  • pentaerythritol tetraacrylate corresponding to a polymerizable compound.
  • polymerizable compound 2 indicated as “polymerizable compound 2” was used in the same manner as in Example 1.
  • a curable composition 29 was obtained.
  • Example 30 Preparation of curable composition 30
  • a curable composition 30 was obtained in the same manner as in Example 1, except that 100.00 parts by mass of dipentaerythritol hexaacrylate and 10.49 parts by mass of pentaerythritol tetraacrylate were used. It was.
  • Example 31 Preparation of curable composition 31
  • OXE-01 manufactured by BASF, corresponding to an oxime initiator.
  • photo radical polymerization initiator 3 referred to as “photo radical polymerization initiator 3”.
  • the curable composition 31 was obtained by the same method.
  • Example 32 Preparation of curable composition 32
  • a compound represented by the following formula (I-1) (corresponding to an oxime initiator, represented as “photoradical initiator 4” in Table 1) was used.
  • a curable composition 33 was obtained in the same manner as in Example 1.
  • the following formula (I-1) was synthesized with reference to the method described in paragraphs 0344 to 0345 of JP-T-2014-500852.
  • Example 33 Preparation of curable composition 33
  • a curable composition 34 was obtained in the same manner as in Example 1 except that PEG13 was used instead of PBG1.
  • Comparative Example 1 A comparative curable composition was obtained in the same manner as in Example 1 except that a binder polymer was used in place of PEG1 (a total of 14.10 parts by mass of binder polymer).
  • Each curable composition was applied by spin coating so that the dry film thickness was 2.0 ⁇ m on a glass plate having a thickness of 0.7 mm and a size of 100 mm ⁇ 100 mm (Corning 1737, manufactured by Corning). Thereafter, the glass plate coated with the curable composition was subjected to heat treatment (pre-baking) 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 with an exposure amount of 1000 mJ / cm 2 with a high-pressure mercury lamp. Then, the glass plate which has the coating film by which the whole surface exposure was carried out was heated at 200 degreeC for 300 second on the hotplate, and the cured film was obtained.
  • Table 1 The measurement results of reflectance and the composition of each curable composition are summarized in Table 1 below.
  • the numerical value of each component column in Table 1 represents a mass part.
  • “molecular weight of the generated base” means the molecular weight calculated from the structural formula of the base (primary amine or secondary amine) generated by decomposition of the photobase generator.
  • the “quantity ratio” means a mass ratio of the photobase generator and the dispersant (the mass of the photobase generator / the mass of the dispersant).
  • the cured film formed of the curable composition containing the predetermined component had excellent low reflectivity. Moreover, since each cured film had the outstanding light-shielding property, it turned out that it can be used as a light-shielding film. On the other hand, the cured film formed of the curable composition of Comparative Example 1 that does not contain the predetermined photobase generator did not achieve the desired effect.
  • Example 1 When comparing Example 1 and Example 20, it was found that the light-shielding film formed of the curable composition containing the fluorine-containing resin had better low reflectivity.
  • Example 1 Example 13, Example 31, and Example 32 are compared, the light-shielding film formed by the curable composition containing the oxime-based initiator as the radical initiator is more excellent. It was found to have reflectivity.
  • Example 26 Comparing Example 1 and Example 26, it was found that the light-shielding film formed from the curable composition containing two or more organic solvents had a better low reflectance. .
  • Example 1 When Example 1 was compared with Example 23, it was found that the light-shielding film formed of the curable composition containing the titanium compound (titanium black) had a better low reflectance. .
  • Example 1, Example 27, and Example 28 are compared, 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 is shown. Was found to have better low reflectivity.
  • Example 1 When Example 1 is compared with Example 29, the light-shielding film formed of the curable composition containing a polymerizable compound having 5 or more ethylenically unsaturated groups has a more excellent low reflectance. I found out.
  • a lens film was formed by the following operation.
  • SP-172 manufactured by ADEKA an arylsulfonium salt derivative
  • EHPE-3150 manufactured by Daicel Chemical Industries
  • ⁇ Curable composition layer forming step> The curable composition of Example 1 was applied on a lens film of a glass substrate (hereinafter referred to as “support”) on which the lens film was formed, and the curable composition 1 was applied by a hot plate having a surface temperature of 120 ° C. The support was heated for 120 seconds. Thus, a coating film (corresponding to a curable composition layer) having a thickness of 2.0 ⁇ m was obtained.
  • the obtained curable composition layer was exposed with the exposure amount of 500 mJ / cm ⁇ 2 > through the photomask which has a 10 mm hole pattern using the high pressure mercury lamp.
  • ⁇ Development process> The curable composition layer after the exposure was subjected to paddle development for 60 seconds at a temperature of 23 ° C. using a 0.3% aqueous solution of tetramethylammonium hydroxide as a developer. Thereafter, the curable composition layer subjected to the development treatment was rinsed with a spin shower, and the rinsed composition layer was washed with pure water to obtain a patterned light-shielding film. .
  • a coating film was formed on the patterned light-shielding film produced by the above-described method using the above-described lens film-forming composition. Thereafter, the shape was transferred with a quartz mold having a lens shape, and the coating film was cured with a high pressure mercury lamp at an exposure amount of 400 mJ / cm 2 , thereby producing a wafer level lens array having a plurality of wafer level lenses. The produced wafer level lens array was cut and a lens module was produced using the obtained wafer level lens, and then an imaging device and a sensor substrate were attached to produce an imaging unit (corresponding to a solid-state imaging device).
  • the obtained wafer level lens was free from residue at the lens opening and had good transparency. Further, the light shielding layer had low reflection, high uniformity of the coated surface, and high light shielding properties.
  • a color filter having a black matrix was produced by the following operation.
  • the curable composition of Example 1 was applied to a glass wafer by spin coating, and then the glass wafer on which the curable composition was applied was heated on a hot plate at 120 ° C. for 2 minutes to form a coating film (cured). Corresponded to the composition layer). The film thickness of the obtained coating film was 2.0 ⁇ m.
  • the curable composition layer was exposed at a dose of 500 mJ / cm 2 through a photomask having an Island pattern with a pattern of 0.1 mm.
  • the curable composition layer after the exposure was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide as a developer.
  • the curable composition layer that has been subjected to the development treatment is rinsed by a spin shower, and the curable composition layer that has been further rinsed is washed with pure water to form a patterned light-shielding film (black Matrix).
  • chromatic color curable composition In the same manner as in Example 1, except that the titanium black was replaced with the following chromatic pigments, red (R) colored curable composition R-1 and green (G) colored cured, respectively. Composition G-1 and a colored curable composition B-1 for blue (B) were prepared.
  • the red (R) colored curable composition R-1 is used in the black matrix produced above, and the red (R) is colored 80 ⁇ 80 ⁇ m in the same manner as the black matrix produced above. A pattern was formed. Further, in the same manner, a green (G) chromatic coloring pattern is obtained using the green (G) colored curable composition G-1, and a blue color using the blue (B) colored curable composition B-1. A chromatic color pattern of (B) was sequentially formed to produce a color filter having a black matrix for a liquid crystal display device.
  • a liquid crystal display device equipped with the obtained color filter can obtain a clear image with high contrast and is extremely excellent in visibility even under external light.
  • the light-shielding layer has a high optical density and can achieve a sufficient light-shielding property to prevent the light from passing through the backlight. It is estimated that the visibility is extremely excellent.

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Abstract

The present invention provides a curable composition with which it is possible to produce a cured film having exceptional low-reflection properties. The present invention also provides a light-shielding film obtained by curing the curable composition, a solid-state imaging device including the light-shielding film, and a color filter. This curable composition contains a colorant, a radical photopolymerization initiator, a polymerizable compound, an acid/base generator, and a dispersant.

Description

硬化性組成物、遮光膜、固体撮像装置、および、カラーフィルタCurable composition, light shielding film, solid-state imaging device, and color filter
　本発明は、硬化性組成物、遮光膜、固体撮像装置、および、カラーフィルタに関する。 The present invention relates to a curable composition, a light shielding film, a solid-state imaging device, and a color filter.
　特許文献１にはアルカリ可溶性樹脂、光重合性モノマー、光重合開始剤、特定の構造を有する化合物、および遮光剤を含有するブラックカラムスペーサ用感光性樹脂硬化性組成物が記載されている。 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.
特開２０１３－２３１９３５号公報JP 2013-231935 A
　デジタルカメラおよびスマートフォン等に搭載される固体撮像装置は、撮影レンズに加え、その背後にＣＣＤ（Charge-Coupled Device：電荷結合素子）およびＣＭＯＳ（Complementary Metal Oxide Semiconductor：相補性金属酸化膜半導体）等の固体撮像素子を有する。この固体撮像装置には、裏面側の遮光、画素間の赤外領域の遮光によるノイズ発生防止、および、画質の向上等の目的で、遮光膜が設けられている。 Solid-state imaging devices mounted on digital cameras and smartphones have a CCD (Charge-Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) behind the taking lens. It has a solid-state image sensor. This solid-state imaging device is provided with a light shielding film for the purpose of light shielding on the back surface side, prevention of noise generation due to light shielding in the infrared region between pixels, and improvement of image quality.
　本発明者らは、特許文献１に記載された感光性樹脂硬化性組成物を硬化させて得られた膜の光線反射率（後述する方法により測定した光線反射率、以下では単に「反射率」という。）について検討したところ、反射率が高く、昨今、遮光膜に要求される低反射性のレベルに達していないことを知見した。 The inventors of the present invention have disclosed a 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, it was found that the reflectance was high and the level of low reflectivity required for a light-shielding film has not been achieved.
　そこで、本発明は、優れた低反射性を有する硬化膜を作製することができる硬化性組成物を提供することを課題とする。また、本発明は、上述の硬化性組成物を硬化して得られる遮光膜、ならびに、上述の遮光膜を有する固体撮像装置、および、カラーフィルタを提供することも課題とする。 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-described curable composition, a solid-state imaging device having the above-described light-shielding film, and a color filter.
　本発明者らは、上記課題を達成すべく鋭意検討した結果、特定の成分を含有する硬化性組成物により上記課題を解決することができることを見出し、本発明を完成させた。
　すなわち、以下の構成により上記課題を達成することができることを見出した。 As a result of intensive 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 has been found that the above-described problem can be achieved by the following configuration.
（１）　着色剤と、光ラジカル重合開始剤と、重合性化合物と、塩基発生剤と、分散剤と、を含有する硬化性組成物。
（２）　塩基発生剤が光塩基発生剤を含有する、（１）に記載の硬化性組成物。
（３）　分散剤に対する光塩基発生剤の質量比が、０．０８～０．５である、（２）に記載の硬化性組成物。
（４）　光塩基発生剤が、後述する一般式（ＰＢＧ）で表される（２）または（３）のいずれかに記載の硬化性組成物。
（５）　光塩基発生剤から発生する塩基がアミン化合物であって、アミン化合物の分子量が１５０以下である（２）～（４）のいずれかに記載の硬化性組成物。
（６）　光ラジカル重合開始剤が、オキシム系開始剤である（１）～（５）のいずれかに記載の硬化性組成物。
（７）　着色剤が、遮光性顔料である（１）～（６）のいずれかに記載の硬化性組成物。
（８）　遮光性顔料が、チタン化合物である（７）に記載の硬化性組成物。
（９）　さらに、含フッ素樹脂を含有する（１）～（８）のいずれかに記載の硬化性組成物。
（１０）　さらに、２種以上の有機溶剤を含有する（１）～（９）のいずれかに記載の硬化性組成物。
（１１）　（１）～（１０）のいずれかに記載の硬化性組成物を硬化して得られる遮光膜。
（１２）　（１１）に記載の遮光膜を有する、固体撮像装置。
（１３）　（１２）に記載の遮光膜を有する、カラーフィルタ。 (1) A curable composition containing a colorant, a radical photopolymerization 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 a 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 radical photopolymerization initiator is an oxime 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), further containing a fluorine-containing resin.
(10) The curable composition according to any one of (1) to (9), further comprising two or more 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 imaging device having the light-shielding film according to (11).
(13) A color filter having the light shielding film according to (12).
　本発明によれば、優れた低反射性を有する硬化膜を作製することができる硬化性組成物を提供することができる。また、本発明によれば、上述の硬化性組成物を硬化して得られる遮光膜、ならびに、上述の遮光膜を有する固体撮像装置、および、カラーフィルタを提供することができる。 According to the present invention, a curable composition capable of producing a cured film having excellent low reflectivity can be provided. Moreover, according to this invention, the light shielding film obtained by hardening | curing the above-mentioned curable composition, the solid-state imaging device which has the above-mentioned light shielding film, and a color filter can be provided.
第１実施形態の固体撮像装置を示す斜視図である。It is a perspective view which shows the solid-state imaging device of 1st Embodiment. 第１実施形態の固体撮像装置の分解斜視図である。It is a disassembled perspective view of the solid-state imaging device of 1st Embodiment. 第１実施形態の固体撮像装置を示す断面図である。It is sectional drawing which shows the solid-state imaging device of 1st Embodiment. 第２実施形態の固体撮像装置を示す断面図である。It is sectional drawing which shows the solid-state imaging device of 2nd Embodiment. 第３実施形態の固体撮像装置を示す断面図である。It is sectional drawing which shows the solid-state imaging device of 3rd Embodiment. 第４実施形態の固体撮像装置を示す断面図である。It is sectional drawing which shows the solid-state imaging device of 4th Embodiment.
　以下、本発明について詳細に説明する。
　以下に記載する構成要件の説明は、本発明の代表的な実施形態に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。
　なお本明細書における基（原子群）の表記において、置換および無置換を記していない表記は、本発明の効果を損ねない範囲で、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。このことは、各化合物についても同義である。
　また、本明細書中における「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、および、電子線等を意味する。また、本明細書において光とは、活性光線または放射線を意味する。本明細書中における「露光」とは、特に断らない限り、水銀灯およびエキシマレーザーに代表される遠紫外線、Ｘ線、ならびに、ＥＵＶ光などによる露光のみならず、電子線およびイオンビーム等の粒子線による描画も露光に含める。
　また、本明細書において、「（メタ）アクリレート」はアクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」はアクリルおよびメタクリルの双方、または、いずれかを表す。
　また、本明細書において、「単量体」と「モノマー」とは同義である。本明細書における単量体は、オリゴマーおよびポリマーと区別され、特に断らない限り、重量平均分子量が２，０００以下の化合物をいう。本明細書において、重合性化合物とは、重合性官能基を有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性官能基とは、重合反応に関与する基を言う。
　また、本明細書において「準備」というときには、特定の材料を合成ないし調合等して備えることのほか、購入等により所定の物を調達することを含む意味である。
　また、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atom group) in the present specification, the description that does not describe substitution and non-substitution includes 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 is included. 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 also about each compound.
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In the present specification, light means actinic rays or radiation. In the present specification, “exposure” means not only exposure with deep ultraviolet rays, X-rays, EUV light, etc., typified by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in exposure.
In the present specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acryl and methacryl.
In this specification, “monomer” and “monomer” are synonymous. The monomer in the present specification is distinguished from an oligomer and a polymer, and means 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. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In addition, the term “preparation” in the present specification means that a specific material is synthesized or blended, and a predetermined item is procured by purchase or the like.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
［硬化性組成物］
　本発明の硬化性組成物は、着色剤と、光ラジカル重合開始剤と、重合性化合物と、塩基発生剤と、分散剤と、を含有する。 [Curable composition]
The curable composition of the present invention contains a colorant, a radical photopolymerization initiator, a polymerizable compound, a base generator, and a dispersant.
　このような構成を有する本発明の硬化性組成物によれは、優れた低反射性を有する硬化膜を作製することができる。
　この効果が得られる機序は、詳細には明らかではないが、本発明者らは以下のように推測している。 According to the curable composition of the present invention having such a configuration, 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 presume as follows.
　後述する方法により基材上に本発明の硬化性組成物を塗布して塗膜を形成し、この塗膜を硬化させることにより硬化膜（以下、単に「硬化膜」ともいう。）を作製することができる。本発明の硬化性組成物は光ラジカル重合開始剤と、塩基発生剤と、を含有するため、上述の塗膜に所定波長の放射線を照射すると、光ラジカル重合開始剤による重合性化合物の重合反応と、塩基発生剤からの塩基の発生反応と、が競合的に進むと推測される。この傾向は、塩基発生剤が光塩基発生剤を含有する場合に、より顕著である。
　放射線が入射した面に近い部分（塗膜中の浅い部分、すなわち、塗膜表面からの深さが浅い領域、以下、「上側領域」という。）では、上述の反応が進行し、硬化が進行するとともに、塩基発生剤が分解して塩基が発生し、塗膜中を塩基が拡散する。一方、放射線の入射面から遠い部分（塗膜中の深い部分、すなわち、基材表面に近い領域、以下、「下側領域」という。）においては、到達する放射線量が上側領域と比較して少ない。従って、上述のとおり、光ラジカル重合開始剤の反応（ラジカル発生）と、塩基発生剤による塩基発生が競合的に進行する系においては、下側領域における光ラジカル重合開始剤による重合性化合物の重合反応の進行速度は、上側領域と比較して遅いものと推測される。とくに、本発明の硬化性組成物が光塩基発生剤を含有する場合には、ラジカル発生に必要な放射線が塩基発生にも使われ得る。従って、相対的に到達する放射線量が少ない下側領域においては、光ラジカル重合開始剤による重合性化合物の重合反応の進行速度が、上側領域と比較してより遅いものと推測される。さらに、下側領域には、塩基発生剤から発生した塩基が上側領域から拡散してくるため、重合反応の進行がより抑制される。
　上記のとおり、上側領域と下側領域で重合反応の速度および／または進行度合いが異なるものと推測される。そのため、この塗膜を硬化して得られた硬化膜は、上側領域と下側領域で硬化収縮により生じる応力が異なるため、上側領域に微細なシワが発生し、これが硬化膜の低反射性に寄与しているものと推測される。 A 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 produce a cured film (hereinafter also simply referred to as “cured film”). be able to. Since the curable composition of the present invention contains a radical photopolymerization initiator and a base generator, when the coating film is irradiated with radiation of a predetermined wavelength, the polymerization reaction of the polymerizable compound by the radical photopolymerization initiator. And the base generation reaction from the base generator are presumed to 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 (the shallow portion in the coating film, that is, the region where the depth from the coating film surface is shallow, hereinafter referred to as the “upper region”), the above reaction proceeds and curing proceeds. At the same time, the base generator decomposes to generate a base, and the base diffuses in the coating film. On the other hand, in a portion far from the radiation incident surface (a deep portion in the coating film, that is, a region close to the substrate surface, hereinafter referred to as a “lower region”), the amount of radiation that reaches is higher than that of the upper region. Few. Therefore, as described above, in a system in which the reaction of the radical photopolymerization initiator (radical generation) and the base generation by the base generator proceed competitively, the polymerization of the polymerizable compound by the radical photopolymerization initiator in the lower region. The rate of progress of the reaction is assumed to be slow compared to the upper region. In particular, when the curable composition of the present invention contains a photobase generator, the radiation necessary for radical generation can also be used for base generation. Therefore, in the lower region where the amount of radiation that reaches 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 that in the upper region. Furthermore, since the base generated from the base generator diffuses from the upper region in the lower region, the progress of the polymerization reaction is further suppressed.
As described above, it is presumed that the speed and / or progress of the polymerization reaction are different between the upper region and the lower region. For this reason, the cured film obtained by curing this coating film has different wrinkles due to curing shrinkage between the upper region and the lower region, so that fine wrinkles are generated in the upper region, which reduces the low reflectivity of the cured film. Presumed to have contributed.
　以下では、本発明の硬化性組成物の各成分について詳述する。 Hereinafter, each component of the curable composition of the present invention will be described in detail.
〔着色剤〕
　本発明の硬化性組成物は、着色剤を含有する。着色剤は、公知の着色剤を用いることができるが、なかでも顔料を含有することが好ましい。顔料としては、例えば、カラーフィルタ製造に用いる場合であれば、カラーフィルタの色画素を形成するＲ（レッド）、Ｇ（グリーン）、および、Ｂ（ブルー）等の有彩色系の顔料（有彩色顔料）を用いることができる。また、硬化膜を遮光膜またはブラックマトリクスとして用いる場合、硬化膜が優れた遮光性を有する点で、着色剤は遮光性顔料を含有することが好ましい。 [Colorant]
The curable composition of the present invention contains a colorant. A known colorant can be used as the colorant, and among these, it is preferable to contain a pigment. As the pigment, for example, when used in the production of a color filter, chromatic pigments (chromatic colors such as R (red), G (green), and B (blue)) that form color pixels of the color filter. Pigment). Moreover, when using a cured film as a light shielding film or a black matrix, it is preferable that a coloring agent contains a light shielding pigment at the point which the cured film has the outstanding light-shielding property.
　遮光性顔料としては、公知の遮光性顔料を用いることができ、少量で高い光学濃度（Ｏｐｔｉｃａｌ　Ｄｅｎｓｉｔｙ：ＯＤ値）を実現できる観点から、カーボンブラック、チタン化合物、酸化鉄、酸化マンガン、および、グラファイト等が好ましく、なかでも、カーボンブラックおよびチタン化合物からなる群から選択される少なくとも１種を含有することがより好ましく、チタン化合物がさらに好ましい。なお、遮光性顔料の具体例としては、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　１等の有機顔料、および、Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　７等の無機顔料が挙げられる。 As the light-shielding pigment, a known light-shielding pigment can be used. From the viewpoint of realizing a high optical density (Optical Density: OD value) in a small amount, carbon black, titanium compound, iron oxide, manganese oxide, and graphite. Among them, it is preferable to contain at least one selected from the group consisting of carbon black and a titanium compound, and a titanium compound is 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.
　チタン化合物は、公知のものを用いることができ、例えば、酸化チタンおよびチタンブラックなどが挙げられる。なかでも、４００～１０００ｎｍの広い範囲の光線に対して遮光性を有し、遮光膜のパターン形成に用いられることがある波長域（４００ｎｍ未満）の光線透過率が高い点で、チタンブラックが好ましい。 A well-known thing can be used for a titanium compound, For example, a titanium oxide, titanium black, etc. are mentioned. Of these, titanium black is preferable in that it has a light-shielding property for light in a wide range of 400 to 1000 nm, and has a high light transmittance in a wavelength region (less than 400 nm) that may be used for pattern formation of a light-shielding film. .
　チタンブラックとは、チタン原子を含有する黒色粒子である。好ましくは低次酸化チタン酸窒化チタン、および、窒化チタン等である。チタンブラック粒子は、分散性向上および凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。チタンブラック粒子は、酸化ケイ素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、または、酸化ジルコニウムで表面を被覆することが可能である。また、特開２００７－３０２８３６号公報に表されるような撥水性物質での処理も可能である。
　チタンブラックは、典型的には、チタンブラック粒子であり、個々の粒子の一次粒径および平均一次粒子径のいずれもが小さいことが好ましい。
　具体的には、チタンブラックの平均一次粒子径は、１０ｎｍ～４５ｎｍの範囲が好ましい。なお、本発明における粒径、即ち、粒子直径とは、粒子の外表面の投影面積と等しい面積をもつ円の直径である。粒子の投影面積は、電子顕微鏡写真での撮影により得られた３００個の粒子の面積を測定して平均し、撮影倍率を補正することにより得られる。 Titanium black is black particles containing titanium atoms. Preferred are low order titanium oxide titanium oxynitride and titanium nitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. 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, treatment with a water-repellent substance as disclosed in JP 2007-302836 A is also possible.
Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small.
Specifically, the average primary particle diameter of titanium black is preferably in the range of 10 nm to 45 nm. In the present invention, the particle diameter, that is, the particle diameter is a 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.
　チタンブラックの比表面積は特に制限されないが、かかるチタンブラックを撥水化剤で表面処理した後の撥水性が所定の性能となるために、ＢＥＴ（Brunauer, Emmett, Teller）法にて測定した値が通常５ｍ２／ｇ以上１５０ｍ２／ｇ以下程度、特に２０ｍ２／ｇ以上１２０ｍ２／ｇ以下であることが好ましい。
　チタンブラックの市販品の例としては、チタンブラック１０Ｓ、１２Ｓ、１３Ｒ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ、１３Ｒ－Ｎ、１３Ｍ－Ｔ（商品名：以上、三菱マテリアル（株）製）、ティラック（Ｔｉｌａｃｋ）Ｄ（商品名：赤穂化成（株）製）などが挙げられる。 The specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method in order that the water repellency after surface treatment of such titanium black with a water repellent agent becomes a predetermined performance. Is usually about 5 m 2 / g or more and 150 m 2 / g or less, 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, 13R-N, 13M-T (trade names: above, manufactured by Mitsubishi Materials Corporation), Tilac ( Tilac) D (trade name: manufactured by Ako Kasei Co., Ltd.).
　さらに、チタンブラックを、チタンブラックおよびＳｉ原子を含む被分散体として含有することも好ましい。
　この形態において、チタンブラックは、硬化性組成物中において被分散体として含有されるものであり、被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が質量換算で０．０５以上であることが好ましい。
　ここで、上記被分散体は、チタンブラックが一次粒子の状態であるもの、および、凝集体（二次粒子）の状態であるものの双方を包含する。
　なお、本発明における被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）は、０．５（質量換算）を超えると被分散体を使用した硬化性組成物の製造が困難な傾向となる場合があるため、その上限は０．５であることが好ましい。
　また、被分散体を使用した遮光膜を光リソグラフィー等によりパターニングした際に、除去部に残渣が残りにくく、遮光能が優れる点で、被分散体のＳｉ／Ｔｉは、０．０５以上０．５以下であることがより好ましく、０．０７以上０．４以下であることがさらに好ましい。
　被分散体のＳｉ／Ｔｉを変更する（例えば、０．０５以上とする）ためには、以下のような手段を用いることができる。
　先ず、酸化チタンとシリカ粒子とを分散機を用いて分散することにより分散物を得て、この分散物を高温（例えば、８５０～１０００℃）にて還元処理することにより、チタンブラック粒子を主成分とし、ＳｉとＴｉとを含有する被分散体を得ることができる。
　ここで、被分散体のＳｉ／Ｔｉを変更するための具体的な態様について説明する。
　Ｓｉ／Ｔｉが、例えば、０．０５以上等に調整されたチタンブラックは、例えば、特開２００８－２６６０４５号公報の段落番号〔０００５〕および段落番号〔００１６〕～〔００２１〕に記載の方法により作製することができる。 Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a dispersion in the curable composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.00 on a mass basis. It is preferable that it is 05 or more.
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In addition, when the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion in the present invention exceeds 0.5 (in terms of mass), 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 object to be dispersed is patterned by photolithography or the like, Si / Ti of the object to be dispersed is 0.05 or more and 0.0. 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 object to be dispersed (for example, 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 subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly formed. A dispersed material containing Si and Ti as components can be obtained.
Here, the specific aspect for changing Si / Ti of a to-be-dispersed body is demonstrated.
Titanium black in which Si / Ti is adjusted to 0.05 or more, for example, can be obtained by, for example, the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of JP-A-2008-266045. Can be produced.
　本発明においては、チタンブラックおよびＳｉ原子を含む被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）を好適な範囲（例えば０．０５以上）に調整することで、この被分散体を含む硬化性組成物を用いて遮光膜を形成した際に、遮光膜の形成領域外における硬化性組成物由来の残渣物が低減される。なお、残渣物は、チタンブラック粒子、樹脂成分等の硬化性組成物に由来する成分を含むものである。
　残渣物が低減される理由は未だ明確ではないが、上記のような被分散体は小粒径となる傾向があり（例えば、粒径が３０ｎｍ以下）、さらに、この被分散体のＳｉ原子が含まれる成分が増すことにより、膜全体の下地との吸着性が低減され、これが、遮光膜の形成における未硬化の硬化性組成物（特に、チタンブラック）の現像除去性の向上に寄与すると推測している。
　また、チタンブラックは、紫外光から赤外光までの広範囲に亘る波長領域の光に対する遮光性に優れることから、上記したチタンブラックおよびＳｉ原子を含む被分散体（好ましくはＳｉ／Ｔｉが質量換算で０．０５以上であるもの）を用いて形成された遮光膜は優れた遮光性を発揮する。
　なお、被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）は、例えば、特開２０１３－２４９４１７号公報の段落００３３に記載の方法（１－１）または方法（１－２）を用いて測定できる。
　また、硬化性組成物を硬化して得られた遮光膜に含有される被分散体について、その被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が０．０５以上か否かを判断するには、特開２０１３－２４９４１７号公報の段落００３５に記載の方法（２）を用いる。 In the present invention, by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), this coverage is achieved. 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 includes 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 above-mentioned dispersed material tends to have a small particle size (for example, the particle size is 30 nm or less). By increasing the amount of the components contained, the adsorptivity of the entire film with the underlayer is reduced, which is assumed to contribute to the improvement in the development removability of the uncured curable composition (particularly titanium black) in the formation of the light shielding film. is doing.
In addition, titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is converted into mass) The light-shielding film formed by using a material having a thickness 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, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
In addition, regarding the dispersion to be contained in the light shielding film obtained by curing the curable composition, the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is 0.05 or more. In order to determine whether or not, the method (2) described in paragraph 0035 of JP2013-249417A is used.
　チタンブラックおよびＳｉ原子を含む被分散体において、チタンブラックは、上記したものを使用できる。
　また、この被分散体においては、チタンブラックと共に、分散性および着色性等を調整する目的で、Ｃｕ、Ｆｅ、Ｍｎ、Ｖ、Ｎｉ等の複合酸化物、酸化コバルト、酸化鉄、カーボンブラック、および、アニリンブラック等からなる黒色顔料を、１種または２種以上を組み合わせて、被分散体として併用してもよい。
　この場合、全被分散体中の５０質量％以上をチタンブラックからなる被分散体が占めることが好ましい。
　また、この被分散体においては、遮光性の調整等を目的として、本発明の効果を損なわない限りにおいて、チタンブラックと共に、他の着色剤（有機顔料や染料など）を所望により併用してもよい。
　以下、被分散体にＳｉ原子を導入する際に用いられる材料について述べる。被分散体にＳｉ原子を導入する際には、シリカなどのＳｉ含有物質を用いればよい。
　用いうるシリカとしては、沈降シリカ、フュームドシリカ、コロイダルシリカ、および、合成シリカなどを挙げることができ、これらを適宜選択して使用すればよい。
　さらに、シリカ粒子の粒径が遮光膜を形成した際に膜厚よりも小さい粒径であると遮光性がより優れるため、シリカ粒子として微粒子タイプのシリカを用いることが好ましい。なお、微粒子タイプのシリカの例としては、例えば、特開２０１３－２４９４１７号公報の段落００３９に記載のシリカが挙げられ、これらの内容は本明細書に組み込まれる。
　本発明の硬化性組成物は、チタンブラックを１種含有するものであってもよく、２種以上を含有してもよい。 In the dispersion containing titanium black and Si atoms, the above-described titanium black can be used.
Further, in this dispersion, for the purpose of adjusting dispersibility and colorability together with titanium black, complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, and A black pigment made of aniline black or the like may be used alone or in combination of two or more as a dispersion.
In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black.
In addition, in this dispersion, for the purpose of adjusting the light shielding property, other colorants (such as organic pigments and dyes) may be used in combination with titanium black as long as the effects of the present invention are not impaired. Good.
Hereinafter, materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These can be selected and used as appropriate.
Furthermore, if 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 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 kind of titanium black or may contain two or more kinds.
　上記顔料を分散させるプロセスとしては、分散に用いる機械力として圧縮、圧搾、衝撃、剪断、およびキャビテーションなどを使用するプロセスなどが挙げられる。これらのプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散、およびマイクロフルイダイザーなどが挙げられる。また「分散技術大全、株式会社情報機構発行、２００５年７月１５日」および「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」に記載のプロセスおよび分散機を好適に使用できる。また、ソルトミリング工程による顔料の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理、および条件等は、例えば、特開２０１５－１９４５２１号公報、及び、特開２０１２－０４６６２９号公報等に記載のものを使用することができる。
　なかでも、サンドミル（ビーズミル）が好ましい。またサンドミル（ビーズミル）における顔料の分散処理においては、径の小さいビーズを使用する、または、ビーズの充填率を大きくする等により分散効率を高めた条件で処理することが好ましく、更に分散処理後に濾過および／または遠心分離などで素粒子を除去することが好ましい。 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 mill, sand mill, roll mill, ball mill, high speed impeller, sand grinder, flow jet mixer, high pressure wet atomization, ultrasonic dispersion, and microfluidizer. In addition, “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion Technology and Industrial Application Centered on Suspension (Solid / Liquid Dispersion System)” The process and the disperser described in “Issuance, October 10, 1978” can be preferably used. Moreover, you may perform the refinement | miniaturization process of the pigment by a salt milling process. As materials, equipment, processing, conditions and the like used in the salt milling process, for example, those described in JP-A-2015-194521, JP-A-2012-046629, etc. can be used.
Of these, a sand mill (bead mill) is preferable. In addition, in the pigment dispersion treatment in the sand mill (bead mill), it is preferable to use beads having a small diameter or to increase the dispersion efficiency by increasing the filling rate of the beads. It is preferable to remove elementary particles by centrifugation and / or the like.
　本発明の硬化性組成物は、着色剤に加えて、必要に応じて体質顔料を含んでいてもよい。このような体質顔料としては、例えば、硫酸バリウム、炭酸バリウム、炭酸カルシウム、シリカ、塩基性炭酸マグネシウム、アルミナ白、グロス白、および、ハイドロタルサイト等を挙げることができる。これらの体質顔料は、単独でまたは２種以上を混合して使用することができる。体質顔料の使用量は、着色剤１００質量部に対して、通常、０～１００質量部、好ましくは５～５０質量部、より好ましくは１０～４０質量部である。本発明において、着色剤および体質顔料は、場合により、それらの表面をポリマーで改質して使用することができる。 The curable composition of the present invention may contain extender pigments as 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 extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the colorant. In the present invention, the colorant and extender can be used with their surface modified with a polymer in some cases.
　着色剤は１種を単独で用いても、２種以上を併用してもよい。着色剤としては、赤色、青色、黄色、緑色、および、紫色等の着色有機顔料を含有してもよい。遮光性顔料と着色有機顔料とを併用する場合には、着色有機顔料を遮光性顔料に対して１～４０質量％用いることが好ましい。色味を調整する観点で、赤色顔料と遮光性顔料とを併用することが好ましく、特に限定はされないが赤色顔料としてはピグメントレッド２５４であることが好ましい。また、遮光性を高める観点から黄色顔料と遮光性顔料とを併用することが好ましく、特に限定はされないが黄色顔料としてはピグメントイエロー１５０であることが好ましい。 Coloring agents may be used alone or in combination of two or more. As a coloring agent, you may contain colored organic pigments, such as red, blue, yellow, green, and purple. When the light-shielding pigment and the colored organic pigment are used in combination, the colored organic pigment is preferably used in an amount of 1 to 40% by mass 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 not particularly limited. Moreover, it is preferable to use a yellow pigment and a light-shielding pigment in combination from the viewpoint of enhancing the light-shielding property, and although it is not particularly limited, Pigment Yellow 150 is preferable as the yellow pigment.
　本発明の硬化性組成物中における着色剤の含有量は、硬化性組成物中の全固形分に対して、２０～８０質量％が好ましく、３０～７０質量％がより好ましく、３５～６０質量％がさらに好ましい。 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 more preferably 35 to 60% by mass with respect to the total solid content in the curable composition. % Is more preferable.
〔光ラジカル重合開始剤〕
　本発明の硬化性組成物は、光ラジカル重合開始剤を含有する。光ラジカル重合開始剤としては、重合性化合物の重合を開始する能力を有する限り、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視光領域において感光性を有するものが好ましい。また、光ラジカル重合開始剤は、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。また、光ラジカル重合開始剤は、約３００ｎｍ～８００ｎｍ（３３０ｎｍ～５００ｎｍが好ましい。）の範囲内に少なくとも約５０の分子吸光係数を有する化合物を、少なくとも１種含有していることが好ましい。 [Photo radical polymerization initiator]
The curable composition of the present invention contains a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known radical photopolymerization initiators. For example, those having photosensitivity from the ultraviolet region to the visible light region are preferable. In addition, the photo radical polymerization initiator may be an activator that generates an active radical by generating some action with a photo-excited sensitizer. The radical photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).
　光ラジカル重合開始剤としては、少なくとも芳香族基を有する化合物であることが好ましく、例えば、（ビス）アシルホスフィンオキシドまたはそのエステル類、アセトフェノン系化合物、α－アミノケトン化合物、ベンゾフェノン系化合物、ベンゾインエーテル系化合物、ケタール誘導体化合物、チオキサントン化合物、オキシムエステル化合物、ヘキサアリールビイミダゾール化合物、トリハロメチル化合物、アゾ化合物、有機過酸化物、ジアゾニウム化合物、ヨードニウム化合物、スルホニウム化合物、アジニウム化合物、ベンゾインエーテル系化合物、ケタール誘導体化合物、メタロセン化合物等のオニウム塩化合物、有機硼素塩化合物、および、ジスルホン化合物などが挙げられる。感度の観点から、オキシムエステル化合物、アシルホスフィンオキシド系化合物、アセトフェノン系化合物、α－アミノケトン化合物、トリハロメチル化合物、ヘキサアリールビイミダゾール化合物、または、チオール化合物が好ましく、オキシムエステル化合物（オキシム系開始剤、形態は後述する）がより好ましい。着色剤として黒色顔料を用いた場合においては、光ラジカル重合開始剤としてオキシムエステル化合物を用いることで、優れたリソグラフィ性が得られやすい。 The radical photopolymerization initiator is preferably a compound having at least an aromatic group. For example, (bis) acylphosphine oxide or its esters, acetophenone compounds, α-aminoketone compounds, benzophenone compounds, benzoin ether compounds 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 onium salt compounds such as compounds, metallocene compounds, organoboron salt compounds, and disulfone compounds. From the viewpoint of sensitivity, oxime ester compounds, acylphosphine oxide compounds, acetophenone compounds, α-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, or thiol compounds are preferred, and oxime ester compounds (oxime initiators, The form is more preferable). When a black pigment is used as the colorant, excellent lithographic properties can be easily obtained by using an oxime ester compound as a radical photopolymerization initiator.
　光ラジカル重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、および、アシルホスフィン化合物も好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、特許第４２２５８９８号公報に記載のアシルホスフィンオキシド系開始剤も用いることができる。
　ヒドロキシアセトフェノン系開始剤としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、および、ＩＲＧＡＣＵＲＥ－１２７（商品名：いずれもＢＡＳＦ社製）を用いることができる。アミノアセトフェノン系開始剤としては、市販品であるＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、および、ＩＲＧＡＣＵＲＥ－３７９（商品名：いずれもＢＡＳＦ社製）を用いることができる。アミノアセトフェノン系開始剤として、３６５ｎｍまたは４０５ｎｍ等の長波光源に吸収波長がマッチングされた特開２００９－１９１１７９公報に記載の化合物も用いることができる。また、アシルホスフィン系開始剤としては市販品であるＩＲＧＡＣＵＲＥ－８１９およびＤＡＲＯＣＵＲ－ＴＰＯ（商品名：いずれもＢＡＳＦ社製）を用いることができる。 As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone 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, compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
＜オキシム系開始剤＞
　光ラジカル重合開始剤として、より好ましくはオキシム系開始剤が挙げられる。特にオキシム系開始剤は高感度で重合効率が高く、色材（着色剤）濃度によらず硬化でき、色材の濃度を高く設計しやすいため好ましい。
　オキシム系開始剤の具体例としては、特開２００１－２３３８４２号公報記載の化合物、特開２０００－８００６８号公報記載の化合物、および、特開２００６－３４２１６６号公報記載の化合物を用いることができる。オキシム系開始剤の具体例としては、例えば、３－ベンゾイロキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイロキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、および２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。 <Oxime initiator>
As the radical photopolymerization initiator, an oxime initiator is more preferable. In particular, an oxime-based initiator is preferable because it has high sensitivity and high polymerization efficiency, can be cured regardless of the colorant (colorant) concentration, and can be easily designed with a high colorant concentration.
Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166. Specific examples of the oxime initiator include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane. -3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
　オキシム系開始剤としては、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１６５３－１６６０）、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１５６－１６２、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年）ｐｐ．２０２－２３２、特開２０００－６６３８５号公報記載の化合物、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、および、特開２００６－３４２１６６号公報の各公報に記載の化合物等が挙げられる。
　市販品ではＩＲＧＡＣＵＲＥ－ＯＸＥ０１（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２（ＢＡＳＦ社製）も好適に用いられる。また、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０４、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０９、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０５（常州強力電子新材料有限公司社（ＣＨＡＮＧＺＨＯＵ　ＴＲＯＮＬＹ　ＮＥＷ　ＥＬＥＣＴＲＯＮＩＣ　ＭＡＴＥＲＩＡＬＳ　ＣＯ．，ＬＴＤ）製）、アデカアークルズＮＣＩ－９３０（ＡＤＥＫＡ社製）も用いることができる。 Examples of oxime initiators include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, and JP-A No. 2006-342166. It is done.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Also, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcles NC 930 (manufactured by ADEKA) can also be used.
　また上記記載以外のオキシム系開始剤として、カルバゾールＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物、ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号公報に記載の化合物、色素部位にニトロ基が導入された特開２０１０－１５０２５号公報、米国特許公開２００９－２９２０３９号記載の化合物、および、国際公開特許２００９－１３１１８９号公報に記載のケトオキシム系開始剤、トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号公報に記載の化合物、４０５ｎｍに吸収極大を有しｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報記載の化合物などを用いてもよい。好ましくは、例えば、特開２０１３－２９７６０号公報の段落０２７４～０２７５を参酌することができ、この内容は本願明細書に組み込まれる。 Further, as oxime initiators other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N-position, and those described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety Compounds, compounds described in Japanese Patent Application Laid-Open No. 2010-15025, US Patent Publication No. 2009-292039, and ketoxime initiator and triazine skeleton described in International Patent Publication No. 2009-131189, in which a nitro group is introduced at the dye moiety And a compound described in US Pat. No. 7,556,910 containing an oxime skeleton in the same molecule, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like It may be used. Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
　光ラジカル重合開始剤として、フルオレン環を有するオキシム系開始剤を用いることもできる。フルオレン環を有するオキシム系開始剤の具体例としては、特開２０１４－１３７４６６号公報記載の化合物が挙げられる。この内容は本明細書に組み込まれることとする。 An oxime initiator having a fluorene ring can also be used as a photo radical polymerization initiator. Specific examples of the oxime initiator having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.
　光ラジカル重合開始剤として、フッ素原子を有するオキシム系開始剤を用いることもできる。フッ素原子を有するオキシム系開始剤の具体例としては、特開２０１０－２６２０２８号公報記載の化合物、特表２０１４－５００８５２号公報記載の化合物２４、３６～４０、および、特開２０１３－１６４４７１号公報記載の化合物（Ｃ－３）などが挙げられる。この内容は本明細書に組み込まれることとする。 As the photo radical polymerization initiator, an oxime initiator having a fluorine atom can also be used. Specific examples of the oxime initiator having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. And the compound (C-3) described. This content is incorporated herein.
　光ラジカル重合開始剤として、ニトロ基を有するオキシム系開始剤を用いることができる。ニトロ基を有するオキシム系開始剤の具体例としては、特開２０１３－１１４２４９号公報の段落００３１～００４７、特開２０１４－１３７４６６号公報の段落０００８～００１２、００７０～００７９に記載されている化合物、アデカアークルズＮＣＩ－８３１（ＡＤＥＫＡ社製）が挙げられる。 As the photo radical polymerization initiator, an oxime initiator having a nitro group can be used. Specific examples of the oxime initiator having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Adeka Arkles NCI-831 (manufactured by ADEKA) can be mentioned.
　オキシム系開始剤の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of the oxime initiator are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　光ラジカル重合開始剤としては、３５０ｎｍ～５００ｎｍの波長領域に極大吸収波長を有する化合物が好ましく、３６０ｎｍ～４８０ｎｍの波長領域に吸収波長を有する化合物がより好ましく、３６５ｎｍおよび４０５ｎｍの吸光度が高い化合物が特に好ましい。 As the radical photopolymerization initiator, a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm is preferable, a compound having an absorption wavelength in a wavelength region of 360 nm to 480 nm is more preferable, and a compound having high absorbance at 365 nm and 405 nm is particularly preferable. preferable.
　光ラジカル重合開始剤の３６５ｎｍまたは４０５ｎｍにおけるモル吸光係数は、感度の観点から、１，０００～３００，０００であることが好ましく、２，０００～３００，０００であることがより好ましく、５，０００～２００，０００であることが特に好ましい。化合物のモル吸光係数の測定は、公知の方法を用いることができる。具体的には、例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの化合物の濃度で測定することが好ましい。
　光ラジカル重合開始剤は、必要に応じて２種以上を組み合わせて使用してもよい。 The molar extinction coefficient at 365 nm or 405 nm of the photo radical polymerization initiator is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, from the viewpoint of sensitivity, and 5,000. It is particularly preferred that it is ~ 200,000. A known method can be used to measure 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) using an ethyl acetate solvent at a compound concentration of 0.01 g / L.
Two or more kinds of radical photopolymerization initiators may be used in combination as necessary.
　光ラジカル重合開始剤の含有量は、硬化性組成物の全固形分に対し０．１～５０質量％が好ましく、より好ましくは０．５～３０質量％であり、さらに好ましくは１～２０質量％である。この範囲で、より良好な感度とパターン形成性が得られる。 The content of the photo radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1 to 20% by mass with respect to the total solid content of the curable composition. %. Within this range, better sensitivity and pattern formability can be obtained.
〔重合性化合物〕
　本発明の硬化性組成物は重合性化合物を含有する。重合性化合物は、少なくとも１個の付加重合可能なエチレン性不飽和基を有し、沸点が常圧で１００℃以上である化合物が好ましい。重合性化合物中のエチレン性不飽和基の数は特に制限されないが、硬化膜がより優れた低反射性を有する点で、２以上が好ましく、４以上が好ましく、５以上がより好ましい。上限は特に制限されないが、合成上の点から、１０以下が好ましい。なお、エチレン性不飽和基としては、例えば、（メタ）アクリロイル基、（メタ）アクリルアミド基、ビニル基などが挙げられる。
　少なくとも１個の付加重合可能なエチレン性不飽和基を有し、沸点が常圧で１００℃以上である化合物としては、例えば、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の単官能のアクリレートおよびメタクリレート；ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイロキシエチル）イソシアヌレート、グリセリンおよびトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後（メタ）アクリレート化したもの、ペンタエリスリトールまたはジペンタエリスリトールのポリ（メタ）アクリレート化したもの、特公昭４８－４１７０８号、特公昭５０－６０３４号、特開昭５１－３７１９３号の各公報に記載のウレタンアクリレート類、特開昭４８－６４１８３号、特公昭４９－４３１９１号、特公昭５２－３０４９０号の各公報に記載のポリエステルアクリレート類、ならびに、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートおよびメタクリレートを挙げることができる。さらに、日本接着協会誌Ｖｏｌ．２０、Ｎｏ.７、３００～３０８頁に光硬化性モノマーおよびオリゴマーとして紹介されているものも使用できる。
　また、特開平１０－６２９８６号公報において一般式（１）および一般式（２）としてその具体例と共に記載の多官能アルコールに、エチレンオキサイドまたはプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も用いることができる。
　なかでも、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、およびこれらのアクリロイル基がエチレングリコール残基、または、プロピレングリコール残基を介してジペンタエリスリトールに連結している構造が好ましい。これらのオリゴマータイプも使用できる。
　また、特公昭４８－４１７０８号、特開昭５１－３７１９３号、特公平２－３２２９３号、および特公平２－１６７６５号の各公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号、特公昭５６－１７６５４号、特公昭６２－３９４１７号、および特公昭６２－３９４１８号の各公報記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。さらに、特開昭６３－２７７６５３号、特開昭６３－２６０９０９号、および特開平１－１０５２３８号の各公報に記載される、分子内にアミノ構造またはスルフィド構造を有する付加重合性化合物類を用いることによっては、非常に感光スピードに優れた光重合性硬化性組成物を得ることができる。市販品としては、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（商品名、日本製紙ケミカル（株）製）、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（商品名、日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、および、ＡＩ－６００（商品名、共栄社化学（株）製）などが挙げられる。
　また、酸基を有するエチレン性不飽和化合物類も好適であり、市販品としては、例えば、東亞合成株式会社製のカルボキシル基含有３官能アクリレートであるＴＯ－７５６、およびカルボキシル基含有５官能アクリレートであるＴＯ－１３８２などが挙げられる。本発明に用いられる重合性化合物としては、４官能以上のアクリレート化合物がより好ましい。 (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 is preferably 2 or more, more preferably 4 or more, and more preferably 5 or more, in that the cured film has more excellent low reflectivity. The upper limit is not particularly limited, but is preferably 10 or less from the viewpoint of synthesis. Examples of the ethylenically unsaturated group include (meth) acryloyl group, (meth) acrylamide group, and 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, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) A polyfunctional alcohol such as ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane, which is obtained by adding ethylene oxide or propylene oxide and then (meth) acrylated, or poly ((pentaerythritol) or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49- Mention is made of polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-A Nos. 43191 and 52-30490, and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid. In That. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers, can also be used.
Further, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol described in JP-A-10-62986 and general examples thereof as general formula (1) and general formula (2) and then (meth) acrylated Can also be used.
Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are linked to dipentaerythritol via an ethylene glycol residue or a propylene glycol residue. Is preferred. These oligomer types can also be used.
Further, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58- Urethane compounds having an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the situation, a photopolymerizable curable composition having an excellent photosensitive speed can be obtained. Commercially available products include urethane oligomers UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name, Nippon Kasei) Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).
Further, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned. The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.
　重合性化合物は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　２種以上の重合性化合物を組み合わせて用いる場合、その組み合わせ態様は、硬化性組成物に要求される物性等に応じて適宜設定することができる。重合性化合物の好適な組み合わせ態様の一つとしては、例えば、上述した多官能のアクリレート化合物から選択した２種以上の重合性化合物を組み合わせる態様が挙げられ、その一例としては、ジペンタエリスリトールヘキサアクリレートおよびペンタエリスリトールトリアクリレートの組み合わせが挙げられる。
　本発明の硬化性組成物における重合性化合物の含有量は、硬化性組成物中の全固形分に対して、３質量％～５５質量％が好ましく、１０質量％～５０質量％がより好ましい。 A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more kinds of polymerizable compounds are used in combination, the combination mode can be appropriately set according to physical properties required for the curable composition. As one suitable combination aspect of a polymeric compound, the aspect which combines 2 or more types of polymeric compounds selected from the polyfunctional acrylate compound mentioned above is mentioned, for example, As an example, dipentaerythritol hexaacrylate is mentioned. 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 and more preferably 10% by mass to 50% by mass with respect to the total solid content in the curable composition.
〔塩基発生剤〕
　本発明の硬化性組成物は塩基発生剤を含有する。塩基発生剤としては、熱塩基発生剤および光塩基発生剤が挙げられる。 [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.
＜熱塩基発生剤＞
　熱塩基発生剤の種類は特に制限されないが、例えば、４０℃以上に加熱すると塩基を発生する酸性化合物（Ａ１）、および、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有するアンモニウム塩（Ａ２）から選ばれる少なくとも一種が挙げられる。
　上記酸性化合物（Ａ１）および上記アンモニウム塩（Ａ２）は、加熱すると塩基を発生する。
　なお、本明細書において、酸性化合物とは、化合物を容器に１ｇ採取し、イオン交換水とテトラヒドロフランとの混合液（質量比は水／テトラヒドロフラン＝１／４）を５０ｍＬ加えて、室温で１時間攪拌する。その溶液をｐＨメーターを用いて、２０℃にて測定した値が７未満である化合物を意味する。 <Heat base generator>
The type of the thermal base generator is not particularly limited. 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 an pKa1 of 0 to 4 and an ammonium cation And at least one selected from.
The acidic compound (A1) and the ammonium salt (A2) generate a base when heated.
In the present specification, an acidic compound means that 1 g of a compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added to the mixture at room temperature for 1 hour. Stir. The value of the solution measured at 20 ° C. using a pH meter is less than 7.
　酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度は、４０℃以上が好ましく、１２０～２００℃がより好ましい。塩基発生温度の上限は、１９０℃以下が好ましく、１８０℃以下がより好ましく、１６５℃以下がさらに好ましい。塩基発生温度の下限は、１３０℃以上が好ましく、１３５℃以上がより好ましい。
　塩基発生温度は、例えば、示差走査熱量測定を用い、化合物を耐圧カプセル中５℃／分で２５０℃まで加熱し、最も温度が低い発熱ピークのピーク温度を読み取り、ピーク温度を塩基発生温度として測定することができる。 The base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, and 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 further preferably 165 ° C. or lower. The lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher.
The base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
　熱塩基発生剤により発生する塩基は、２級アミンまたは３級アミンが好ましく、３級アミンがより好ましい。また、熱塩基発生剤により発生する塩基の沸点は、８０℃以上であることが好ましく、１００℃以上であることが好ましく、１４０℃以上であることが最も好ましい。また、発生する塩基の分子量は、８０～２０００が好ましい。下限は１００以上がより好ましい。上限は５００以下がより好ましい。なお、分子量の値は、構造式から求めた理論値である。 The base generated by the hot base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. The base generated by the thermal base generator preferably has a boiling point of 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 molecular weight value is a theoretical value obtained from the structural formula.
　上記酸性化合物（Ａ１）は、アンモニウム塩および後述する一般式（ＴＭ１）で表されるカチオンを有する化合物から選ばれる１種以上を含むことが好ましい。 The acidic compound (A1) preferably contains one or more selected from ammonium salts and compounds having a cation represented by the general formula (TM1) described later.
　上記アンモニウム塩（Ａ２）は、酸性化合物であることが好ましい。なお、上記アンモニウム塩（Ａ２）は、４０℃以上（好ましくは１２０～２００℃）に加熱すると塩基を発生する酸性化合物を含む化合物であってもよいし、４０℃以上（好ましくは１２０～２００℃）に加熱すると塩基を発生する酸性化合物を除く化合物であってもよい。
　以下、熱塩基発生剤について詳細に説明する。 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 thermal base generator will be described in detail.
（アンモニウム塩）
　アンモニウム塩とは、下記一般式（ＴＭ１）、または一般式（ＴＭ２）で表されるアンモニウムカチオンと、アニオンとの塩を意味する。アニオンは、アンモニウムカチオンのいずれかの一部と共有結合を介して結合していてもよく、アンモニウムカチオンの分子外に有していてもよいが、アンモニウムカチオンの分子外に有していることが好ましい。なお、アニオンが、アンモニウムカチオンの分子外に有するとは、アンモニウムカチオンとアニオンが共有結合を介して結合していない場合をいう。以下、カチオン部の分子外のアニオンを対アニオンともいう。
Figure JPOXMLDOC01-appb-C000004
　上記一般式（ＴＭ１）および一般式（ＴＭ２）中において、Ｒ１～Ｒ６は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ７は炭化水素基を表す。Ｒ１とＲ２、Ｒ３とＲ４、Ｒ５とＲ６、Ｒ５とＲ７はそれぞれ結合して環を形成してもよい。 (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, and may be outside the molecule of the ammonium cation, but may be outside the molecule of the ammonium cation. preferable. In addition, that an anion has outside the molecule | numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple | bonded through a covalent bond. Hereinafter, the anion outside the molecule of the cation moiety is also referred to as a counter anion.
Figure JPOXMLDOC01-appb-C000004
In the above general formulas (TM1) and (TM2), R 1 to R 6 each independently represents 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 , R 5 and R 7 may be bonded to form a ring.
　アンモニウム塩は、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有することが好ましい。アニオンのｐＫａ１の上限は、３．５以下がより好ましく、３．２以下が一層好ましい。下限は、０．５以上が好ましく、１．０以上がより好ましい。
　アニオンの種類は、カルボン酸アニオン、フェノールアニオン、リン酸アニオンおよび硫酸アニオンから選ばれる１種が好ましく、塩の安定性と熱分解性を両立させられるという理由からカルボン酸アニオンがより好ましい。すなわち、アンモニウム塩は、アンモニウムカチオンとカルボン酸アニオンとの塩がより好ましい。
　カルボン酸アニオンは、２個以上のカルボキシル基を持つ２価以上のカルボン酸のアニオンが好ましく、２価のカルボン酸のアニオンがより好ましい。
　本発明において、カルボン酸アニオンは、ｐＫａ１が４以下のカルボン酸のアニオンであることが好ましい。ｐＫａ１は、３．５以下がより好ましく、３．２以下が更に好ましい。
　ここでｐＫａ１とは、酸の第一解離定数の逆数の対数を表し、Ｄｅｔｅｒｍｉｎａｔｉｏｎ　ｏｆ　Ｏｒｇａｎｉｃ　Ｓｔｒｕｃｔｕｒｅｓ　ｂｙ　Ｐｈｙｓｉｃａｌ　Ｍｅｔｈｏｄｓ（著者：Ｂｒｏｗｎ，　Ｈ．　Ｃ．，　ＭｃＤａｎｉｅｌ，　Ｄ．　Ｈ．，　Ｈａｆｌｉｇｅｒ，　Ｏ．，　Ｎａｃｈｏｄ，　Ｆ．　Ｃ．；　編纂：Ｂｒａｕｄｅ，　Ｅ．　Ａ．，　Ｎａｃｈｏｄ，　Ｆ．　Ｃ．；　Ａｃａｄｅｍｉｃ　Ｐｒｅｓｓ，　Ｎｅｗ
　Ｙｏｒｋ，　１９５５）や、Ｄａｔａ　ｆｏｒ　Ｂｉｏｃｈｅｍｉｃａｌ　Ｒｅｓｅａｒｃｈ（著者：Ｄａｗｓｏｎ，　Ｒ．Ｍ．Ｃ．ｅｔ　ａｌ；　Ｏｘｆｏｒｄ，　Ｃｌａｒｅｎｄｏｎ　Ｐｒｅｓｓ，　１９５９）に記載の値を参照することができる。これらの文献に記載の無い化合物については、ＡＣＤ／ｐＫａ（ＡＣＤ／Ｌａｂｓ製）のソフトを用いて構造式より算出した値を用いることとする。 The ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of the anion pKa1 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 kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate 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 a carboxylic acid anion having a pKa1 of 4 or less. 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 the determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafrigerch, O., Hafliger, O., Hafliger, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafliger, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch, O., Hafrigerch. F. C .; Compilation: Braude, EA, Nachod, FC, Academic Press, New.
York, 1955), and Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
　本発明において、カルボン酸アニオンは、下記一般式（Ｘ１）で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000005
　上記一般式（Ｘ１）において、ＥＷＧは、電子吸引性基を表す。 In the present invention, the carboxylate anion is preferably represented by the following general formula (X1).
Figure JPOXMLDOC01-appb-C000005
In the general formula (X1), EWG represents an electron-withdrawing group.
　電子吸引性基とは、ハメットの置換基定数σｍが正の値を示すものを意味する。ここでσｍは、都野雄甫による総説、有機合成化学協会誌第２３巻第８号（１９６５）Ｐ．６３１－６４２に詳しく説明されている。なお、本発明の電子吸引性基は、上記文献に記載された置換基に限定されるものではない。
　σｍが正の値を示す置換基の例としては例えば、ＣＦ3基（σｍ＝０．４３）、ＣＦ3ＣＯ基（σｍ＝０．６３）、ＨＣ≡Ｃ基（σｍ＝０．２１）、ＣＨ2＝ＣＨ基（σｍ＝０．０６）、Ａｃ基（σｍ＝０．３８）、ＭｅＯＣＯ基（σｍ＝０．３７）、ＭｅＣＯＣＨ＝ＣＨ基（σｍ＝０．２１）、ＰｈＣＯ基（σｍ＝０．３４）、および、Ｈ2ＮＣＯＣＨ2基（σｍ＝０．０６）などが挙げられる。なお、Ｍｅはメチル基を表し、Ａｃはアセチル基を表し、Ｐｈはフェニル基を表す。 The electron-withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is a review by Yugo Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) P.I. 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 has a positive value include, for example, CF 3 group (σm = 0.43), CF 3 CO group (σm = 0.63), HC≡C group (σm = 0.21), 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), H 2 NCOCH 2 group (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.
　ＥＷＧは、下記一般式（ＥＷＧ－１）～（ＥＷＧ－６）で表される基を表すことが好ましい。
Figure JPOXMLDOC01-appb-C000006
　式中、Ｒｘ１～Ｒｘ３は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヒドロキシル基またはカルボキシル基を表し、Ａｒは芳香族環基を表す。
　アルキル基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１０が更に好ましい。アルキル基は直鎖、分岐、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は、置換基を有していてもよく、無置換であってもよい。アルキル基が有してもよい置換基（以下、「置換基群Ａ」ともいう。）としては、例えばフッ素原子、塩素原子、臭素原子及びヨウ素原子等のハロゲン原子；メトキシ基、エトキシ基及びｔｅｒｔ－ブトキシ基等のアルコキシ基；フェノキシ基及びｐ－トリルオキシ基等のアリールオキシ基；メトキシカルボニル基、ブトキシカルボニル基及びフェノキシカルボニル基等のアルコキシカルボニル基；アセトキシ基、プロピオニルオキシ基及びベンゾイルオキシ基等のアシルオキシ基；アセチル基、ベンゾイル基、イソブチリル基、アクリロイル基、メタクリロイル基及びメトキサリル基等のアシル基；メチルスルファニル基及びｔｅｒｔ－ブチルスルファニル基等のアルキルスルファニル基；フェニルスルファニル基及びｐ－トリルスルファニル基等のアリールスルファニル基；メチル基、エチル基、ｔｅｒｔ－ブチル基及びドデシル基等のアルキル基；フッ化アルキル等のハロゲン化アルキル；シクロペンチル基、シクロヘキシル基、シクロヘプチル基、アダマンチル基等のシクロアルキル基；フェニル基、ｐ－トリル基、キシリル基、クメニル基、ナフチル基、アンスリル基及びフェナントリル基等のアリール基；ヒドロキシル基；カルボキシル基；ホルミル基；スルホン酸基；シアノ基；アルキルアミノカルボニル基；アリールアミノカルボニル基；スルホンアミド基；シリル基；アミノ基；モノアルキルアミノ基；ジアルキルアミノ基；アリールアミノ基；ジアリールアミノ基；チオキシ基；又はこれらの組み合わせが挙げられる。なかでも、カルボキシル基が好ましい。
　アルケニル基の炭素数は、２～３０が好ましく、２～２０がより好ましく、２～１０が更に好ましい。アルケニル基は直鎖、分岐、および、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルケニル基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述の置換基群Ａとして説明したものが挙げられる。置換基としては、カルボキシル基が好ましい。
　アリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。アリール基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述の置換基群Ａとして説明したものが挙げられる。置換基としては、カルボキシル基が好ましい。
　芳香族環基としては、具体的には、置換または無置換のベンゼン環、ナフタレン環、ペンタレン環、インデン環、アズレン環、ヘプタレン環、インデセン環、ペリレン環、ペンタセン環、アセタフタレン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環、および、フェナジン環が挙げられる。中でも、保存安定性と高感度化の観点から、ベンゼン環、ナフタレン環、アントラセン環、フェノチアジン環、またはカルバゾール環が好ましく、ベンゼン環またはナフタレン環が最も好ましい。
　芳香族環基が有していてもよい置換基の例としては、上述の置換基群Ａとして説明したものが挙げられる。置換基としては、カルボキシル基が好ましい。 EWG preferably represents a group represented by the following general formulas (EWG-1) to (EWG-6).
Figure JPOXMLDOC01-appb-C000006
In the formula, R x1 to R x3 each 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 alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent 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 group -Alkoxy groups such as butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acetoxy group, propionyloxy group and benzoyloxy group 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-tolylsulfa An arylsulfanyl group such as a methyl group; an alkyl group such as a methyl group, an ethyl group, a tert-butyl group and a dodecyl group; a halogenated alkyl such as a fluorinated alkyl; Alkyl group; aryl group such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxyl group; carboxyl group; formyl group; sulfonic acid group; cyano group; Arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; diarylamino group; thioxyl group; Of these, a carboxyl group is preferred.
The alkenyl group has preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 10 carbon atoms. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned. 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 still more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned. As the substituent, a carboxyl group is preferable.
Specific examples of the aromatic ring group include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, Anthracene ring, naphthacene 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, indolizine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring Phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and a phenazine ring. Among these, 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.
As an example of the substituent which the aromatic ring group may have, what was demonstrated as the above-mentioned substituent group A is mentioned. As the substituent, a carboxyl group is preferable.
　カルボン酸アニオンは、下記一般式（Ｘ）で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000007
　一般式（Ｘ）において、Ｌ１０は、単結合、または、アルキレン基、アルケニレン基、アリーレン基、－ＮＲＸ－およびこれらの組み合わせから選ばれる２価の連結基を表し、ＲＸは、水素原子、アルキル基、アルケニル基またはアリール基を表す。 The carboxylate anion is preferably represented by the following general formula (X).
Figure JPOXMLDOC01-appb-C000007
In the general formula (X), L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR X —, and a combination thereof, and R X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.
　Ｌ１０が表すアルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１０が更に好ましい。アルキレン基は直鎖、分岐、および、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルキレン基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述の置換基群Ａとして説明したものが挙げられる。
　Ｌ１０が表すアルケニレン基の炭素数は、２～３０が好ましく、２～２０がより好ましく、２～１０が更に好ましい。アルケニレン基は直鎖、分岐、および、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルケニレン基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述の置換基群Ａとして説明したものが挙げられる。
　Ｌ１０が表すアリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。アリーレン基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述の置換基群Ａとして説明したものが挙げられる。 The alkylene group represented by L 10 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkylene group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
The number of carbon atoms of the alkenylene group represented by L 10 is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10. The alkenylene group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkenylene group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
The number of carbon atoms of the arylene group represented by L 10 is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The arylene group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
　ＲＸが表すアルキル基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１０が更に好ましい。アルキル基は直鎖、分岐、および、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述の置換基群Ａとして説明したものが挙げられる。
　ＲＸが表すアルケニル基の炭素数は、２～３０が好ましく、２～２０がより好ましく、２～１０が更に好ましい。アルケニル基は直鎖、分岐、および、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルケニル基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述の置換基群Ａとして説明したものが挙げられる。
　ＲＸが表すアリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。アリール基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述の置換基群Ａとして説明したものが挙げられる。 The number of carbon atoms of the alkyl group represented by R X is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
The alkenyl group represented by R X preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
The number of carbon atoms of the aryl group represented by R X is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. As a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
　カルボン酸アニオンの具体例としては、マレイン酸アニオン、フタル酸アニオン、Ｎ－フェニルイミノ二酢酸アニオンおよびシュウ酸アニオンが挙げられる。これらを好ましく用いることができる。 Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
　アンモニウムカチオンは、下記一般式（Ｙ１－１）～（Ｙ１－６）のいずれかで表されることが好ましい。
Figure JPOXMLDOC01-appb-C000008
 The ammonium cation is preferably represented by any one of the following general formulas (Y1-1) to (Y1-6).
Figure JPOXMLDOC01-appb-C000008
　上記一般式において、Ｒ１０１は、ｎ価の有機基を表し、
　Ｒ１０２～Ｒ１１１は、それぞれ独立に水素原子、または、炭化水素基を表し、
　Ｒ１５０およびＲ１５１は、それぞれ独立に炭化水素基を表し、
　Ｒ１０４とＲ１０５、Ｒ１０４とＲ１５０、Ｒ１０７とＲ１０８、および、Ｒ１０９とＲ１１０は、互いに結合して環を形成していてもよく、
　Ａｒ１０１およびＡｒ１０２は、それぞれ独立に、アリール基を表し、
　ｎは、１以上の整数を表し、
　ｍは、０～５の整数を表す。 In the above general formula, R 101 represents an n-valent organic group,
R 102 to R 111 each independently represents a hydrogen atom or a hydrocarbon group,
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 bonded 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 of 0 to 5.
　Ｒ１０１は、ｎ価の有機基を表す。１価の有機基としては、アルキル基、アルキレン基、芳香族環基などが挙げられる。２価以上の有機基としては、１価の有機基から水素原子を１個以上除いてｎ価の基としたものが挙げられる。
　Ｒ１０１は、芳香族環基であることが好ましい。芳香族環基の具体例としては、後述するＡｒ１０で説明したものが挙げられる。 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 valent organic group include those obtained by removing one or more hydrogen atoms from a monovalent organic group to form 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.
　Ｒ１０２～Ｒ１１１は、それぞれ独立に水素原子、または、炭化水素基を表し、Ｒ１５０およびＲ１５１は、それぞれ独立に炭化水素基を表す。
　Ｒ１０２～Ｒ１１１、およびＲ１５１が表す炭化水素基としては、アルキル基、アルケニル基またはアリール基が好ましい。アルキル基、アルケニル基およびアリール基はさらに置換基を有していてもよい。
　Ｒ１５０が表す炭化水素基としては、アルキレン基が挙げられる。なお、アルキレン基はさらに置換基を有していてもよい。なお、置換基としては、上述の置換基群Ａとして説明したものが挙げられる。 R 102 to R 111 each independently represent a hydrogen atom or a hydrocarbon group, and R 150 and R 151 each independently represent a hydrocarbon group.
The hydrocarbon group represented by R 102 to R 111 and R 151 is preferably an alkyl group, an alkenyl group or an aryl group. 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. In addition, as a substituent, what was demonstrated as the above-mentioned substituent group A is mentioned.
　アルキル基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１０が更に好ましい。アルキル基は直鎖、分岐、および、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は、置換基を有していてもよく、無置換であってもよい。
　アルケニル基の炭素数は、２～３０が好ましく、２～２０がより好ましく、２～１０が更に好ましい。アルケニル基は直鎖、分岐、および、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルケニル基は、置換基を有していてもよく、無置換であってもよい。
　アリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。アリール基は、置換基を有していてもよく、無置換であってもよい。 The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted.
The alkenyl group has preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 10 carbon atoms. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, and 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 still more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted.
　Ａｒ１０１およびＡｒ１０２は、それぞれ独立に、アリール基を表す。
　アリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。アリール基は、置換基を有していてもよく、無置換であってもよい。 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 still more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted.
　Ｒ１０４とＲ１０５、Ｒ１０４とＲ１５０、Ｒ１０７とＲ１０８、および、Ｒ１０９とＲ１１０は、互いに結合して環を形成していてもよい。環としては、脂環（非芳香性の炭化水素環）、芳香族環、および、複素環などが挙げられる。環は単環であってもよく、複環であってもよい。上記の基が結合して環を形成する場合の連結基としては、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族環基およびそれらの組み合わせからなる群より選ばれる２価の連結基で連結することができる。具体例としては、例えば、ピロリジン環、ピロール環、ピペリジン環、ピリジン環、イミダゾール環、ピラゾール環、オキサゾール環、チアゾール環、ピラジン環、モルホリン環、チアジン環、インドール環、イソインドール環、ベンゾイミダゾール環、プリン環、キノリン環、イソキノリン環、キノキサリン環、シンノリン環、および、カルバゾール環、などが挙げられる。 R 104 and R 105 , R 104 and R 150 , R 107 and R 108 , and R 109 and R 110 may be bonded to each other to form a ring. Examples of the ring include an alicyclic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be monocyclic or multicyclic. In the case where the above groups are bonded to form a ring, the linking group is composed of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic ring group, and combinations thereof. They can be linked by 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. , Purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring, and the like.
　アンモニウムカチオンは、一般式（Ｙ１－１）または（Ｙ１－２）で表される構造が好ましく、一般式（Ｙ１－１）または（Ｙ１－２）で表され、Ｒ１０１が芳香族環基である構造がより好ましく、一般式（Ｙ１－１）で表され、Ｒ１０１が芳香族環基である構造が特に好ましい。 The ammonium cation preferably has a structure represented by the general formula (Y1-1) or (Y1-2), 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.
　上記熱塩基発生剤は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。２種以上の熱塩基発生剤を組み合わせて用いる場合、その組み合わせ態様は、硬化性組成物に要求される物性等、例えば基材との密着性等に応じて適宜設定することができる。また、後述する光塩基発生剤と組み合わせて用いてもよい。 The thermal base generator may be used alone or in combination of two or more. When two or more thermal base generators are used in combination, the combination mode can be appropriately set according to physical properties required for the curable composition, for example, adhesion to the substrate. Moreover, you may use in combination with the photobase generator mentioned later.
　本発明の硬化性組成物における熱塩基発生剤の含有量は、硬化性組成物中の全固形分に対して、０．１～１５質量％が好ましく、１～１０質量％がより好ましく、２～７質量％がさらに好ましい。なお、２種以上の塩基発生剤を組み合わせて用いる場合、それぞれの含有量の合計が、上記範囲内であることが好ましい。 The content of the thermal base 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. More preferably, it is 7% by mass. In addition, when using in combination of 2 or more types of base generators, it is preferable that the sum total of each content exists in the said range.
＜光塩基発生剤＞
　本発明の硬化性組成物はより優れた本発明の効果を有する点で、光塩基発生剤を含有することが好ましい。光塩基発生剤としては特に限定されず、その具体例としては、例えば、特開２０１５－０８７６１２号公報の段落０２０７～０２３８、特開２００８－２４７７４７号公報の段落００２６～００３９、および、国際公開第２０１０／０６４６３１号の段落０００９～００５２の記載を参酌することができ、この内容は本願明細書に組み込まれる。また、国際公開第２００９／１２２６６４号の段落００１８～０１０５の記載、特許第５２２３６３３号の段落００２５～００７２の記載を参酌することができ、この内容は本願明細書に組み込まれる。また、特開２０１５－２８５４０号公報の段落００５３～００７０の記載にあるイオン性光塩基発生剤であってもよく、この内容は本願明細書に組み込まれる。 <Photobase generator>
The curable composition of the present invention preferably contains a photobase generator from the viewpoint of having more excellent effects of the present invention. The photobase generator is not particularly limited, and specific examples thereof include, for example, paragraphs 0207 to 0238 of JP-A-2015-087612, paragraphs 0026 to 0039 of JP-A-2008-247747, and International Publication No. The description of paragraphs 0009 to 0052 of 2010/064631 can be referred to, the contents of which are incorporated herein. In addition, 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, it may be an ionic photobase generator described in paragraphs 0053 to 0070 of JP-A-2015-28540, the contents of which are incorporated herein.
　光塩基発生剤としては、硬化膜が優れた低反射性を有する点で、光でアミンを放出する化合物が好ましい。例えば、特開２０１３－８０２０６号記載の光塩基発生剤が好ましく、この内容は本願明細書に組み込まれる。 As the photobase generator, a compound that releases an amine by light is preferable in that the cured film has excellent low reflectivity. For example, a photobase generator described in JP2013-80206 is preferable, and the contents thereof are incorporated in the present specification.
　光塩基発生剤の市販品としては、特に限定されないが、和光純薬工業（株）のＷＰＢＧシリーズ「ＷＰＢＧ－０８２」、「ＷＰＢＧ－１６７」、「ＷＰＢＧ－１６８」、「ＷＰＢＧ－０１８」、「ＷＰＢＧ－０２７」、「ＷＰＢＧ－１４０」等を使用することもできる。硬化膜が優れた低反射性を有する点で、「ＷＰＢＧ－０１８」「ＷＰＢＧ－０２７」を好ましく用いることができる。 A commercial product of the photobase generator is not particularly limited. However, WPBG series “WPBG-082”, “WPBG-167”, “WPBG-168”, “WPBG-018”, “WPBG-018”, “Wako Pure Chemical Industries, Ltd.” WPBG-027 "," WPBG-140 ", etc. can also be used. “WPBG-018” and “WPBG-027” can be preferably used in that the cured film has excellent low reflectivity.
　光塩基発生剤としては、硬化膜が優れた低反射性を有する点で、下記一般式（ＰＢＧ）で表される光塩基発生剤が好ましい。 As the photobase generator, a photobase generator represented by the following general formula (PBG) is preferable in that the cured film has excellent low reflectivity.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記一般式（ＰＥＧ）中、ＲａおよびＲｂはそれぞれ独立に水素原子または１価の有機基を表し、硬化膜がより優れた低反射性を有する点で、芳香族炭化水素基、脂肪族炭化水素基、または、これらの組み合わせであることが好ましく、例えば、アルキル基およびアリール基などが挙げられる。中でも、硬化膜がより優れた低反射性を有する点で、ＲａおよびＲｂは、アルキル基が好ましく、炭素数１～９の直鎖状または分岐鎖状のアルキル基がより好ましく、炭素数１～４の直鎖状または分岐鎖状のアルキル基がさらに好ましく、メチル基、エチル基、イソプロピル基がとくに好ましく、メチル基がもっとも好ましい。
　また、ＲａおよびＲｂは互いに結合して環を形成してもよい。ＲａおよびＲｂが互いに結合して形成される環状アミノ基としては、たとえば、１－アジリジニル基、１－アゼチジニル基、１－ピロリジニル基、１－ピペリジニル基、１－ヘキサメチレンイミノ基、１－ヘプタメチレンイミノ基、１－オクタメチレンイミノ基、１－ノナメチレンイミノ基、１－１－イミダゾリル基、４，５－ジヒドロ－１－イミダゾリル基、１－ピロリル基、１－ピラゾリル基、１－イミダゾリジニル基、１－ピペラジニル基、および、モルホリノ基などが挙げられる。なかでも、硬化膜がより優れた低反射性を有する点で、不飽和結合を有さない炭素数２～９の環状アミノ基が好ましく、１－アジリジニル基、１－アゼチジニル基、１－ピロリジニル基、または、１－ピペリジニル基がより好ましく、１－ピロリジニル基がさらに好ましい。 In the general formula (PEG), R a and R b each independently represent a hydrogen atom or a monovalent organic group, and an aromatic hydrocarbon group or aliphatic group in that the cured film has more excellent 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, R a and R b are preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 9 carbon atoms, and more preferably a carbon number, in that the cured film has more excellent low reflectivity. 1-4 linear or branched alkyl groups are more preferred, methyl group, ethyl group and isopropyl group are particularly preferred, and methyl group is most preferred.
R a and R b may be bonded to each other to form a ring. Examples of the cyclic amino group formed by combining R a and R b with each other include, for example, 1-aziridinyl group, 1-azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group, 1- Heptamethyleneimino group, 1-octamethyleneimino group, 1-nonamethyleneimino group, 1-1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolidinyl Group, 1-piperazinyl group, morpholino group and the like. Of these, a cyclic amino group having 2 to 9 carbon atoms that does not have an unsaturated bond is preferable in that the cured film has excellent low reflectivity, and includes a 1-aziridinyl group, 1-azetidinyl group, and 1-pyrrolidinyl group. Alternatively, a 1-piperidinyl group is more preferable, and a 1-pyrrolidinyl group is more preferable.
　上記一般式（ＰＢＧ）中、Ａｒａはアリール基またはヘテロアリール基を表す。アリール基およびヘテロアリール基はさらに１価の有機基を置換基として有していてもよい。なかでも、硬化膜がより優れた低反射性を有する点で、Ａｒａは縮環構造を有するアリール基またはヘテロアリール基であることが好ましい。硬化膜がさらに優れた低反射性を有する点で、Ａｒａの縮環数は２～５が好ましく、３～４がより好ましい。このとき、縮環にはヘテロ環を含んでもよく、各縮環は、置換基として１価の有機基を１つ以上有していてもよい。また、上述の縮環構造はπ共役系であることがさらに好ましい。縮環構造がπ共役系である場合、３５０ｎｍ～５００ｎｍの波長領域に極大吸収波長を有し、光ラジカル重合開始剤と競合的に反応するため、優れた低反射性を有する硬化膜が得られやすい。好ましいＡｒａの具体的態様としては、以下の一般式（ＣＲ１）～（ＣＲ５）が挙げられ、硬化膜がより優れた低反射性を有する点で、一般式（ＣＲ１）～（ＣＲ４）がより好ましく、一般式（ＣＲ１）～（ＣＲ３）がさらに好ましい。なお、式中＊は結合位置を示し、各環は置換基として１価の有機基を１つ以上有していてもよい。 In the general formula (PBG), Ar a represents an aryl group or a heteroaryl group. The aryl group and heteroaryl group may further have a monovalent organic group as a substituent. Among these, 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. Cured film in that it has a more excellent low reflectivity is, the number of condensed rings in Ar a is preferably 2-5, 3-4 is more preferable. At this time, the condensed ring may include a heterocycle, and each condensed ring may have one or more monovalent organic groups as a substituent. The condensed ring structure described above is more preferably 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 examples 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. The general formulas (CR1) to (CR3) are more preferable. In the formula, * represents a bonding position, and each ring may have one or more monovalent organic groups as a substituent.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記光塩基発生剤に上述の所定の波長の光が照射されると、光塩基発生剤が分解し、塩基が生じる。発生する塩基は、より優れた低反射性を有する硬化膜を作製することができる点で、アミン化合物であることが好ましい。アミン化合物としては、第１級アミン、第２級アミン、および、第３級アミンが挙げられ、第１級アミン、または、第２アミンであることが好ましい。
　なお、光塩基発生剤として一般式（ＰＢＧ）で表される光塩基発生剤を用いた場合、下記一般式（ＢＡ）で表される第１級アミンまたは第２級アミンが塩基として発生する。この光塩基発生剤から発生する塩基の分子量は、硬化膜がより優れた低反射性を有する点で、１５０以下であることが好ましく、１００以下であることがより好ましく、７０以下であることがさらに好ましい。このメカニズムは定かではないが、分子量が低く、拡散し易い塩基が発生し、塗膜中を拡散することで、上側領域と下側領域で重合性化合物の重合反応の速度および／または進行度合いに差が生じる。そのため、上側領域と下側領域で硬化収縮により生じる応力が異なるため、上側領域に微細なシワが発生し、これが硬化膜の低反射性に寄与しているものと推測される。
　なお、本明細書において、塩基の分子量とは、構造式から算出できる分子量を意味する。 When the photobase generator is irradiated with light having the 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. As an amine compound, a primary amine, a secondary amine, and a tertiary amine are mentioned, It is preferable that it is a primary amine or a secondary amine.
When the 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 the 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. Further preferred. Although this mechanism is not clear, a base having a low molecular weight and easy to diffuse is generated and diffuses in the coating film, so that the rate and / or progress of the polymerization reaction of the polymerizable compound in the upper region and the lower region can be increased. There is a difference. For this reason, since the stress generated by the curing shrinkage is different between the upper region and the lower region, fine wrinkles are generated in the upper region, which is presumed to contribute to the low reflectivity of the cured film.
In the present specification, the molecular weight of the base means a molecular weight that can be calculated from the structural formula.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記一般式（ＢＡ）中、ＲａおよびＲｂは一般式（ＰＢＧ）中の定義と同様である。 In the general formula (BA), R a and R b are the same as defined in the general formula (PBG).
　光塩基発生剤は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　２種以上の光塩基発生剤を組み合わせて用いる場合、その組み合わせ態様は、硬化性組成物に要求される物性等、例えば基材との密着性等に応じて適宜設定することができる。
　本発明の硬化性組成物における光塩基発生剤の含有量は、硬化性組成物中の全固形分に対して、０．１～１５質量％が好ましく、１～１０質量％がより好ましく、２～７質量％がさらに好ましい。なお、２種以上の光塩基発生剤を組み合わせて用いる場合、それぞれの含有量の合計が、上記範囲内であることが好ましい。 A photobase generator may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more kinds of photobase generators are used in combination, the combination mode can be appropriately set according to physical properties required for the curable composition, for example, 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. More preferably, it is 7% by mass. In addition, when using combining 2 or more types of photobase generators, it is preferable that the sum total of each content exists in the said range.
　光塩基発生剤の含有量は、後述する分散剤の含有量との関係で、分散剤に対する光塩基発生剤の質量比（光塩基発生剤の質量／分散剤の質量）が０．０５～０．７である場合が多く、硬化膜がより優れた低反射性を有する点で、０．０８～０．５であることが好ましい。 The content of the photobase generator is related to the content of the dispersant described later, and the mass ratio of the photobase generator to the dispersant (the mass of the photobase generator / the mass of the dispersant) is 0.05 to 0. .7 in many cases, and 0.08 to 0.5 is preferable in that the cured film has more excellent low reflectivity.
〔分散剤〕
　本発明の硬化性組成物は、分散剤を含有する。分散剤は着色剤、および、光塩基発生剤（以下、「被分散体」という。）の分散性向上に寄与する。 [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 “to-be-dispersed”).
　分散剤としては、例えば、公知の顔料分散剤を適宜選択して用いることができる。なかでも、高分子化合物が好ましい。
　分散剤としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、および、顔料誘導体等を挙げることができる。
　高分子化合物は、その構造からさらに直鎖状高分子、末端変性型高分子、グラフト型高分子、およびブロック型高分子に分類することができる。 As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
　高分子化合物は、被分散体および所望により併用する体質顔料等との相互作用性を有する。そのため、高分子化合物は、被分散体の表面に吸着し、再凝集を防止するように作用する。そのため、着色剤表面へのアンカー部位を有する末端変性型高分子、グラフト型高分子、および、ブロック型高分子が好ましい構造として挙げることができる。着色剤表面へのアンカー部位は、酸基または水酸基が好ましく、酸基がより好ましく、着色剤の分散安定性が良好で、現像が良好でパターン形成性に優れる観点から、カルボキシル基が特に好ましい。
　一方で、チタンブラックや、上記したチタンブラックおよびＳｉ原子を含む被分散体の表面を改質することにより、これらに対する高分子化合物の吸着性を促進させることもできる。 The polymer compound has an interaction property with the object to be dispersed and, if desired, an extender used together. Therefore, the high molecular compound is adsorbed on the surface of the dispersion and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the colorant surface can be cited as preferred structures. The anchor site to the surface of the colorant is preferably an acid group or a hydroxyl group, more preferably an acid group, and a carboxyl group is particularly preferred from the viewpoint of good dispersion stability of the colorant, good development, and excellent pattern formability.
On the other hand, by adsorbing the surface of titanium black or the above-described dispersion to be dispersed containing titanium black and Si atoms, the adsorptivity of the polymer compound to these can be promoted.
　高分子化合物は、グラフト鎖を有する構造単位を有することが好ましい。なお、本明細書において、「構造単位」とは「繰り返し単位」と同義である。
　このようなグラフト鎖を有する構造単位を有する高分子化合物は、グラフト鎖によって溶剤との親和性を有するために、被分散体の分散性、および、経時後の分散安定性に優れるものである。また、硬化性組成物においては、グラフト鎖の存在により重合性化合物またはその他の併用可能な樹脂などとの親和性を有するので、アルカリ現像で残渣を生じにくくなる。
　グラフト鎖が長くなると立体反発効果が高くなり分散性は向上するが、一方グラフト鎖が長すぎると被分散体への吸着力が低下して分散性は低下する傾向となる。このため、グラフト鎖は、水素原子を除いた原子数が４０～１００００の範囲であるものが好ましく、水素原子を除いた原子数が５０～２０００であるものがより好ましく、水素原子を除いた原子数が６０～５００であるものがさらに好ましい。
　ここで、グラフト鎖とは、共重合体の主鎖の根元（主鎖から枝分かれしている基において主鎖に結合する原子）から、主鎖から枝分かれしている基の末端までを示す。 The polymer compound preferably has a structural unit having a graft chain. In this specification, “structural unit” is synonymous with “repeating unit”.
Such a polymer compound having a structural unit having a graft chain has an affinity for a solvent due to the graft chain, and thus has excellent dispersibility of the dispersion and dispersion stability after aging. In addition, since the curable composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved. On the other hand, when the graft chain is too long, the adsorptive power to the dispersion is lowered and the dispersibility tends to be lowered. Therefore, the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
　グラフト鎖は、ポリマー構造を有することが好ましく、このようなポリマー構造としては、例えば、ポリアクリレート構造（例えば、ポリ（メタ）アクリル構造）、ポリエステル構造、ポリウレタン構造、ポリウレア構造、ポリアミド構造、および、ポリエーテル構造などを挙げることができる。
　グラフト鎖と溶剤との相互作用性を向上させ、それにより着色剤の分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造およびポリアクリレート構造からなる群から選ばれた少なくとも１種を有するグラフト鎖であることが好ましく、ポリエステル構造およびポリエーテル構造の少なくともいずれかを有するグラフト鎖であることがより好ましい。 The graft chain preferably has a polymer structure, and examples of such a polymer structure include a polyacrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and Examples thereof include a polyether structure.
In order to improve the interaction between the graft chain and the solvent and thereby increase the dispersibility of the colorant, the graft chain is made of at least one selected from the group consisting of a polyester structure, a polyether structure and a polyacrylate structure. The graft chain is preferably a graft chain, and more preferably a graft chain having at least one of a polyester structure and a polyether structure.
　このようなポリマー構造をグラフト鎖として有するマクロモノマーとしては、特に限定されないが、好ましくは、反応性二重結合性基を有するマクロモノマーを好適に使用することができる。 The macromonomer having such a polymer structure as a graft chain is not particularly limited, but a macromonomer having a reactive double bond group can be preferably used.
　高分子化合物が有するグラフト鎖を有する構造単位に対応し、高分子化合物の合成に好適に用いられる市販のマクロモノマーとしては、ＡＡ－６（商品名、東亜合成（株））、ＡＡ－１０（商品名、東亜合成（株）製）、ＡＢ－６（商品名、東亜合成（株）製）、ＡＳ－６（商品名、東亜合成（株））、ＡＮ－６（商品名、東亜合成（株）製）、ＡＷ－６（商品名、東亜合成（株）製）、ＡＡ－７１４（商品名、東亜合成（株）製）、ＡＹ－７０７（商品名、東亜合成（株）製）、ＡＹ－７１４（商品名、東亜合成（株）製）、ＡＫ－５（商品名、東亜合成（株）製）、ＡＫ－３０（商品名、東亜合成（株）製）、ＡＫ－３２（商品名、東亜合成（株）製）、ブレンマーＰＰ－１００（商品名、日油（株）製）、ブレンマーＰＰ－５００（商品名、日油（株）製）、ブレンマーＰＰ－８００（商品名、日油（株）製）、ブレンマーＰＰ－１０００（商品名、日油（株）製）、ブレンマー５５－ＰＥＴ－８００（商品名、日油（株）製）、ブレンマーＰＭＥ－４０００（商品名、日油（株）製）、ブレンマーＰＳＥ－４００（商品名、日油（株）製）、ブレンマーＰＳＥ－１３００（商品名、日油（株）製）、および、ブレンマー４３ＰＡＰＥ－６００Ｂ（商品名、日油（株）製）などが用いられる。このなかでも、好ましくは、ＡＡ－６（商品名、東亜合成（株）製）、ＡＡ－１０（商品名、東亜合成（株））、ＡＢ－６（商品名、東亜合成（株）製）、ＡＳ－６（商品名、東亜合成（株））、ＡＮ－６（商品名、東亜合成（株）製）、および、ブレンマーＰＭＥ－４０００（商品名、日油（株）製）などが用いられる。 Corresponding to the structural unit having a graft chain of the polymer compound, commercially available macromonomers suitably used for the synthesis of the polymer compound include AA-6 (trade name, Toa Gosei Co., Ltd.), AA-10 ( Product name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.) Co., Ltd.), AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (product) Name, manufactured by Toa Gosei Co., Ltd.), Blemmer PP-100 (trade name, manufactured by NOF Corporation), Blemmer PP-500 ( Product name, NOF Corporation), BLEMMER PP-800 (trade name, NOF Corporation), BLEMMER PP-1000 (trade name, NOF Corporation), BLEMMER 55-PET-800 (product) Name, manufactured by NOF Corporation), BREMMER PME-4000 (trade name, manufactured by NOF Corporation), BREMMER PSE-400 (trade name, manufactured by NOF Corporation), Blemmer PSE-1300 (trade name, NOF Corporation) and BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corporation) are used. Of these, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PME-4000 (trade name, manufactured by NOF Corporation), etc. It is done.
　高分子化合物は、グラフト鎖を有する構造単位として、下記一般式（１）～一般式（４）のいずれかで表される構造単位を含むことが好ましく、下記一般式（１Ａ）、下記一般式（２Ａ）、一般式（３Ａ）、一般式（３Ｂ）、および一般式（４）のいずれかで表される構造単位を含むことがより好ましい。 The polymer compound preferably includes a structural unit represented by any one of the following general formulas (1) to (4) as a structural unit having a graft chain. It is more preferable that the structural unit represented by any one of (2A), general formula (3A), general formula (3B), and general formula (4) is included.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記一般式（１）～一般式（４）において、Ｗ１、Ｗ２、Ｗ３、およびＷ４はそれぞれ独立に酸素原子またはＮＨを表す。Ｗ１、Ｗ２、Ｗ３、およびＷ４は酸素原子であることが好ましい。
　一般式（１）～一般式（４）において、Ｘ１、Ｘ２、Ｘ３、Ｘ４、およびＸ５は、それぞれ独立に、水素原子または１価の有機基を表す。Ｘ１、Ｘ２、Ｘ３、Ｘ４、およびＸ５としては、合成上の制約の観点からは、それぞれ独立に、水素原子または炭素数１～１２のアルキル基であることが好ましく、それぞれ独立に、水素原子またはメチル基であることがより好ましく、メチル基がさらに好ましい。 In the general formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH. W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
In the 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. X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, from the viewpoint of synthesis constraints. In addition, a hydrogen atom or a methyl group is more preferable, and a methyl group is more preferable.
　一般式（１）～一般式（４）において、Ｙ１、Ｙ２、Ｙ３、およびＹ４は、それぞれ独立に、２価の連結基を表し、連結基は特に構造上制約されない。Ｙ１、Ｙ２、Ｙ３、およびＹ４で表される２価の連結基として、具体的には、下記の（Ｙ－１）～（Ｙ－２１）の連結基などが例として挙げられる。下記に示した構造において、Ａ、Ｂはそれぞれ、一般式（１）～一般式（４）における左末端基、右末端基との結合位置を意味する。下記に示した構造のうち、合成の簡便性から、(Ｙ－２)または（Ｙ－１３）であることがより好ましい。 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 limited in structure. Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups. . In the structures shown below, A and B mean the bonding positions with the left end group and the right end group in the general formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　一般式（１）～一般式（４）において、Ｚ１、Ｚ２、Ｚ３、およびＺ４は、それぞれ独立に１価の有機基を表す。有機基は、特に限定されないが、具体的には、アルキル基、水酸基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、およびアミノ基などが挙げられる。これらの中でも、Ｚ１、Ｚ２、Ｚ３、およびＺ４で表される有機基としては、特に分散性向上の観点から、立体反発効果を有するものが好ましく、各々独立に炭素数５から２４のアルキル基またはアルコキシ基が好ましく、その中でも、特に各々独立に炭素数５から２４の分岐アルキル基、炭素数５から２４の環状アルキル基、または、炭素数５から２４のアルコキシ基が好ましい。なお、アルコキシ基中に含まれるアルキル基は、直鎖状、分岐鎖状、環状のいずれでもよい。 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 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. It is 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 particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. 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 is particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.
　一般式（１）～一般式（４）において、ｎ、ｍ、ｐ、およびｑは、それぞれ独立に、１から５００の整数である。
　また、一般式（１）および一般式（２）において、ｊおよびｋは、それぞれ独立に、２～８の整数を表す。一般式（１）および一般式（２）におけるｊおよびｋは、分散安定性および現像性の観点から、４～６の整数が好ましく、５がもっとも好ましい。 In the general formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.
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 formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
　一般式（３）中、Ｒ３は分岐若しくは直鎖のアルキレン基を表し、炭素数１～１０のアルキレン基が好ましく、炭素数２または３のアルキレン基がより好ましい。ｐが２～５００のとき、複数存在するＲ３は互いに同じであっても異なっていてもよい。
　一般式（４）中、Ｒ４は水素原子または１価の有機基を表し、この１価の有機基としては特に構造上限定はされない。Ｒ４として好ましくは、水素原子、アルキル基、アリール基、およびヘテロアリール基が挙げられ、より好ましくは、水素原子、またはアルキル基である。Ｒ４がアルキル基である場合、アルキル基としては、炭素数１～２０の直鎖状アルキル基、炭素数３～２０の分岐状アルキル基、または炭素数５～２０の環状アルキル基が好ましく、炭素数１～２０の直鎖状アルキル基がより好ましく、炭素数１～６の直鎖状アルキル基がさらに好ましい。一般式（４）において、ｑが２～５００のとき、グラフト共重合体中に複数存在するＸ５およびＲ４は互いに同じであっても異なっていてもよい。 In general formula (3), R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
In the general formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R 4 is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, 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 more 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.
　また、高分子化合物は、２種以上の構造が異なる、グラフト鎖を有する構造単位を有することができる。即ち、高分子化合物の分子中に、互いに構造の異なる一般式（１）～一般式（４）で示される構造単位を含んでいてもよい。また、一般式（１）～一般式（４）においてｎ、ｍ、ｐ、およびｑがそれぞれ２以上の整数を表す場合、一般式（１）および一般式（２）においては、側鎖中にｊおよびｋが互いに異なる構造を含んでいてもよい。一般式（３）および一般式（４）においては、分子内に複数存在するＲ３、Ｒ４およびＸ５は互いに同じであっても異なっていてもよい。 In addition, the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, in the molecule of the polymer compound, structural units represented by the general formulas (1) to (4) having different structures may be included. In the general formulas (1) to (4), when n, m, p, and q each represent an integer of 2 or more, in the general formula (1) and the general formula (2), j and k may include different structures. In the general formula (3) and the general formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
　一般式（１）で表される構造単位としては、分散安定性および現像性の観点から、下記一般式（１Ａ）で表される構造単位であることがより好ましい。
　また、一般式（２）で表される構造単位としては、分散安定性および現像性の観点から、下記一般式（２Ａ）で表される構造単位であることがより好ましい。 The structural unit represented by the general formula (1) is more preferably a 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 a structural unit represented by the following general formula (2A) from the viewpoint of dispersion stability and developability.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　一般式（１Ａ）中、Ｘ１、Ｙ１、Ｚ１およびｎは、一般式（１）におけるＸ１、Ｙ１、Ｚ１およびｎと同義であり、好ましい範囲も同様である。一般式（２Ａ）中、Ｘ２、Ｙ２、Ｚ２およびｍは、一般式（２）におけるＸ２、Ｙ２、Ｚ２およびｍと同義であり、好ましい範囲も同様である。 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.
　また、一般式（３）で表される構造単位としては、分散安定性および現像性の観点から、下記一般式（３Ａ）または一般式（３Ｂ）で表される構造単位であることがより好ましい。 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. .
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　一般式（３Ａ）または（３Ｂ）中、Ｘ３、Ｙ３、Ｚ３およびｐは、一般式（３）におけるＸ３、Ｙ３、Ｚ３およびｐと同義であり、好ましい範囲も同様である。 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 .
　高分子化合物は、グラフト鎖を有する構造単位として、一般式（１Ａ）で表される構造単位を有することがより好ましい。 The polymer compound preferably has a structural unit represented by the general formula (1A) as a structural unit having a graft chain.
　高分子化合物において、グラフト鎖を有する構造単位（例えば、上記一般式（１）～一般式（４）で表される構造単位）は、質量換算で、高分子化合物の総質量に対し２～９０％の範囲で含まれることが好ましく、５～３０％の範囲で含まれることがより好ましい。グラフト鎖を有する構造単位が、この範囲内で含まれると被分散体（特に、チタンブラック粒子）の分散性が高く、遮光膜を形成する際の現像性が良好である。 In the polymer compound, the structural unit having a graft chain (for example, the structural unit represented by the general formula (1) to the general formula (4)) is 2 to 90 relative to the total mass of the polymer compound in terms of mass. % Is preferably included, and more preferably in the range of 5 to 30%. When the structural unit having a graft chain is contained within this range, the dispersoid (particularly, titanium black particles) has high dispersibility and good developability when a light-shielding film is formed.
　また、高分子化合物は、グラフト鎖を有する構造単位とは異なる（すなわち、グラフト鎖を有する構造単位には相当しない）疎水性構造単位を有することが好ましい。ただし、本発明において、疎水性構造単位は、酸基（例えば、カルボキシル基、スルホン酸基、リン酸基、フェノール性水酸基等）を有さない構造単位である。 Further, the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding 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, carboxyl group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).
　疎水性構造単位は、好ましくは、ＣｌｏｇＰ値が１．２以上の化合物（モノマー）に由来する（対応する）構造単位であり、より好ましくは、ＣｌｏｇＰ値が１．２～８の化合物に由来する構造単位である。これにより、本発明の効果をより確実に発現することができる。 The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
　ＣｌｏｇＰ値は、Ｄａｙｌｉｇｈｔ　Ｃｈｅｍｉｃａｌ　Ｉｎｆｏｒｍａｔｉｏｎ　Ｓｙｓｔｅｍ，　Ｉｎｃ．から入手できるプログラム“ＣＬＯＧＰ”で計算された値である。このプログラムは、Ｈａｎｓｃｈ，　Ｌｅｏのフラグメントアプローチ（下記文献参照）により算出される“計算ｌｏｇＰ”の値を提供する。フラグメントアプローチは化合物の化学構造に基づいており、化学構造を部分構造（フラグメント）に分割し、そのフラグメントに対して割り当てられたｌｏｇＰ寄与分を合計することにより化合物のｌｏｇＰ値を推算している。その詳細は以下の文献に記載されている。本発明では、プログラムＣＬＯＧＰ　ｖ４．８２により計算したＣｌｏｇＰ値を用いる。
　Ａ．　Ｊ．　Ｌｅｏ，　Ｃｏｍｐｒｅｈｅｎｓｉｖｅ　Ｍｅｄｉｃｉｎａｌ　Ｃｈｅｍｉｓｔｒｙ，　Ｖｏｌ．４，　Ｃ．　Ｈａｎｓｃｈ，　Ｐ．　Ｇ．　Ｓａｍｍｎｅｎｓ，　Ｊ．　Ｂ．　Ｔａｙｌｏｒ　ａｎｄ　Ｃ．　Ａ．　Ｒａｍｓｄｅｎ，　Ｅｄｓ．，　ｐ．２９５，　Ｐｅｒｇａｍｏｎ　Ｐｒｅｓｓ，　１９９０　Ｃ．　Ｈａｎｓｃｈ　＆　Ａ．　Ｊ．　Ｌｅｏ．　ＳＵｂｓｔｉｔｕｅｎｔ　Ｃｏｎｓｔａｎｔｓ　Ｆｏｒ　Ｃｏｒｒｅｌａｔｉｏｎ　Ａｎａｌｙｓｉｓ　ｉｎ　Ｃｈｅｍｉｓｔｒｙ　ａｎｄ　Ｂｉｏｌｏｇｙ．　Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ．　Ａ．Ｊ．　Ｌｅｏ．　Ｃａｌｃｕｌａｔｉｎｇ　ｌｏｇＰｏｃｔ　ｆｒｏｍ　ｓｔｒｕｃｔｕｒｅ．　Ｃｈｅｍ．　Ｒｅｖ．，　９３，　１２８１－１３０６，　１９９３． ClogP values are available from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.
　ｌｏｇＰは、分配係数Ｐ（Ｐａｒｔｉｔｉｏｎ　Ｃｏｅｆｆｉｃｉｅｎｔ）の常用対数を意味し、ある有機化合物が油（一般的には１－オクタノール）と水の２相系の平衡でどのように分配されるかを定量的な数値として表す物性値であり、以下の式で示される。
　　ｌｏｇＰ＝ｌｏｇ（Ｃｏｉｌ／Ｃｗａｔｅｒ）
　式中、Ｃｏｉｌは油相中の化合物のモル濃度を、Ｃｗａｔｅｒは水相中の化合物のモル濃度を表す。
　ｌｏｇＰの値が０をはさんでプラスに大きくなると油溶性が増し、マイナスで絶対値が大きくなると水溶性が増すことを意味し、有機化合物の水溶性と負の相関があり、有機化合物の親疎水性を見積るパラメータとして広く利用されている。 log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines 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 represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.
　高分子化合物は、疎水性構造単位として、下記一般式（ｉ）～一般式（ｉｉｉ）で表される単量体に由来の構造単位から選択された１種以上の構造単位を有することが好ましい。 The polymer compound preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units. .
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記一般式（ｉ）～一般式（ｉｉｉ）中、Ｒ１、Ｒ２、およびＲ３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素、塩素、臭素等）、または炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）を表す。
　Ｒ１、Ｒ２、およびＲ３は、好ましくは水素原子、または炭素数が１～３のアルキル基であり、より好ましくは、水素原子またはメチル基である。Ｒ２およびＲ３は、水素原子であることがさらに好ましい。
　Ｘは、酸素原子（－Ｏ－）またはイミノ基（－ＮＨ－）を表し、酸素原子であることが好ましい。 In the above general formulas (i) to (iii), R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or a carbon number of 1 Represents an alkyl group of ˜6 (for example, methyl group, ethyl group, propyl group, etc.).
R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R 2 and R 3 are more preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
　Ｌは、単結合または２価の連結基である。２価の連結基としては、２価の脂肪族基（例えば、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、および、置換アルキニレン基）、２価の芳香族基（例えば、アリーレン基、置換アリーレン基）、２価の複素環基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ基（－ＮＲ３１－、ここでＲ３１は脂肪族基、芳香族基または複素環基）、カルボニル基（－ＣＯ－）、および、これらの組合せ等が挙げられる。 L is a single bond or a divalent linking group. As the divalent linking group, 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), a divalent aromatic group (for example, Arylene group, substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.
　２価の脂肪族基は、環状構造または分岐構造を有していてもよい。脂肪族基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０がさらに好ましい。脂肪族基は不飽和脂肪族基であっても飽和脂肪族基であってもよいが、飽和脂肪族基であることが好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基および複素環基等が挙げられる。 The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
　２価の芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０がさらに好ましい。また、芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基および複素環基等が挙げられる。 The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
　２価の複素環基は、複素環として５員環または６員環を有することが好ましい。複素環に他の複素環、脂肪族環または芳香族環が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシル基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基または複素環基）、脂肪族基、芳香族基、および、複素環基が挙げられる。 The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. The heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 represents a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group.
　Ｌは、単結合、アルキレン基またはオキシアルキレン構造を含む２価の連結基であることが好ましい。オキシアルキレン構造は、オキシエチレン構造またはオキシプロピレン構造であることがより好ましい。また、Ｌは、オキシアルキレン構造を２以上繰り返して含むポリオキシアルキレン構造を含んでいてもよい。ポリオキシアルキレン構造としては、ポリオキシエチレン構造またはポリオキシプロピレン構造が好ましい。ポリオキシエチレン構造は、－（ＯＣＨ２ＣＨ２）ｎ－で表され、ｎは、２以上の整数が好ましく、２～１０の整数であることがより好ましい。 L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
　Ｚとしては、脂肪族基（例えば、アルキル基、置換アルキル基、不飽和アルキル基、および、置換不飽和アルキル基、）、芳香族基（例えば、アリーレン基、置換アリーレン基）、複素環基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ基（－ＮＲ３１－、ここでＲ３１は脂肪族基、芳香族基または複素環基）、カルボニル基（－ＣＯ－）、および、これらの組合せ等が挙げられる。 Z includes 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, a substituted arylene group), a heterocyclic group, Oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 is an aliphatic group, aromatic group or heterocyclic group) , A carbonyl group (—CO—), and combinations thereof.
　脂肪族基は、環状構造または分岐構造を有していてもよい。脂肪族基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０がさらに好ましい。脂肪族基には、さらに環集合炭化水素基および架橋環式炭化水素基が含まれ、環集合炭化水素基の例としては、ビシクロヘキシル基、パーヒドロナフタレニル基、ビフェニル基、および、４－シクロヘキシルフェニル基などが含まれる。架橋環式炭化水素環として、例えば、ピナン、ボルナン、ノルピナン、ノルボルナン、ビシクロオクタン環（ビシクロ［２．２．２］オクタン環、および、ビシクロ［３．２．１］オクタン環等）などの２環式炭化水素環、ホモブレダン、アダマンタン、トリシクロ［５．２．１．０２，６］デカン、および、トリシクロ［４．３．１．１２，５］ウンデカン環などの３環式炭化水素環、テトラシクロ［４．４．０．１２，５．１７，１０］ドデカン、および、パーヒドロ－１，４－メタノ－５，８－メタノナフタレン環などの４環式炭化水素環などが挙げられる。また、架橋環式炭化水素環には、縮合環式炭化水素環、例えば、パーヒドロナフタレン（デカリン）、パーヒドロアントラセン、パーヒドロフェナントレン、パーヒドロアセナフテン、パーヒドロフルオレン、パーヒドロインデン、および、パーヒドロフェナレン環などの５～８員シクロアルカン環が複数個縮合した縮合環も含まれる。
　脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基および複素環基が挙げられる。ただし、脂肪族基は、置換基として酸基を有さない。 The aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included. Examples of the bridged cyclic hydrocarbon ring include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring and bicyclo [3.2.1] octane ring). Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, 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 . 1 7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
　芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０がさらに好ましい。また、芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基および複素環基が挙げられる。ただし、芳香族基は、置換基として酸基を有さない。 The carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
　複素環基は、複素環として５員環または６員環を有することが好ましい。複素環に他の複素環、脂肪族環または芳香族環が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシル基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基または複素環基）、脂肪族基、芳香族基および複素環基が挙げられる。ただし、複素環基は、置換基として酸基を有さない。 The heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. The heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.
　上記一般式（ｉｉｉ）中、Ｒ４、Ｒ５、およびＲ６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素、塩素、臭素等）、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）、Ｚ、またはＬ－Ｚを表す。ここでＬおよびＺは、上記におけるものと同義である。Ｒ４、Ｒ５、およびＲ６としては、水素原子、または炭素数が１～３のアルキル基が好ましく、水素原子がより好ましい。 In the general formula (iii), R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, , Methyl group, ethyl group, propyl group, etc.), Z, or LZ. Here, L and Z are as defined above. R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　本発明においては、上記一般式（ｉ）で表される単量体として、Ｒ１、Ｒ２、およびＲ３が水素原子またはメチル基であって、Ｌが単結合またはアルキレン基若しくはオキシアルキレン構造を含む２価の連結基であって、Ｘが酸素原子またはイミノ基であって、Ｚが脂肪族基、複素環基または芳香族基である化合物が好ましい。
　また、上記一般式（ｉｉ）で表される単量体として、Ｒ１が水素原子またはメチル基であって、Ｌがアルキレン基であって、Ｚが脂肪族基、複素環基または芳香族基である化合物が好ましい。また、上記一般式（ｉｉｉ）で表される単量体として、Ｒ４、Ｒ５、およびＲ６が水素原子またはメチル基であって、Ｚが脂肪族基、複素環基または芳香族基である化合物が好ましい。 In the present invention, as the monomer represented by the general formula (i), R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, 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.
Further, as the monomer represented by the 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. As the monomer represented by the general formula (iii), R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.
　一般式（ｉ）～一般式（ｉｉｉ）で表される代表的な化合物の例としては、アクリル酸エステル類、メタクリル酸エステル類、および、スチレン類などから選ばれるラジカル重合性化合物が挙げられる。
　なお、一般式（ｉ）～一般式（ｉｉｉ）で表される代表的な化合物の例としては、特開２０１３－２４９４１７号公報の段落００８９～００９３に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。 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 typical compounds represented by the general formula (i) to the general formula (iii), the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are as follows. Incorporated herein.
　高分子化合物において、疎水性構造単位は、質量換算で、高分子化合物の総質量に対し１０～９０％の範囲で含まれることが好ましく、２０～８０％の範囲で含まれることがより好ましい。含有量が上記範囲において十分なパターン形成が得られる。 In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
　高分子化合物は、被分散体（特に、チタンブラック）と相互作用を形成しうる官能基を導入することができる。ここで、高分子化合物は、被分散体と相互作用を形成しうる官能基を有する構造単位をさらに有することが好ましい。
　この被分散体と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、および、反応性を有する官能基等が挙げられる。
　高分子化合物が、酸基、塩基性基、配位性基、または、反応性を有する官能基を有する場合、それぞれ、酸基を有する構造単位、塩基性基を有する構造単位、配位性基を有する構造単位、または、反応性を有する構造単位を有することが好ましい。
　特に、高分子化合物が、さらに、酸基として、カルボキシル基などのアルカリ可溶性基を有することで、高分子化合物に、アルカリ現像によるパターン形成のための現像性を付与することができる。
　すなわち、高分子化合物にアルカリ可溶性基を導入することで、本発明の硬化性組成物は、被分散体の分散に寄与する分散剤としての高分子化合物がアルカリ可溶性を有することになる。このような高分子化合物を含有する硬化性組成物は、露光部の遮光性に優れたものとなり、且つ、未露光部のアルカリ現像性が向上される。
　また、高分子化合物が酸基を有する構造単位を有することにより、高分子化合物が溶剤となじみやすくなり、塗布性も向上する傾向となる。
　これは、酸基を有する構造単位における酸基が被分散体と相互作用しやすく、高分子化合物が被分散体を安定的に分散すると共に、被分散体を分散する高分子化合物の粘度が低くなっており、高分子化合物自体も安定的に分散されやすいためであると推測される。 In the polymer compound, a functional group capable of forming an interaction with a dispersion target (particularly titanium black) can be introduced. Here, the polymer compound preferably 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 object to be dispersed include an acid group, a basic group, a coordination group, and a reactive functional group.
When the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, the structural unit having an acid group, the structural unit having a basic group, or a coordinating group, respectively. It is preferable to have a structural unit having or a reactive structural unit.
In particular, since the polymer compound further has an alkali-soluble group such as a carboxyl group as an acid group, the polymer compound can be provided with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of the dispersion is alkali-soluble in the curable composition of the present invention. The curable composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when a high molecular compound has a structural unit which has an acid group, it becomes easy for a high molecular compound to become compatible with a solvent, and it exists in the tendency for applicability | paintability to improve.
This is because the acid group in the structural unit having an acid group easily interacts with the dispersion, the polymer compound stably disperses the dispersion, and the viscosity of the polymer compound that disperses the dispersion is low. This is presumably because the polymer compound itself is easily dispersed stably.
　ただし、酸基としてのアルカリ可溶性基を有する構造単位は、上記したグラフト鎖を有する構造単位と同一の構造単位であっても、異なる構造単位であってもよいが、酸基としてのアルカリ可溶性基を有する構造単位は、上記した疎水性構造単位とは異なる構造単位である（すなわち、上記した疎水性構造単位には相当しない）。 However, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. Is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
　被分散体と相互作用を形成しうる官能基である酸基としては、例えば、カルボキシル基、スルホン酸基、リン酸基、または、フェノール性水酸基などがあり、好ましくは、カルボキシル基、スルホン酸基、および、リン酸基のうち少なくとも１種であり、より好ましいものは、着色剤への吸着力が良好で、且つ、着色剤の分散性が高い点で、カルボキシル基である。
　すなわち、高分子化合物は、カルボキシル基、スルホン酸基、および、リン酸基のうち少なくとも１種を有する構造単位をさらに有することが好ましい。 Examples of the acid group which is a functional group capable of forming an interaction with the dispersion target include a carboxyl group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably a carboxyl group or a sulfonic acid group. , And at least one of phosphoric acid groups, and more preferable is a carboxyl group in that the adsorbing power to the colorant is good and the dispersibility of the colorant is high.
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.
　高分子化合物は、酸基を有する構造単位を１種または２種以上有してもよい。
　高分子化合物は、酸基を有する構造単位を含有してもしなくてもよいが、含有する場合、酸基を有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは５～８０％であり、より好ましくは、アルカリ現像による画像強度のダメージ抑制という観点から、１０～６０％である。 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. However, 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. Preferably, it is 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
　被分散体と相互作用を形成しうる官能基である塩基性基としては、例えば、第１級アミノ基、第２級アミノ基、第３級アミノ基、Ｎ原子を含むヘテロ環、および、アミド基などがあり、より好ましいものは、着色剤への吸着力が良好で、且つ、着色剤の分散性が高い点で、第３級アミノ基である。高分子化合物は、これらの塩基性基を１種或いは２種以上有することができる。
　高分子化合物は、塩基性基を有する構造単位を含有してもしなくてもよいが、含有する場合、塩基性基を有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは０．０１％以上５０％以下であり、より好ましくは、現像性阻害抑制という観点から、０．０１％以上３０％以下である。 Examples of the basic group that is a functional group capable of forming an interaction with the dispersion target include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide Among them, a tertiary amino group is more preferable because it has a good adsorptive power to the colorant and a 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 calculated by mass conversion to the total mass of the polymer compound. 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 suppression of developability inhibition.
　被分散体と相互作用を形成しうる官能基である配位性基、および反応性を有する官能基としては、例えば、アセチルアセトキシ基、トリアルコキシシリル基、イソシアネート基、酸無水物、酸塩化物などが挙げられる。より好ましいものは、着色剤への吸着力が良好で、着色剤の分散性が高い点で、アセチルアセトキシ基である。高分子化合物は、これらの基を１種または２種以上有してもよい。
　高分子化合物は、配位性基を有する構造単位、または、反応性を有する官能基を有する構造単位を含有してもしなくてもよいが、含有する場合、これらの構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは１０％以上８０％以下であり、より好ましくは、現像性阻害抑制という観点から、２０％以上６０％以下である。 Examples of the coordinating group, which is a functional group capable of forming an interaction with the dispersion, and the reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, acid chloride Etc. More preferred is an acetylacetoxy group in that the adsorbing power to the colorant is good and the dispersibility of the colorant is high. 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: In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of inhibition of developability inhibition with respect to the total mass of the polymer compound.
　本発明における高分子化合物が、グラフト鎖以外に、被分散体と相互作用を形成しうる官能基を有する場合、上述したような、各種の黒色顔料と相互作用を形成しうる官能基を含有していればよい。これらの官能基がどのように導入されているかは特に限定はされないが、高分子化合物は、下記一般式（ｉｖ）～一般式（ｖｉ）で表される単量体に由来の構造単位から選択された１種以上の構造単位を有することが好ましい。 In the case where the polymer compound in the present invention has a functional group capable of forming an interaction with the object 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. It only has to be. Although how these functional groups are introduced is not particularly limited, the polymer compound is selected from structural units derived from monomers represented by the following general formula (iv) to general formula (vi) It is preferable to have one or more structural units.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　一般式（ｉｖ）～一般式（ｖｉ）中、Ｒ１１、Ｒ１２、およびＲ１３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）、または炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）を表す。
　一般式（ｉｖ）～一般式（ｖｉ）中、Ｒ１１、Ｒ１２、およびＲ１３は、より好ましくは、それぞれ独立に水素原子、または炭素数が１～３のアルキル基であり、さらに好ましくは、それぞれ独立に水素原子またはメチル基である。一般式（ｉｖ）中、Ｒ１２およびＲ１３は、それぞれ水素原子であることがとくに好ましい。 In general formula (iv) to general formula (vi), R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
In general formula (iv) to general formula (vi), R 11 , R 12 , and R 13 are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably Each independently represents a hydrogen atom or a methyl group. In general formula (iv), R 12 and R 13 are each particularly preferably a hydrogen atom.
　一般式（ｉｖ）中のＸ１は、酸素原子（－Ｏ－）またはイミノ基（－ＮＨ－）を表し、酸素原子であることが好ましい。
　また、一般式（ｖ）中のＹは、メチン基または窒素原子を表す。 X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (v) represents a methine group or a nitrogen atom.
　また、一般式（ｉｖ）～一般式（ｖ）中のＬ１は、単結合または２価の連結基を表す。２価の連結基の例としては、２価の脂肪族基（例えば、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、および置換アルキニレン基）、２価の芳香族基（例えば、アリーレン基、および置換アリーレン基）、２価の複素環基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ結合（－ＮＲ３１’－、ここでＲ３１’は脂肪族基、芳香族基または複素環基）、カルボニル結合（－ＣＯ－）、および、これらの組合せ等が挙げられる。 In the general formulas (iv) to (v), L 1 represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups, and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ — Here, R 31 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
　２価の脂肪族基は、環状構造または分岐構造を有していてもよい。脂肪族基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０がさらに好ましい。脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシル基、芳香族基および複素環基が挙げられる。 The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
　２価の芳香族基の炭素数は、６～２０が好ましく、６～１５がさらに好ましく、６～１０がもっとも好ましい。また、芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、ヒドロキシル基、脂肪族基、芳香族基および複素環基を挙げられる。 The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
　２価の複素環基は、複素環として５員環または６員環を有することが好ましい。複素環に他の複素環、脂肪族環または芳香族環のうち１つ以上が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基または複素環基）、脂肪族基、芳香族基および複素環基を挙げられる。 The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
　Ｌ１は、単結合、アルキレン基またはオキシアルキレン構造を含む２価の連結基であることが好ましい。オキシアルキレン構造は、オキシエチレン構造またはオキシプロピレン構造であることがより好ましい。また、Ｌは、オキシアルキレン構造を２以上繰り返して含むポリオキシアルキレン構造を含んでいてもよい。ポリオキシアルキレン構造としては、ポリオキシエチレン構造またはポリオキシプロピレン構造が好ましい。ポリオキシエチレン構造は、－（ＯＣＨ２ＣＨ２）ｎ－で表され、ｎは、２以上の整数が好ましく、２～１０の整数であることがより好ましい。 L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
　一般式（ｉｖ）～一般式（ｖｉ）中、Ｚ１は、グラフト鎖以外に着色剤と相互作用を形成しうる官能基を表し、カルボキシル基または第三級アミノ基であることが好ましく、カルボキシル基であることがより好ましい。 In the general formulas (iv) to (vi), Z 1 represents a functional group capable of interacting with the colorant in addition to the graft chain, and is preferably a carboxyl group or a tertiary amino group, More preferably, it is a group.
　一般式（ｖｉ）中、Ｒ１４、Ｒ１５、およびＲ１６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素、塩素、臭素等）、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）、－Ｚ１、またはＬ１－Ｚ１を表す。ここでＬ１およびＺ１は、上記におけるＬ１およびＺ１と同義であり、好ましい例も同様である。Ｒ１４、Ｒ１５、およびＲ１６としては、それぞれ独立に水素原子、または炭素数が１～３のアルキル基が好ましく、水素原子がより好ましい。 In general formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), - represents a Z 1 or L 1 -Z 1,. Wherein L 1 and Z 1 has the same meaning as L 1 and Z 1 in the above, are the preferable examples. R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　本発明においては、一般式（ｉｖ）で表される単量体として、Ｒ１１、Ｒ１２、およびＲ１３がそれぞれ独立に水素原子またはメチル基であって、Ｌ１がアルキレン基またはオキシアルキレン構造を含む２価の連結基であって、Ｘが酸素原子またはイミノ基であって、Ｚがカルボキシル基である化合物が好ましい。
　また、一般式（ｖ）で表される単量体として、Ｒ１１が水素原子またはメチル基であって、Ｌ１がアルキレン基であって、Ｚ１がカルボキシル基であって、Ｙがメチン基である化合物が好ましい。
　さらに、一般式（ｖｉ）で表される単量体として、Ｒ１４、Ｒ１５、およびＲ１６がそれぞれ独立に水素原子またはメチル基であって、Ｌが単結合またはアルキレン基であって、Ｚがカルボキシル基である化合物が好ましい。 In the present invention, as the monomer represented by the general formula (iv), R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure. A compound in which X is an oxygen atom or an imino group and Z is a carboxyl group is preferable.
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. Is preferred.
Furthermore, as the monomer represented by the general formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z A compound in which is a carboxyl group is preferred.
　以下に、一般式（ｉｖ）～一般式（ｖｉ）で表される単量体（化合物）の代表的な例を示す。
　単量体の例としては、メタクリル酸、クロトン酸、イソクロトン酸、分子内に付加重合性二重結合および水酸基を有する化合物（例えば、メタクリル酸２－ヒドロキシエチル）とコハク酸無水物との反応物、分子内に付加重合性二重結合および水酸基を有する化合物とフタル酸無水物との反応物、分子内に付加重合性二重結合および水酸基を有する化合物とテトラヒドロキシフタル酸無水物との反応物、分子内に付加重合性二重結合および水酸基を有する化合物と無水トリメリット酸との反応物、分子内に付加重合性二重結合および水酸基を有する化合物とピロメリット酸無水物との反応物、アクリル酸、アクリル酸ダイマー、アクリル酸オリゴマー、マレイン酸、イタコン酸、フマル酸、４－ビニル安息香酸、ビニルフェノール、および、４－ヒドロキシフェニルメタクリルアミドなどが挙げられる。 The following are typical examples of monomers (compounds) represented by general formula (iv) to general formula (vi).
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 a phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic 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 anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and - such as hydroxyphenyl methacrylamide.
　被分散体と相互作用を形成しうる官能基を有する構造単位の含有量は、被分散体との相互作用、分散安定性、および現像液への浸透性の観点から、高分子化合物の全質量に対して、０．０５質量％～９０質量％が好ましく、１．０質量％～８０質量％がより好ましく、１０質量％～７０質量％がさらに好ましい。 The content of the structural unit having a functional group capable of forming an interaction with the dispersion is determined based on the total mass of the polymer compound from the viewpoint of the interaction with the dispersion, the dispersion stability, and the permeability to the developer. Is preferably 0.05% to 90% by weight, more preferably 1.0% to 80% by weight, and still more preferably 10% to 70% by weight.
　さらに、画像強度などの諸性能を向上する目的で、本発明の効果を損なわない限りにおいて、高分子化合物は、グラフト鎖を有する構造単位、疎水性構造単位、および、着色剤と相互作用を形成しうる官能基を有する構造単位とは異なる、種々の機能を有する他の構造単位（例えば、分散物に用いられる分散媒との親和性を有する官能基などを有する構造単位）をさらに有していてもよい。
　このような、他の構造単位としては、例えば、アクリロニトリル類、および、メタクリロニトリル類などから選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。
　高分子化合物は、これらの他の構造単位を１種或いは２種以上用いることができ、その含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは０％以上８０％以下であり、とくに好ましくは、１０％以上６０％以下である。含有量が上記範囲において、十分なパターン形成性が維持される。 Furthermore, for the purpose of improving various properties such as image strength, the polymer compound interacts 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. And further having other structural units having various functions (for example, structural units having functional groups having affinity with the dispersion medium used in the dispersion). May be.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles.
The polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
　高分子化合物の酸価は、０ｍｇＫＯＨ／ｇ以上２５０ｍｇＫＯＨ／ｇ以下の範囲であることが好ましく、０ｍｇＫＯＨ／ｇ以上１６０ｍｇＫＯＨ／ｇ以下の範囲であることがより好ましく、さらに好ましくは１０ｍｇＫＯＨ／ｇ以上１４０ｍｇＫＯＨ／ｇ以下の範囲であり、とくに好ましくは２０ｍｇＫＯＨ／ｇ以上１２０ｍｇＫＯＨ／ｇ以下の範囲である。
　高分子化合物の酸価が１６０ｍｇＫＯＨ／ｇ以下であれば、遮光膜を形成する際の現像時におけるパターン剥離がより効果的に抑えられる。また、高分子化合物の酸価が１０ｍｇＫＯＨ／ｇ以上であればアルカリ現像性がより良好となる。また、高分子化合物の酸価が２０ｍｇＫＯＨ／ｇ以上であれば、被分散体の沈降をより抑制でき、粗大粒子数をより少なくすることができ、硬化性組成物の経時安定性をより向上できる。 The acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 250 mgKOH / g, more preferably in the range of 0 mgKOH / g to 160 mgKOH / g, and still more preferably 10 mgKOH / g to 140 mgKOH / g. The range is not more than g, and particularly preferably not less than 20 mgKOH / g and not more than 120 mgKOH / g.
If the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming the light-shielding film can be more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable. In addition, when the acid value of the polymer compound is 20 mgKOH / g or more, sedimentation of the dispersion can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the curable composition can be further improved. .
　本発明において、高分子化合物の酸価は、例えば、高分子化合物中における酸基の平均含有量から算出することができる。また、高分子化合物の構成成分である酸基を含有する構造単位の含有量を変化させることで所望の酸価を有する樹脂を得ることができる。 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. Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
　本発明における高分子化合物の重量平均分子量は、遮光膜を形成する際において、現像時のパターン剥離抑制と現像性の観点から、ＧＰＣ（ゲル浸透クロマトグラフィー、Gel Permeation Chromatography）法によるポリスチレン換算値として、４，０００以上３００，０００以下であることが好ましく、５，０００以上２００，０００以下であることがより好ましく、６，０００以上１００，０００以下であることがさらに好ましく、１０，０００以上５０，０００以下であることがとくに好ましい。
　ＧＰＣ法は、ＨＬＣ－８０２０ＧＰＣ（東ソー（株）製）を用い、カラムとしてＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｈ、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ４０００、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ２０００（東ソー（株）製、４．６ｍｍＩＤ×１５ｃｍ）を、溶離液としてＴＨＦ（テトラヒドロフラン）を用いる方法に基づく。 The weight average molecular weight of the polymer compound in the present invention is a polystyrene conversion value by GPC (Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition and developability at the time of developing a light-shielding film. 4,000 to 300,000, preferably 5,000 to 200,000, more preferably 6,000 to 100,000, and more preferably 10,000 to 50. It is especially preferable that it is 1,000 or less.
The GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
　高分子化合物は、公知の方法に基づいて合成でき、高分子化合物を合成する際に用いられる溶剤としては、例えば、エチレンジクロリド、シクロヘキサノン、メチルエチルケトン、アセトン、メタノール、エタノール、プロパノール、ブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、２－メトキシエチルアセテート、１－メトキシ－２－プロパノール、１－メトキシ－２－プロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、トルエン、酢酸エチル、乳酸メチル、および、乳酸エチルなどが挙げられる。これらの溶剤は単独で用いても２種以上混合して用いてもよい。 The polymer compound can be synthesized based on a known method, and examples of the solvent used when 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, dimethyl sulfoxide, toluene, Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
　本発明に用いうる高分子化合物の具体例としては、ＢＹＫ　Ｃｈｅｍｉｅ社製「Ｄｉｓｐｅｒｂｙｋ－１６１、１６２、１６３、１６４、１６５、１６６、１７０、１９０（商品名、高分子共重合物）」、ＥＦＫＡ社製「ＥＦＫＡ４０４７、４０５０、４０１０、４１６５（商品名、ポリウレタン系）、ＥＦＫＡ４３３０、４３４０（商品名、ブロック共重合体）」等が挙げられる。
　これらの高分子化合物は、単独で使用してもよく、２種以上を組み合わせて使用してもよい。 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 “EFKA 4047, 4050, 4010, 4165 (trade name, polyurethane type), EFKA 4330, 4340 (trade name, block copolymer)” and the like can be mentioned.
These polymer compounds may be used alone or in combination of two or more.
　なお、高分子化合物の具体例の例としては、特開２０１３－２４９４１７号公報の段落０１２７～０１２９に記載の高分子化合物を参照でき、これらの内容は本明細書に組み込まれる。 As specific examples 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.
　また、分散剤としては、上述した高分子化合物以外に、特開２０１０－１０６２６８号公報の段落００３７～０１１５（対応するＵＳ２０１１／０１２４８２４の段落００７５～０１３３欄）のグラフト共重合体が使用でき、これらの内容は援用でき、本明細書に組み込まれる。
　また、上記以外にも、特開２０１１－１５３２８３号公報の段落００２８～００８４（対応するＵＳ２０１１／０２７９７５９の段落００７５～０１３３欄）の酸性基が連結基を介して結合してなる側鎖構造を有する構成成分を含む高分子化合物が使用でき、これらの内容は援用でき、本明細書に組み込まれる。 As the dispersant, in addition to the above-described polymer compound, graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 in US2011 / 0124824) can be used. Is incorporated herein by reference.
In addition to the above, it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 (corresponding to columns 0075 to 0133 of US 2011/0279759) of JP 2011-153283 A are bonded via a linking group. Polymeric compounds containing constituents can be used, the contents of which can be incorporated and incorporated herein.
　本発明の硬化性組成物における分散剤の含有量は、硬化性組成物の全固形分に対して、０．１～５０質量％が好ましく、０．５～３０質量％がより好ましい。 The content of the dispersant in the curable composition of the present invention is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, based on the total solid content of the curable composition.
〔その他の成分〕
＜含フッ素樹脂＞
　本発明の硬化性組成物は、より優れた低反射性を有する硬化膜が得られる点から、さらに含フッ素樹脂を含有してもよい。本明細書において、含フッ素樹脂とは、フッ素原子を有するオリゴマーまたはポリマーのことを言う。なお、含フッ素樹脂は、前述の分散剤および後述のバインダーポリマーには含まれないものとする。含フッ素樹脂としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、同Ｆ７８１Ｆ（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、および、同ＫＨ－４０（以上、旭硝子（株）製）等が挙げられる。
　含フッ素樹脂は、１種を用いてもよいし、２種類以上を組み合わせてもよい。
　含フッ素樹脂の添加量は、硬化膜がより優れた低反射性を有する点で、硬化性組成物の全質量に対して、０．０１～３質量％が好ましく、０．５～１．５質量％がより好ましい。 [Other ingredients]
<Fluorine-containing resin>
The curable composition of the present invention may further contain a fluorine-containing resin from the viewpoint of obtaining a cured film having more excellent low reflectivity. In the present specification, the fluorine-containing resin refers to an oligomer or polymer having a fluorine atom. In addition, a fluorine-containing resin shall not be contained in the above-mentioned dispersing agent and the below-mentioned binder polymer. Examples of the fluororesin include, for example, MegaFuck F171, F172, F173, F176, F177, F141, F142, F143, F143, F144, R30, F437, F475, F479, and F482. F554, F780, F781F (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC -103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).
One type of fluorine-containing resin may be used, or two or more types may be combined.
The addition amount of the fluorine-containing resin is preferably 0.01 to 3% by mass with respect to the total mass of the curable composition in that the cured film has more excellent low reflectivity, and preferably 0.5 to 1.5%. The mass% is more preferable.
　なお、エチレン性不飽和基を側鎖に有する含フッ素重合体を含フッ素樹脂として用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落００５０～００９０および段落０２８９～０２９５に記載された化合物、例えばＤＩＣ社製のメガファックＲＳ－１０１、ＲＳ－１０２、および、ＲＳ－７１８Ｋ等が挙げられる。
　エチレン性不飽和基を側鎖に有する含フッ素重合体と含フッ素樹脂とを併用する場合、その添加量は両者の合計が上述の好適範囲となるようにすることが好ましい。 A fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-containing resin. Specific examples thereof include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, such as MegaFac RS-101, RS-102, and RS-718K manufactured by DIC. Can be mentioned.
When using together the fluoropolymer which has an ethylenically unsaturated group in a side chain, and a fluororesin, it is preferable that the addition amount makes both become the above-mentioned suitable range.
＜バインダーポリマー＞
　本発明の硬化性組成物は、バインダーポリマーを含有していてもよい。
　バインダーポリマーとしては、線状有機ポリマーを用いることが好ましい。このような線状有機ポリマーとしては、公知のものを任意に使用することができる。好ましくは、水現像または弱アルカリ水現像を可能とするために、水または弱アルカリ水に可溶性または膨潤性である線状有機ポリマーが選択される。なかでも、バインダーポリマーとしては、アルカリ可溶性樹脂（アルカリ可溶性を促進する基を有する樹脂）がとくに好ましい。
　バインダーポリマーとしては、線状有機ポリマーであって、分子（好ましくは、アクリル系共重合体、スチレン系共重合体を主鎖とする分子）中に少なくとも１つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、または、アクリル／アクリルアミド共重合体樹脂が好ましく、現像性制御の観点からは、アクリル系樹脂、アクリルアミド系樹脂、または、アクリル／アクリルアミド共重合体樹脂が好ましい。
　アルカリ可溶性を促進する基（以下、酸基ともいう）としては、例えば、カルボキシル基、リン酸基、スルホン酸基、フェノール性水酸基などが挙げられるこれら酸基は、１種であってもよいし、２種以上であってもよい。 <Binder polymer>
The curable composition of the present invention may contain a binder polymer.
As the binder polymer, a linear organic polymer is preferably used. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. Among these, 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 an alkali having at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or styrene copolymer as a main chain). It can select suitably from soluble resin. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin is preferable, and from the viewpoint of developing property control, an acrylic resin, Acrylamide resins or acrylic / acrylamide copolymer resins are preferred.
As the group that promotes alkali solubility (hereinafter, also referred to as an acid group), for example, these acid groups include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like. Two or more types may be used.
　バインダーポリマーとしては、例えば、側鎖にカルボキシル基を有するラジカル重合体、例えば特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５４－９２７２３号、特開昭５９－５３８３６号、特開昭５９－７１０４８号に記載されているもの、すなわち、カルボキシル基を有するモノマーを単独或いは共重合させた樹脂、酸無水物を有するモノマーを単独或いは共重合させ酸無水物ユニットを加水分解若しくはハーフエステル化若しくはハーフアミド化させた樹脂、および、エポキシ樹脂を不飽和モノカルボン酸および酸無水物で変性させたエポキシアクリレート等が挙げられる。カルボキシル基を有するモノマーの例としては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、および、４－カルボキシルスチレン等が挙げられ、酸無水物を有するモノマーの例としては、無水マレイン酸等が挙げられる。また、同様に側鎖にカルボキシル基を有する酸性セルロース誘導体も例として挙げられる。この他に水酸基を有する重合体に環状酸無水物を付加させたものなどが有用である。
　また、欧州特許第９９３９６６号、欧州特許第１２０４０００号、特開２００１－３１８４６３号等の各公報に記載の酸基を有するアセタール変性ポリビニルアルコール系バインダーポリマーは、膜強度および現像性のバランスに優れており、好適である。
　さらに、この他に水溶性線状有機ポリマーとして、ポリビニルピロリドンおよびポリエチレンオキサイド等が有用である。また、硬化皮膜の強度を上げるために、アルコール可溶性ナイロン、および、２，２－ビス－（４－ヒドロキシフェニル）－プロパンとエピクロロヒドリンとの反応物であるポリエーテル等も有用である。 Examples of the binder polymer include radical polymers having a carboxyl group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Those described in JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins having a carboxyl group alone or copolymerized, monomers having an acid anhydride And a copolymer obtained by hydrolyzing, half-esterifying, or half-amidating an acid anhydride unit, and an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxyl styrene. Examples of monomers having an acid anhydride include And maleic anhydride. Similarly, acidic cellulose derivatives having a carboxyl group in the side chain are also exemplified. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
Further, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent Nos. 993966, 120204000, and 2001-318463 has an excellent balance between film strength and developability. It is preferable.
In addition, polyvinyl pyrrolidone and polyethylene oxide are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
　特に、これらの中でも、〔ベンジル（メタ）アクリレート／（メタ）アクリル酸／必要に応じてその他の付加重合性ビニルモノマー〕共重合体、および〔アリル（メタ）アクリレート／（メタ）アクリル酸／必要に応じてその他の付加重合性ビニルモノマー〕共重合体は、膜強度、感度、および、現像性のバランスに優れており、好適である。
　市販品としては、例えばアクリベースＦＦ－１８７、ＦＦ－４２６（藤倉化成社製）、アクリキュア－ＲＤ－Ｆ８（日本触媒（株））、ダイセルオルネクス（株）製サイクロマーＰ（ＡＣＡ）２３０ＡＡなどが挙げられる。
　なお、バインダーポリマーには、上述したグラフト鎖を有する構造単位（上記一般式（１）～一般式（４）のいずれかで表される構造単位）が含まれていてもよい。 In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity, and developability.
Commercially available products include, for example, Acrybase FF-187, FF-426 (Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai Co., Ltd.), Daicel Ornex Co., Ltd. Cyclomer P (ACA) 230AA, etc. Is mentioned.
The binder polymer may contain a structural unit having a graft chain as described above (a structural unit represented by any one of the general formulas (1) to (4)).
　バインダーポリマーの製造には、例えば、公知のラジカル重合法による方法を適用することができる。ラジカル重合法でアルカリ可溶性樹脂を製造する際の温度、圧力、ラジカル開始剤の種類およびその量、ならびに、溶剤の種類等々の重合条件は、当業者において容易に設定可能であり、実験的に条件を定めるようにすることもできる。 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 radical polymerization can be easily set by those skilled in the art, and experimental conditions It is also possible to determine.
　本発明の硬化性組成物におけるバインダーポリマーの含有量は、硬化性組成物の全固形分に対して、０．１～３０質量％であることが好ましく、０．３～２５質量％であることがより好ましい。 The content of the binder polymer in the curable composition of the present invention is preferably 0.1 to 30% by mass, and preferably 0.3 to 25% by mass with respect to the total solid content of the curable composition. Is more preferable.
＜溶剤＞
　本発明の硬化性組成物は、溶剤を含有していてもよい。
　溶剤としては、水または有機溶剤が挙げられる。
　有機溶剤の例としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、３－メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、３－メトキシプロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、γ－ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸メチル、および、乳酸エチルなどが挙げられるが、これらに限定されない。 <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 Nomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, acetic acid Examples include, but are not limited to, ethyl, butyl acetate, methyl lactate, and ethyl lactate.
　溶剤は、１種単独で用いてもよいが、硬化物がより優れた低反射性を有する点で、２種以上の有機溶剤を組み合わせて用いることが好ましい。２種以上の有機溶剤を組み合わせて用いることにより、塩基発生剤の溶解性が向上すると考えられ、硬化物の低反射性が向上する。
　有機溶剤を２種以上組み合わせて用いる場合、とくに好ましくは、上記の３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、およびプロピレングリコールメチルエーテルアセテートからなる群から選択される２種以上で構成される。
　硬化性組成物に含まれる溶剤の量としては、硬化性組成物の全質量に対し、１０～９０質量％であることが好ましく、２０～８５質量％であることがより好ましい。 Although a solvent may be used individually by 1 type, it is preferable to use combining 2 or more types of organic solvents at the point which hardened | cured material has the more excellent low reflectivity. By combining and using two or more organic solvents, it is considered that the solubility of the base generator is improved, and the low reflectivity of the cured product is improved.
When two or more 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 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol 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 and more preferably 20 to 85% by mass with respect to the total mass of the curable composition.
＜その他＞
　本発明の硬化性組成物には、紫外線吸収剤が含まれていてもよい。これにより、パターンの形状をより優れた（精細な）ものにすることができる。
　紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、および、トリアジン系の紫外線吸収剤を使用することができる。これらの具体例としては、特開２０１２－０６８４１８号公報の段落０１３７～０１４２（対応するＵＳ２０１２／００６８２９２の段落０２５１～０２５４）の化合物が使用でき、これらの内容が援用でき、本明細書に組み込まれる。
　他にジエチルアミノ－フェニルスルホニル系紫外線吸収剤（大東化学製、商品名：ＵＶ－５０３）なども好適に用いられる。
　紫外線吸収剤としては、特開２０１２－３２５５６号公報の段落０１３４～０１４８に例示される化合物が挙げられる。
　硬化性組成物が紫外線吸収剤を含む場合、紫外線吸収剤の含有量は、硬化性組成物の全固形分に対して、０．００１～１５質量％が好ましく、０．０１～１０質量％がより好ましく、０．１～５質量％がさらに好ましい。 <Others>
The curable composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of a 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 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
In addition, a diethylamino-phenylsulfonyl ultraviolet absorber (trade name: UV-503, manufactured by Daito Chemical Co., Ltd.) is 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, and 0.01 to 10% by mass with respect to the total solid content of the curable composition. More preferred is 0.1 to 5% by mass.
　硬化性組成物には、塗布性をより向上させる観点から、各種の界面活性剤が含まれていてもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、および、シリコーン系界面活性剤などの各種界面活性剤を使用できる。特に、本発明の硬化性組成物は、フッ素系界面活性剤を含有することで、液特性（特に、流動性）がより向上することから、塗布厚の均一性や省液性をより改善することができる。
　なお、本発明の硬化性組成物において、上述の含フッ素樹脂が界面活性剤としての機能を有していてもよい。本発明の硬化性組成物に好適に使用することができるフッ素系界面活性剤は、上述の含フッ素樹脂として例示したものと同様である。
　界面活性剤は、１種を用いてもよいし、２種類以上を組み合わせてもよい。
　界面活性剤の含有量は、硬化性組成物の全固形分に対して、０．００１～２．０質量％が好ましく、０．００５～１．０質量％がより好ましい。 Various surfactants may be contained in the curable composition from the viewpoint of further improving applicability. 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, since the curable composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) are further improved, so that the uniformity of coating thickness and the liquid-saving property are further improved. 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 in the curable composition of the present invention is the same as those exemplified as the above-mentioned fluorine-containing resin.
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 mass%, more preferably 0.005 to 1.0 mass%, based on the total solid content of the curable composition.
＜重合禁止剤＞
　本発明の硬化性組成物においては、組成物の製造中または保存中において、重合性化合物の不要な熱重合を阻止するために、重合禁止剤が含まれることが望ましい。本発明に用いうる重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔｅｒｔ－ブチルカテコール、ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン第一セリウム塩等が挙げられる。本発明の組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、硬化性組成物の全固形分に対して、０．０１～５質量％が好ましい。重合禁止剤は、１種を用いてもよいし、２種以上を組み合わせてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 <Polymerization inhibitor>
In the curable composition of the present invention, a polymerization inhibitor is desirably contained 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, 4,4′-thiobis (3-methyl-6- tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary 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 relative to the total solid content of the curable composition. A polymerization inhibitor may use 1 type and may combine 2 or more types. When two or more types are included, the total amount is preferably within the above range.
　上記成分以外にも、本発明の硬化性組成物には、以下の成分が含まれていてもよい。例えば、増感剤、共増感剤、架橋剤、硬化促進剤、フィラー、熱硬化促進剤、可塑剤、希釈剤、および、感脂化剤などが挙げられる。さらに基材表面への密着促進剤およびその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、酸化防止剤、香料、表面張力調整剤、連鎖移動剤など）等の公知の添加剤が、必要に応じて、硬化性組成物に含まれていてもよい。
　これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号０１８３～０２２８（対応する米国特許出願公開第２０１３／００３４８１２号明細書の［０２３７］～［０３０９］）、特開２００８－２５００７４号公報の段落番号０１０１～０１０２、段落番号０１０３～０１０４、段落番号０１０７～０１０９、および、特開２０１３－１９５４８０号公報の段落番号０１５９～０１８４等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 In addition to the above components, the curable composition of the present invention may contain the following components. Examples thereof include a sensitizer, a co-sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, a diluent, and a fat sensitizer. Furthermore, adhesion promoters to the substrate surface and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, A known additive such as a chain transfer agent may be contained in the curable composition as necessary.
These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No. 2013/0034812 [0237] to [0309]), JP2008-250074A. The descriptions of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP 2013-195480 A can be taken into account, and the contents thereof are described in the present specification. Incorporated.
〔硬化性組成物の調製方法〕
　本発明の硬化性組成物は、上述した各種成分を公知の混合方法（例えば、攪拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機、湿式分散機）により混合して調製することができる。
　各種成分の混合方法については、特に制限されないが、着色剤の分散性を向上する目的で、予め着色剤を他の成分（例えば樹脂や溶剤等）に分散してから他の成分と混合してもよく、分散性がより向上する点で、着色剤を上記分散剤に予め分散させてから他の成分と混合することが好ましい。
　本発明の硬化性組成物は、異物の除去や欠陥の低減などの目的で、フィルタで濾過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているものであれば特に限定されることなく用いることができる。例えば、ＰＴＦＥ（ポリテトラフルオロエチレン）等のフッ素樹脂、ナイロン等のポリアミド系樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量を含む）等によるフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）、ナイロンが好ましい。
　フィルタの孔径は、０．１～７．０μｍ程度が適しており、好ましくは０．２～２．５μｍ程度、より好ましくは０．２～１．５μｍ程度、さらに好ましくは０．３～０．７μｍである。この範囲とすることにより、顔料を含有する着色剤のろ過詰まりを抑えつつ、顔料を含有する着色剤に含まれる不純物や凝集物など、微細な異物を確実に除去することが可能となる。
　フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第１のフィルタでのフィルタリングは、１回でもよいし、２回以上行ってもよい。異なるフィルタを組み合わせて２回以上フィルタリングを行う場合は１回目のフィルタリングの孔径より２回目以降の孔径が同じ、または、大きい方が好ましい。また、上述した範囲内で異なる孔径の第１のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）または株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
　第２のフィルタは、上述した第１のフィルタと同様の材料等で形成されたものを使用することができる。第２のフィルタの孔径は、０．２～１０．０μｍ程度が適しており、好ましくは０．２～７．０μｍ程度、より好ましくは０．３～６．０μｍ程度である。
　本発明の硬化性組成物は、金属、ハロゲンを含む金属塩、酸、アルカリ等の不純物を含まないことが好ましい。これら材料に含まれる不純物の含有量としては、１ｐｐｍ以下が好ましく、１ｐｐｂ以下がより好ましく、１００ｐｐｔ以下が更に好ましく、１０ｐｐｔ以下が特に好ましく、実質的に含まないこと（測定装置の検出限界以下であること）が最も好ましい。 [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 mixing method of 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. In view of further improving the dispersibility, it is preferable to disperse the colorant in the dispersant in advance and then mix it with other components.
The curable composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably 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 still more preferably 0.3 to 0.0 μm. 7 μm. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the colorant containing the pigment while suppressing filtration clogging of the colorant containing the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, more preferably about 0.3 to 6.0 μm.
It is preferable that the curable composition of the present invention does not contain impurities such as metals, metal salts containing halogen, acids and alkalis. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
［遮光膜］
　本発明の硬化性組成物を硬化して得られる硬化膜は、着色剤として遮光性顔料を使用した場合には、優れた低反射性を有する遮光膜として使用するこができる。
　遮光膜の膜厚としては特に限定はないが、遮光膜の反射特性がより優れる点で、乾燥後の膜厚で、０．２～５０μｍが好ましく、０．５～３０μｍがより好ましく、０．７～２５μｍがさらに好ましく、１．０～１０μｍがとくに好ましい。
　上記厚みは平均厚みであり、遮光膜の任意の５点以上の厚みを測定し、それらを算術平均した値である。 [Light-shielding 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 thickness of the light-shielding film is not particularly limited, but is preferably 0.2 to 50 μm, more preferably 0.5 to 30 μm in terms of the film thickness after drying in terms of more excellent reflection characteristics of the light-shielding film. It is more preferably 7 to 25 μm, particularly preferably 1.0 to 10 μm.
The above thickness is an average thickness, and is a value obtained by measuring the thicknesses of any five or more points of the light shielding film and arithmetically averaging them.
〔遮光膜の製造方法〕
　遮光膜の製造方法は特に制限されないが、上述した硬化性組成物を基板上に塗布して塗膜を形成して、塗膜に対して硬化処理を施し、遮光膜を製造する方法が挙げられる。
　硬化処理の方法は特に制限されないが、通常、光硬化処理が選択される。
　なお、使用される基板の種類は特に制限されず、固体撮像装置内の各種部材（例えば、赤外光カットフィルタ、固体撮像素子の外周部、ウェハレベルレンズ外周部、および、固体撮像素子裏面など）などが好ましく挙げられる。 [Method for producing light-shielding film]
Although the manufacturing method in particular of a light shielding film is not restrict | limited, The method of apply | coating the curable composition mentioned above on a board | substrate, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a light shielding film is mentioned. .
The method for the curing treatment is not particularly limited, but usually a photocuring treatment is selected.
The type of substrate to be used is not particularly limited, and various members in the solid-state imaging device (for example, infrared light cut filter, outer peripheral portion of the solid-state imaging device, outer peripheral portion of the wafer level lens, and the back surface of the solid-state imaging device) Etc.) are preferred.
　パターン状の遮光膜を製造する場合の好適態様としては、基板上に、本発明の硬化性組成物を塗布して硬化性組成物層を形成する工程（以下、適宜「硬化性組成物層形成工程」と略称する。）と、マスクを介して硬化性組成物層を露光する工程（以下、適宜「露光工程」と略称する。）と、露光後の硬化性組成物層を現像して遮光膜（パターン状遮光膜）を形成する工程（以下、適宜「現像工程」と略称する。）と、を含む態様が挙げられる。
　具体的には、本発明の硬化性組成物を、直接または他の層を介して基板上に塗布して、硬化性組成物層を形成し（硬化性組成物層形成工程）、所定のマスクパターンを介して露光し、光照射された硬化性組成物層部分だけを硬化させ（露光工程）、現像液で現像することによって（現像工程）、パターン状の遮光膜を製造することができる。
　以下、上記態様における各工程について説明する。 A preferred embodiment in the case of producing a patterned light-shielding film is a step of forming a curable composition layer by applying the curable composition of the present invention on a substrate (hereinafter referred to as “curable composition layer formation” as appropriate). Abbreviated as “step”), a step of exposing the curable composition layer through a mask (hereinafter abbreviated as “exposure step” where appropriate), and a curable composition layer after exposure is developed to block light. And a step of forming a film (patterned light-shielding film) (hereinafter abbreviated as “development step” as appropriate).
Specifically, the curable composition of the present invention is applied directly or via another layer to a substrate to form a curable composition layer (curable composition layer forming step), and a predetermined mask. A pattern-shaped light-shielding film can be produced by exposing only through the pattern, curing only the curable composition layer portion irradiated with light (exposure process), and developing with a developer (development process).
Hereinafter, each process in the said aspect is demonstrated.
＜硬化性組成物層形成工程＞
　硬化性組成物層形成工程では、基板上に、本発明の硬化性組成物を塗布して硬化性組成物層を形成する。
　基板としては、例えば、固体撮像装置内の各種部材（例えば、赤外光カットフィルタ、固体撮像素子の外周部、ウェハレベルレンズ外周部、固体撮像素子裏面など）などが挙げられる。
　基板上への本発明の硬化性組成物の塗布方法としては、スリット塗布、インクジェット法、回転塗布、流延塗布、ロール塗布、および、スクリーン印刷法等の各種の塗布方法を適用することができる。
　基板上に塗布された硬化性組成物は、通常、７０℃以上１１０℃以下で２分以上４分以下程度の条件下で乾燥されることが好ましく、硬化性組成物層が形成される。 <Curable composition layer forming step>
In the curable composition layer forming step, the curable composition of the present invention is applied on the substrate to form a curable composition layer.
Examples of the substrate include various members in the solid-state imaging device (for example, an infrared light cut filter, an outer peripheral portion of the solid-state imaging device, an outer peripheral portion of a wafer level lens, a back surface of the solid-state imaging device, etc.).
As a coating method of the curable composition of the present invention on the substrate, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be applied. .
The curable composition applied on the substrate is usually preferably dried at 70 ° C. or more and 110 ° C. or less for 2 minutes or more and 4 minutes or less, and a curable composition layer is formed.
＜露光工程＞
　露光工程では、硬化性組成物層形成工程において形成された硬化性組成物層をマスクを介して露光し、光照射された硬化性組成物層部分だけを硬化させる。
　露光は放射線の照射により行うことが好ましく、露光に際して用いることができる放射線としては、特に、ｇ線、ｈ線、ｉ線等の紫外線が好ましく用いられ、光源としては高圧水銀灯が好まれる。照射強度は５ｍＪ／ｃｍ２以上１５００ｍＪ／ｃｍ２以下が好ましく、１０ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下がより好ましい。 <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 curable composition layer portion irradiated with light is cured.
The exposure is preferably performed by irradiation with radiation. As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is preferred as a 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.
＜現像工程＞
　露光工程に次いで、現像処理（現像工程）を行い、露光工程における光未照射部分を現像液（例えば、アルカリ水溶液）に溶出させる。
　現像液としては、有機アルカリ現像液が望ましい。現像温度としては通常２０℃以上３０℃以下が好ましく、現像時間は２０秒以上９０秒以下が好ましい。
　アルカリ水溶液としては、例えば、無機系現像液としては水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、メタ硅酸ナトリウムを、濃度が０．００１～１０質量％、好ましくは０．００５～０．５質量％となるように溶解したアルカリ水溶液が挙げられる。有機系現像液としては、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ－［５，４，０］－７－ウンデセン等のアルカリ性化合物を、濃度が０．００１～１０質量％、好ましくは０．００５～０．５質量％となるように溶解したアルカリ水溶液が挙げられる。アルカリ水溶液には、例えばメタノール、エタノール等の水溶性有機溶剤および／または界面活性剤等を適量添加することもできる。なお、このようなアルカリ水溶液からなる現像液を使用した場合には、一般に現像後純水等で洗浄（リンス）することが好ましい。 <Development process>
Subsequent to the exposure process, a development process (development process) is performed, and the light non-irradiated part in the exposure process is eluted in a developer (for example, an alkaline aqueous solution).
As the developer, an organic alkali developer is desirable. The development temperature is usually preferably 20 ° C. or higher and 30 ° C. or lower, and the development time is preferably 20 seconds or longer and 90 seconds or shorter.
As the alkaline aqueous solution, for example, as the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate having a concentration of 0.001 to 10% by mass, preferably An alkaline aqueous solution dissolved so as to be 0.005 to 0.5 mass% can be mentioned. Organic developers include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole , Piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene such that the concentration is 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass. An aqueous alkali solution dissolved in 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. In the case of using a developer composed of such an alkaline aqueous solution, it is generally preferable to rinse (rinse) with pure water after development.
　なお、硬化性組成物層形成工程、露光工程、および現像工程を行った後に、必要により、形成されたパターン状の遮光膜を加熱および／または露光により硬化する硬化工程を実施してもよい。 In addition, after performing a curable composition layer formation process, an exposure process, and a development process, you may implement the hardening process which hardens | cures the formed pattern-shaped light shielding film by heating and / or exposure as needed.
［遮光膜付き赤外光カットフィルタ、固体撮像装置］
　着色剤として遮光性顔料を用いた場合は、上述した硬化膜はいわゆる遮光膜として好適に適用できる。また、このような遮光膜は、固体撮像装置に好適に適用することができる。
　以下では、まず、本発明の遮光膜を有する固体撮像装置の第１実施形態について詳述する。
　図１および図２に示すように、固体撮像装置２は、固体撮像素子としてＣＭＯＳセンサ３と、このＣＭＯＳセンサ３が実装される回路基板４と、回路基板４を保持するセラミック製のセラミック基板５とを備えている。また、固体撮像装置２は、セラミック基板５に保持され、ＣＭＯＳセンサ３に向かう赤外光（ＩＲ）をカットするＩＲカットフィルタ６と、撮影レンズ７と、この撮影レンズ７を保持するレンズホルダ８と、このレンズホルダ８を移動自在に保持する保持筒９とを備えている。また、ＣＭＯＳセンサ３に代えて、ＣＣＤセンサや有機ＣＭＯＳセンサを設けてもよい。
　セラミック基板５は、ＣＭＯＳセンサ３が挿入される開口５ａが形成され、枠状となっており、ＣＭＯＳセンサ３の側面を囲んでいる。この状態で、ＣＭＯＳセンサ３が実装された回路基板４は、接着剤（例えば、エポキシ系接着剤、以下同様）によりセラミック基板５に固定されている。回路基板４には、各種回路パターンが形成されている。 [Infrared light cut filter with light-shielding film, solid-state imaging device]
When a light-shielding pigment is used as the colorant, the above-described cured film can be suitably applied as a so-called light-shielding film. Such a light shielding film can be suitably applied to a solid-state imaging device.
In the following, a first embodiment of a solid-state imaging device having a light shielding film of the present invention will be described in detail.
As shown in FIGS. 1 and 2, the solid-state imaging device 2 includes a CMOS sensor 3 as a solid-state imaging device, a circuit board 4 on which the CMOS sensor 3 is mounted, and a ceramic substrate 5 made of ceramic that holds the circuit board 4. And. The solid-state image pickup device 2 is held on a ceramic substrate 5, an IR cut filter 6 that cuts infrared light (IR) 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 that holds the lens holder 8 movably. Further, instead of the CMOS sensor 3, a CCD sensor or an organic CMOS sensor may be provided.
The ceramic substrate 5 has an opening 5 a into which the CMOS sensor 3 is inserted, 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.
　ＩＲカットフィルタ６は、板状のガラスや青ガラスに赤外光を反射する反射膜が形成され、この反射膜が形成された面が入射面６ａとなる。ＩＲカットフィルタ６は、開口５ａよりも一回り大きいサイズで形成され、開口５ａを覆うように接着剤によりセラミック基板５に固定されている。
　撮影レンズ７の背後（図２および図３における下方）に、ＣＭＯＳセンサ３が配され、撮影レンズ７とＣＭＯＳセンサ３との間に、ＩＲカットフィルタ６が配されている。被写体光は、撮影レンズ７、ＩＲカットフィルタ６を通ってＣＭＯＳセンサ３の受光面に入射する。このとき、赤外光は、ＩＲカットフィルタ６によりカットされる。
　回路基板４は、固体撮像装置２が搭載される電子機器（例えば、デジタルカメラ）に設けられた制御部に接続され、電子機器から固体撮像装置２に電力が供給される。ＣＭＯＳセンサ３は、受光面上に多数のカラー画素が二次元に配列されており、各カラー画素は入射光を光電変換し、発生した信号電荷を蓄積する。 In the IR cut filter 6, a reflection film that reflects infrared light is formed on a plate-like glass or blue glass, and the surface on which the reflection film is formed becomes the incident surface 6a. The IR cut filter 6 is formed in a size slightly 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 disposed behind the photographing lens 7 (downward in FIGS. 2 and 3), and an IR cut filter 6 is disposed 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 imaging device 2 is mounted, and power is supplied from the electronic device to the solid-state imaging device 2. In the CMOS sensor 3, a large number of color pixels are two-dimensionally arranged on the light receiving surface, and each color pixel photoelectrically converts incident light and accumulates generated signal charges.
　図２および図３に示すように、ＩＲカットフィルタ６の入射面６ａの端部には、全周に亘って上述した遮光膜（遮光層）１１が配置されており、遮光膜付き赤外光カットフィルタが形成されている。撮影レンズ７から出射され、セラミック基板５の前面（図２および図３における上面）で反射した反射光Ｒ１が、装置内で反射や屈折を繰り返した後にＣＭＯＳセンサ３に入射した場合、および、撮影レンズ７から出射されたレンズホルダ８の内壁面で反射した反射光Ｒ２が、ＣＭＯＳセンサ３に入射した場合には、撮影画像でフレアが発生する原因となる。遮光膜１１は、ＣＭＯＳセンサ３に向かう反射光Ｒ１、Ｒ２等の有害光を遮光する。遮光膜１１は、例えばスピンコート法、スプレーコート法で塗布されている。なお、図２および図３では、遮光膜１１の厚みを誇張して描いている。 As shown in FIGS. 2 and 3, the light shielding film (light shielding layer) 11 described above is disposed over the entire circumference at the end of the incident surface 6 a of the IR cut filter 6, and infrared light with a light shielding film is provided. A cut filter is formed. The reflected light R1 emitted from the photographing lens 7 and reflected by the front surface (the upper surface in FIGS. 2 and 3) of the ceramic substrate 5 is incident on the CMOS sensor 3 after being repeatedly reflected and refracted in the apparatus, and when photographing. When the reflected light R <b> 2 reflected from the inner wall surface of the lens holder 8 emitted from the lens 7 enters the CMOS sensor 3, flare occurs in the captured image. The light shielding film 11 shields harmful light such as reflected light R <b> 1 and R <b> 2 toward the CMOS sensor 3. The light shielding film 11 is applied by, for example, spin coating or spray coating. 2 and 3, the thickness of the light shielding film 11 is exaggerated.
　図４に第２実施形態の固体撮像装置２０を示す。なお、第１実施形態のものと同様の構成部材には同一の符号を付し、その詳細な説明を省略する。
　固体撮像装置２０は、ＣＭＯＳセンサ３と、回路基板４と、セラミック基板５と、ＩＲカットフィルタ６と、撮影レンズ７と、レンズホルダ８と、保持筒９とを備えている。ＩＲカットフィルタ６の側端面に、全周に亘って上述した遮光膜（遮光層）２１が形成されている。撮影レンズ７から出射され、セラミック基板５の前面で反射した反射光Ｒ３が、装置内で反射や屈折を繰り返した後にＣＭＯＳセンサ３に入射した場合には、撮影画像でフレアが発生する原因となる。遮光膜２１は、ＣＭＯＳセンサ３に向かう反射光Ｒ３等の有害光を遮光する。 FIG. 4 shows a solid-state imaging device 20 according to the second embodiment. In addition, the same code | symbol is attached | subjected to the structural member similar to the thing of 1st Embodiment, and the detailed description is abbreviate | omitted.
The solid-state imaging device 20 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The above-described light shielding film (light shielding layer) 21 is formed on the side end face of the IR cut filter 6 over the entire circumference. When the reflected light R3 emitted from the photographing lens 7 and reflected by the front surface of the ceramic substrate 5 is incident on the CMOS sensor 3 after being repeatedly reflected and refracted in the apparatus, it causes flare in the photographed image. . The light shielding film 21 shields harmful light such as reflected light R <b> 3 directed toward the CMOS sensor 3.
　図５に第３実施形態の固体撮像装置３０を示す。なお、第１実施形態のものと同様の構成部材には同一の符号を付し、その詳細な説明を省略する。
　固体撮像装置３０は、ＣＭＯＳセンサ３と、回路基板４と、セラミック基板５と、ＩＲカットフィルタ６と、撮影レンズ７と、レンズホルダ８と、保持筒９とを備えている。ＩＲカットフィルタ６の入射面６ａの端部および側端面に、全周に亘って上述した遮光膜（遮光層）３１が形成されている。すなわち、第１、第２実施形態を組み合わせたものとなっている。この実施形態では、第１、第２実施形態よりも遮光性能が高くなるので、フレアの発生が確実に抑制される。 FIG. 5 shows a solid-state imaging device 30 according to the third embodiment. In addition, the same code | symbol is attached | subjected to the structural member similar to the thing of 1st Embodiment, and the detailed description is abbreviate | omitted.
The solid-state imaging device 30 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference. That is, the first and second embodiments are combined. In this embodiment, since the light shielding performance is higher than in the first and second embodiments, the occurrence of flare is reliably suppressed.
　図６に第４実施形態の固体撮像装置４０を示す。なお、第１実施形態のものと同様の構成部材には同一の符号を付し、その詳細な説明を省略する。
　固体撮像装置４０は、ＣＭＯＳセンサ３と、回路基板４と、セラミック基板５と、ＩＲカットフィルタ６と、撮影レンズ７と、レンズホルダ８と、保持筒９とを備えている。ＩＲカットフィルタ６の入射面６ａの端部および側端面に、全周に亘って上述した遮光膜（遮光層）３１が形成されている。
　また、セラミック基板５の内壁面には、遮光膜（遮光層）４１が形成されている。撮影レンズ７から出射され、ＩＲカットフィルタ６を通過してセラミック基板５の内壁面で反射した反射光がＣＭＯＳセンサ３に入射した場合には、撮影画像のフレアが発生する原因となる。遮光膜４１は、セラミック基板５の内壁面よりも遮光性能が高くなるので、フレアの発生が確実に抑制される。 FIG. 6 shows a solid-state imaging device 40 of the fourth embodiment. In addition, the same code | symbol is attached | subjected to the structural member similar to the thing of 1st Embodiment, and the detailed description is abbreviate | omitted.
The solid-state imaging device 40 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference.
A light shielding film (light shielding layer) 41 is formed on the inner wall surface of the ceramic substrate 5. When reflected light that is emitted from the photographing lens 7, passes through the IR cut filter 6, and is reflected by the inner wall surface of the ceramic substrate 5 enters the CMOS sensor 3, flare of the photographed image occurs. Since the light shielding film 41 has a light shielding performance higher than that of the inner wall surface of the ceramic substrate 5, the occurrence of flare is reliably suppressed.
［画像表示装置、カラーフィルタ］
　本発明の硬化性組成物を硬化して得られた硬化膜は、液晶表示装置および有機エレクトロルミネッセンス表示装置などの、画像表示装置に用いることができる。また、硬化膜は、カラーフィルタに用いることができる。
　また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各色画素を形成する硬化膜が埋め込まれた構造を有していてもよい。
　この場合の隔壁は各色画素に対して低屈折率であることが好ましい。 [Image display device, color filter]
The cured film obtained by curing the curable composition of the present invention can be used in image display devices such as liquid crystal display devices and organic electroluminescence display devices. The cured film can be used for a color filter.
In addition, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
The partition in this case preferably has a low refractive index for each color pixel.
　表示装置の定義および各表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木　昭夫著、（株）工業調査会　１９９０年発行）」、「ディスプレイデバイス（伊吹　順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、（株）工業調査会　１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。 For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Sangyo Tosho) Issued in the first year). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
　本発明におけるカラーフィルタは、カラーＴＦＴ（Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）方式の液晶表示装置に用いてもよい。カラーＴＦＴ方式の液晶表示装置については、例えば「カラーＴＦＴ液晶ディスプレイ（共立出版（株）１９９６年発行）」に記載されている。さらに、本発明はＩＰＳ（Ｉｎ　Ｐｌａｎｅ　Ｓｗｉｔｃｈｉｎｇ）などの横電界駆動方式、ＭＶＡ（Ｍｕｌｔｉ－ｄｏｍａｉｎ　Ｖｅｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）などの画素分割方式などの視野角が拡大された液晶表示装置、ＳＴＮ（Ｓｕｐｅｒ－Ｔｗｉｓｔ　Ｎｅｍａｔｉｃ）、ＴＮ（Ｔｗｉｓｔｅｄ　Ｎｅｍａｔｉｃ）、ＶＡ（Ｖｅｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）、ＯＣＳ（ｏｎ－ｃｈｉｐ　ｓｐａｃｅｒ）、ＦＦＳ（ｆｒｉｎｇｅ　ｆｉｅｌｄ　ｓｗｉｔｃｈｉｎｇ）、および、Ｒ－ＯＣＢ（Ｒｅｆｌｅｃｔｉｖｅ　Ｏｐｔｉｃａｌｌｙ　Ｃｏｍｐｅｎｓａｔｅｄ　Ｂｅｎｄ）等にも適用できる。
　また、本発明におけるカラーフィルタは、明るく高精細なＣＯＡ（Ｃｏｌｏｒ－ｆｉｌｔｅｒ　Ｏｎ　Ａｒｒａｙ）方式にも供することが可能である。ＣＯＡ方式の液晶表示装置にあっては、カラーフィルタに対する要求特性は、前述のような通常の要求特性に加えて、層間絶縁膜に対する要求特性、すなわち低誘電率および剥離液耐性が必要とされることがある。本発明のカラーフィルタは、耐光性などに優れるので、解像度が高く長期耐久性に優れたＣＯＡ方式の液晶表示装置を提供することができる。なお、低誘電率の要求特性を満足するためには、カラーフィルタ層の上に樹脂被膜を設けてもよい。
　これらの画像表示方式については、例えば、「ＥＬ、ＰＤＰ、ＬＣＤディスプレイ－技術と市場の最新動向－（東レリサーチセンター調査研究部門　２００１年発行）」の４３ページなどに記載されている。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各色画素を形成する硬化膜が埋め込まれた構造を有していてもよい。この場合の隔壁は各色画素に対して低屈折率であることが好ましい。このような構造を有する撮像装置の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報に記載の装置が挙げられる。 The color filter in the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and a super-twist neutral (STN). TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical Compensated).
In addition, the color filter in the present invention can be used for 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 require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling liquid, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)". In addition, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.
　本発明の液晶表示装置は、本発明におけるカラーフィルタ以外に、電極基板、偏光フィルム、位相差フィルム、バックライト、スペーサ、および、視野角保障フィルムなど様々な部材から構成される。本発明のカラーフィルタは、これらの公知の部材で構成される液晶表示装置に適用することができる。これらの部材については、例えば、「'９４液晶ディスプレイ周辺材料・ケミカルズの市場（島　健太郎　（株）シーエムシー　１９９４年発行）」、「２００３液晶関連市場の現状と将来展望（下巻）（表良吉（株）富士キメラ総研、２００３年発行）」に記載されている。
　バックライトに関しては、SID meeting Digest 1380（2005）（A.Konno et.al）や、月刊ディスプレイ　２００５年１２月号の１８～２４ページ（島 康裕）、同２５～３０ページ（八木隆明）などに記載されている。 In addition to the color filter of the present invention, the liquid crystal display device of the present invention includes 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 components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.
　また、硬化性組成物を硬化して得られた硬化膜は、パーソナルコンピュータ、タブレット、携帯電話、スマートフォン、デジタルカメラなどのポータブル機器；プリンタ複合機、スキャナなどのＯＡ（Ｏｆｆｉｃｅ　Ａｕｔｏｍａｔｉｏｎ）機器；監視カメラ、バーコードリーダ、現金自動預け払い機（ＡＴＭ）、ハイスピードカメラ、顔画像認証を使用した本人認証などの産業用機器；車載用カメラ機器；内視鏡、カプセル内視鏡、カテーテルなどの医療用カメラ機器；生体センサー、バイオセンサー、軍事偵察用カメラ、立体地図用カメラ、気象及び海洋観測カメラ、陸地資源探査カメラ、宇宙の天文及び深宇宙ターゲット用の探査カメラなどの宇宙用機器などに使用される光学フィルターやモジュールの遮光部材や遮光層、さらには反射防止部材や反射防止層に用いることができる。 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 multifunction device or a scanner; , Barcode readers, automated teller machines (ATMs), high-speed cameras, industrial devices such as personal authentication using facial image authentication; in-vehicle camera devices; medical treatment such as endoscopes, capsule endoscopes, and catheters Camera equipment: Used in space equipment such as biosensors, biosensors, military reconnaissance cameras, 3D map cameras, weather and ocean observation cameras, land resource exploration cameras, space astronomy and deep space target exploration cameras Optical filters and light shielding members and light shielding layers of modules, It can be used for antireflection member and an anti-reflection layer.
　また、硬化性組成物を硬化して得られた硬化膜は、マイクロＬＥＤ（Light Emitting Diode）およびマイクロＯＬＥＤ（Organic Light Emitting Diode）などの用途にも用いることができる。特に限定されないが、マイクロＬＥＤおよびマイクロＯＬＥＤに使用される光学フィルタおよび光学フィルムのほか、遮光機能および反射防止機能を付与する部材に対して好適に用いられる。
　マイクロＬＥＤおよびマイクロＯＬＥＤの例としては特表２０１５－５００５６２および特表２０１４－５３３８９０のものが挙げられる。 Moreover, the cured film obtained by hardening | curing a curable composition can be used also for uses, such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). Although it does not specifically limit, In addition to the optical filter and optical film which are used for micro LED and micro OLED, it uses suitably with respect to the member which provides a light-shielding function and an antireflection function.
Examples of the micro LED and the micro OLED include those in JP-T-2015-500562 and JP-T-2014-533890.
　また、硬化性組成物を硬化して得られた硬化膜は、量子ドットディスプレイなどの用途にも用いることができる。特に限定されないが、量子ドットディスプレイに使用される光学フィルターおよび光学フィルムのほか、遮光機能および反射防止機能を付与する部材に対して好適に用いられる。
　量子ドットディスプレイの例としては、米国特許出願公開第２０１３／０３３５６７７号、米国特許出願公開第２０１４／００３６５３６号、米国特許出願公開第２０１４／００３６２０３号、および、米国特許出願公開第２０１４／００３５９６０号のものが挙げられる。 Moreover, the cured film obtained by hardening | curing a curable composition can be used also for uses, such as a quantum dot display. Although it does not specifically limit, In addition to the optical filter and optical film which are used for a quantum dot display, it uses suitably with respect to the member which provides a light-shielding function and an antireflection function.
Examples of quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960. Things.
　以下、本発明を実施例によりさらに具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」、「％」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. However, 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, “part” and “%” are based on mass.
〔チタンブラックＡ－１の作製〕
　平均粒径１５ｎｍの酸化チタンＭＴ－１５０Ａ（商品名：テイカ（株）製）を１００ｇ、ＢＥＴ比表面積３００ｍ２／ｇのシリカ粒子ＡＥＲＯＳＩＬ３００（登録商標）３００／３０（エボニック社製）を２５ｇ、および、Ｄｉｓｐｅｒｂｙｋ１９０（商品名：ビックケミー社製）を１００ｇ秤量し、これらをイオン電気交換水７１ｇに加えて、混合物を得た。その後、ＫＵＲＡＢＯ製ＭＡＺＥＲＳＴＡＲ　ＫＫ－４００Ｗを使用して、公転回転数１３６０ｒｐｍ、自転回転数１０４７ｒｐｍにて混合物を３０分間処理することにより均一な混合物水溶液を得た。この混合物水溶液を石英容器に充填し、小型ロータリーキルン（株式会社モトヤマ製）を用いて酸素雰囲気中で９２０℃に加熱した。その後、小型ロータリーキルン内を窒素で雰囲気を置換し、同温度でアンモニアガスを１００ｍＬ／ｍｉｎで５時間流すことにより窒化還元処理を実施した。終了後回収した粉末を乳鉢で粉砕し、Ｓｉ原子を含み、粉末状の比表面積７３ｍ2／ｇのチタンブラック〔チタンブラック粒子およびＳｉ原子を含む被分散体〕を得た（以下では、「チタンブラック」と表記する。ただし、表１中では「着色剤１」と表記する。）。 [Production of Titanium Black A-1]
100 g of titanium oxide MT-150A having an average particle size of 15 nm (trade name: manufactured by Teika Co., Ltd.), 25 g of silica particles AEROSIL300 (registered trademark) 300/30 (manufactured by Evonik) having a BET specific surface area of 300 m 2 / g, and Disperbyk190 (trade name: manufactured by Big Chemie) was weighed 100 g, and these were added to 71 g of ion-electroexchanged water to obtain a mixture. Thereafter, the mixture was treated for 30 minutes at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm using a MAZARSTAR KK-400W manufactured by KURABO to obtain a uniform aqueous mixture solution. This aqueous mixture 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.). Thereafter, the atmosphere in the small rotary kiln was replaced with nitrogen, and nitriding reduction treatment was performed by flowing ammonia gas at 100 mL / min for 5 hours at the same temperature. After the completion, the recovered powder was pulverized in a mortar to obtain titanium black [a dispersion containing titanium black particles and Si atoms] containing Si atoms and having a powder specific surface area of 73 m 2 / g (hereinafter referred to as “titanium”). (Indicated in Table 1 as “Colorant 1”.)
〔チタンブラック分散物（ＴＢ分散液１）の調製〕
　下記組成１に示す成分を、攪拌機（ＩＫＡ社製ＥＵＲＯＳＴＡＲ）を使用して、１５分間混合し、分散物ａを得た。
　なお、以下に記載の顔料分散樹脂（分散剤に該当する）は特開２０１３－２４９４１７号公報の記載を参照して合成した。また、顔料分散樹脂の重量平均分子量は３００００であり、酸価は６０ｍｇＫＯＨ／ｇであり、グラフト鎖の原子数（水素原子を除く）は１１７であった。 [Preparation of titanium black dispersion (TB dispersion 1)]
The component shown in the following composition 1 was mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain dispersion a.
The pigment dispersion resin described below (corresponding to a dispersant) was synthesized with reference to the description in JP-A-2013-249417. The weight average molecular weight of the pigment-dispersed resin was 30000, the acid value was 60 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.
＜組成１＞
・上記のようにして得られたチタンブラック　　　　・・・２５．０質量部
・顔料分散樹脂のプロピレングリコールモノメチルエーテルアセテート２０質量％溶液
　　　　　　　　　　　　　　　　　　　　　　　　・・・３７．５質量部
・プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）（溶剤）
　　　　　　　　　　　　　　　　　　　　　　　　・・・１０．５質量部
・酢酸ブチル（溶剤）　　　　　　　　　　　　　　・・・２７．０質量部 <Composition 1>
-Titanium black obtained as described above ... 25.0 parts by mass-20% by mass solution of propylene glycol monomethyl ether acetate in 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
　上述の顔料分散樹脂の構造は下記式のとおりである。
Figure JPOXMLDOC01-appb-C000018
 The structure of the above-mentioned pigment dispersion resin is as shown in the following formula.
Figure JPOXMLDOC01-appb-C000018
　得られた分散物ａに対し、（株）シンマルエンタープライゼス製のＮＰＭ－Ｐｉｌｏｔを使用して下記条件にて分散処理を行い、チタンブラック分散物（以下、ＴＢ分散液１と表記する。）を得た。 The obtained dispersion a was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. to obtain a titanium black dispersion (hereinafter referred to as TB dispersion 1). Got.
＜分散条件＞
・ビーズ径：φ０．０５ｍｍ、ジルコニア製
・ビーズ充填率：６５体積％
・ミル周速：１０ｍ／ｓｅｃ
・セパレータ周速：１１ｍ／ｓ
・分散処理する混合液量：１５ｋｇ
・循環流量（ポンプ供給量）：６０ｋｇ／ｈｏｕｒ
・処理液温度：１９～２１℃
・冷却水：水
・パス回数：９０パス <Distribution conditions>
・ Bead diameter: φ0.05mm, made of zirconia ・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 11m / s
・ Amount of liquid mixture to be dispersed: 15kg
・ Circulating flow rate (pump supply amount): 60 kg / hour
・ Processing liquid temperature: 19-21 ℃
・ Cooling water: Water ・ Number of passes: 90 passes
〔チタンブラック分散物（ＴＢ分散液２）の調製〕
　顔料分散樹脂に代えて、以下に記載の分散剤ａを用いた以外はＴＢ分散液１と同様にして、ＴＢ分散液２を得た。なお、分散剤ａは特開２０１４－１７７６１４号公報の記載を参照して合成し、式中、ｎは１５を表し、＊は左側構造式中のＺ部との連結部を表す。 [Preparation of Titanium Black Dispersion (TB Dispersion 2)]
A TB dispersion 2 was obtained in the same manner as the TB dispersion 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 No. 2014-177614. In the formula, n represents 15 and * represents a connecting portion with the Z portion in the left structural formula.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
〔チタンブラック分散物（ＴＢ分散物３）の調製〕
　顔料分散樹脂に代えて、以下に記載の分散剤ｂを用いた以外はＴＢ分散液１と同様にして、ＴＢ分散液３を得た。なお、分散剤ｂは特開２０１０－６９３２号公報の記載を参照して合成し、式中、＊は連結部分を表す。 [Preparation of Titanium Black Dispersion (TB Dispersion 3)]
A TB dispersion 3 was obtained in the same manner as the TB dispersion 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, where * represents a linking moiety.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
〔カーボンブラック分散物（ＣＢ分散液）の調製〕
　上記のＴＢ分散液１の調製において、チタンブラックに代えて、カーボンブラック（商品名「カラーブラック　Ｓ１７０」、デグサ社製、平均一次粒子径１７ｎｍ、ＢＥＴ比表面積２００ｍ2／ｇ、ガスブラック方式により製造されたカーボンブラック、表１中では、「着色剤２」と表記する。）を使用した以外は同様の方法により、分散物ｂを作製し、カーボンブラック分散物（以下、ＣＢ分散液と表記する。）を得た。 [Preparation of carbon black dispersion (CB dispersion)]
In the preparation of the TB dispersion 1, carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, manufactured by gas black method instead of titanium black. The dispersion b was prepared in the same manner except that the carbon black thus obtained was expressed as “Colorant 2” in Table 1, and a carbon black dispersion (hereinafter referred to as CB dispersion) was prepared. .)
〔チタンブラックおよびカーボンブラック分散物（ＴＢ／ＣＢ分散液）の調製〕
　上記のＴＢ分散液１の調製において、チタンブラックに代えて、チタンブラック３５部と、上記カーボンブラック１０部との混合部を使用した以外は同様の方法により、分散物ｃを作製し、チタンブラックおよびカーボンブラック分散物（以下、ＴＢ／ＣＢ分散液と表記する。）を得た。 [Preparation of titanium black and carbon black dispersion (TB / CB dispersion)]
In the preparation of the above TB dispersion 1, dispersion c was prepared in the same manner except that instead of titanium black, a mixed part of 35 parts of titanium black and 10 parts of carbon black was used, And a carbon black dispersion (hereinafter referred to as TB / CB dispersion).
〔チタンブラックおよびピグメントイエロー（ＴＢ／ＰＹ分散液）の調製〕
　上記のＴＢ分散液１の調製において、チタンブラック４５部に代えて、チタンブラック４０部とピグメントイエロー１５０（Hangzhou Star-up Pigment Co., Ltd.製、商品名６１５０顔料黄５ＧＮ、表１中では「着色剤３」と表記する。）５部との混合物を使用した以外は同様の方法により、分散物ｄを作製し、チタンブラックおよびピグメントイエロー分散物（以下、ＴＢ／ＰＹ分散液と表記する。）を得た。 [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 Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN, in Table 1) A dispersion d is prepared in the same manner except that a mixture of 5 parts is used, and a titanium black and pigment yellow dispersion (hereinafter referred to as a TB / PY dispersion). .)
〔光塩基発生剤の合成〕
　下記一般式（ＰＢＧ１）～（ＰＢＧ１３）に示した光塩基発生剤は、特開２０１５－０８７６１２号公報、特開２００８－２４７７４７号公報、および、国際公開第２０１０／０６４６３１号の記載を参照して合成した。なお、ＰＢＧ１については和光純薬工業（株）の「ＷＰＢＧ－０１８」（製品名）としても入手可能である。 (Synthesis of photobase generator)
The photobase generators represented by the following general formulas (PBG1) to (PBG13) are described in 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.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
〔実施例１：硬化性組成物１の調製〕
　下記組成を混合することで硬化性組成物１を得た。なお、下記のチタンブラックは上述の方法により作製し、上述の方法により顔料分散樹脂を用いてチタンブラックを分散させたＴＢ分散液１を作製してから、ＴＢ分散液１と他の材料と混合した。また、硬化性組成物１の固形分は３０％となるよう、プロピレングリコールモノメチルエーテルアセテート（有機溶剤に該当する。）により希釈した。 [Example 1: Preparation of curable composition 1]
The curable composition 1 was obtained by mixing the following composition. The following titanium black is prepared by the above method, and after preparing the TB dispersion 1 in which the titanium black is dispersed using the pigment dispersion resin by the above method, the TB dispersion 1 is mixed with other materials. did. Further, the curable composition 1 was diluted with propylene glycol monomethyl ether acetate (corresponding to an organic solvent) so that the solid content was 30%.
・ジペンタエリスリトールヘキサアクリレート　　２０．４９質量部（ＫＡＹＡＲＡＤ ＤＰＨＡ（商品名）、日本化薬社製）重合性化合物に該当する。表１中では、「重合性化合物１」と表記する。）
・ＯＸＥ－０２　　５．９０質量部（ＢＡＳＦ社製、オキシム系開始剤に該当する。表１中では、「光ラジカル重合開始剤１」と表記する。）
・ＰＢＧ１　　２．９５質量部（光塩基発生剤に該当する。）
・含フッ素樹脂１：　　０．０７質量部（以下の化学式で表される混合物（重量平均分子量（Ｍｗ）＝１４０００）） -Dipentaerythritol hexaacrylate 20.49 mass parts (KAYARAD DPHA (brand name), Nippon Kayaku Co., Ltd. product) It corresponds to a polymerizable compound. In Table 1, it is described as “polymerizable compound 1”. )
OXE-02 5.90 parts by mass (manufactured by BASF, corresponding to an oxime initiator. In Table 1, it is represented as “photo radical polymerization initiator 1”.)
-PBG1 2.95 parts by mass (corresponding to a photobase generator)
Fluorine-containing resin 1: 0.07 parts by mass (mixture represented by the following chemical formula (weight average molecular weight (Mw) = 14000))
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
・メガファックＲＳ－７２－Ｋ　　１．００質量部（ＤＩＣ社製、固形分３０％、溶剤：プロピレングリコールモノメチルエーテルアセテート、含フッ素樹脂に該当する。表１中では、「含フッ素樹脂２」と表記する。）
・ｐ－メトキシフェノール　　０．０１質量部（関東化学社製、重合禁止剤）
・バインダーポリマー　　１１．５質量部（ベンジルメタクリレート／メタクリル酸／２－ヒドロキシエチルメタクリレート共重合体、各構造単位の比率６０／２０／２０ｗｔ％、重量平均分子量：１４，０００、アルカリ可溶性樹脂に該当する。）
・顔料分散樹脂　　１３．４６質量部（上述の顔料分散樹脂、分散剤に該当する。）
・チタンブラック　　４５．００質量部（上述のチタンブラック、着色剤に該当する。） -MegaFac RS-72-K 1.00 parts by mass (manufactured by DIC, solid content 30%, solvent: propylene glycol monomethyl ether acetate, fluorine-containing resin. In Table 1, “Fluorine-containing resin 2” write.)
・ 0.01 parts by mass of p-methoxyphenol (manufactured by Kanto Chemical Co., Ltd., 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, corresponding to alkali-soluble resin .)
Pigment dispersion resin 13.46 parts by mass (corresponding to the above-described pigment dispersion resin and dispersant)
Titanium black 45.00 parts by mass (corresponding to the above-described titanium black and colorant)
〔実施例２～１２：硬化性組成物２～１２の調製〕
　実施例１のＰＢＧ１に代えて、ＰＢＧ２～１２（いずれも光塩基発生剤に該当する。）を使用した以外は同様の方法により、硬化性組成物２～１２を得た。 [Examples 2 to 12: Preparation of curable compositions 2 to 12]
Curable compositions 2 to 12 were obtained in the same manner except that PBGs 2 to 12 (both corresponding to photobase generators) were used instead of PBG 1 of Example 1.
〔実施例１３：硬化性組成物１３の調製〕
　実施例１のＯＸＥ－０２に代えて、ＩＲＧＡＣＵＲＥ３７９（ＢＡＳＦ社製、光ラジカル重合開始剤に該当する。表１中では、「光ラジカル重合開始剤２」と表記する。）を使用した以外は同様の方法により、硬化性組成物１３を得た。 [Example 13: Preparation of curable composition 13]
In place of OXE-02 of Example 1, IRGACURE 379 (corresponding to a radical photopolymerization initiator manufactured by BASF Corp. is represented as “photoradical polymerization initiator 2” in Table 1) is the same. The curable composition 13 was obtained by the method.
〔実施例１４：硬化性組成物１４の調製〕
　ＰＢＧ１の使用量を１．０９質量部、バインダーポリマーの使用量を１３．０１質量部とした以外は実施例１と同様の方法により、硬化性組成物１４を得た。 [Example 14: Preparation of curable composition 14]
A curable composition 14 was obtained in the same manner as in Example 1 except that the amount of PBG1 used was 1.09 parts by mass and the amount of the binder polymer used was 13.01 parts by mass.
〔実施例１５：硬化性組成物１５の調製〕
　ＰＢＧ１の使用量を１．０７質量部、バインダーポリマーの使用量を１３．０３質量部とした以外は実施例１と同様の方法により、硬化性組成物１５を得た。 [Example 15: Preparation of curable composition 15]
A curable composition 15 was obtained in the same manner as in Example 1 except that the amount of PBG1 used was 1.07 parts by mass and the amount of the binder polymer used was 13.03 parts by mass.
〔実施例１６：硬化性組成物１６の調製〕
　ＰＢＧ１の使用量を６．６０質量部、バインダーポリマーの使用量を７．５０質量部とした以外は実施例１と同様の方法により、硬化性組成物１６を得た。 [Example 16: Preparation of curable composition 16]
A curable composition 16 was obtained in the same manner as in Example 1 except that the amount of PBG1 used was 6.60 parts by mass and the amount of the binder polymer used was 7.50 parts by mass.
〔実施例１７：硬化性組成物１７の調製〕
　ＰＢＧ１の使用量を６．８５質量部、バインダーポリマーの使用量を７．２５質量部とした以外は実施例１と同様の方法により、硬化性組成物１７を得た。 [Example 17: Preparation of curable composition 17]
A curable composition 17 was obtained in the same manner as in Example 1, except that the amount of PBG1 used was 6.85 parts by mass and the amount of the binder polymer used was 7.25 parts by mass.
〔実施例１８：硬化性組成物１８の調製〕
　含フッ素樹脂１の使用量を０．０７質量部、メガファックＲＳ－７２－Ｋの使用量を０．９３質量部とした以外は実施例１と同様の方法により、硬化性組成物１８を得た。 [Example 18: Preparation of curable composition 18]
A curable composition 18 was obtained in the same manner as in Example 1, except that the amount of fluororesin 1 used was 0.07 parts by mass, and the amount of MegaFac RS-72-K was 0.93 parts by mass. It was.
〔実施例１９：硬化性組成物１９の調製〕
　含フッ素樹脂１の使用量を０．０７質量部、メガファックＲＳ－７２－Ｋの使用量を０．９０質量部、バインダーポリマーの使用量を１１．２５質量部とした以外は実施例１と同様の方法により、硬化性組成物１９を得た。 [Example 19: Preparation of curable composition 19]
Example 1 except that the amount of fluorine-containing resin 1 used was 0.07 parts by mass, the amount of megafac RS-72-K used was 0.90 parts by mass, and the amount of binder polymer used was 11.25 parts by mass. The curable composition 19 was obtained by the same method.
〔実施例２０：硬化性組成物２０の調製〕
　含フッ素樹脂１の使用量を０質量部、メガファックＲＳ－７２－Ｋの使用量を０質量部、バインダーポリマーの使用量を１２．２２質量部とした以外は実施例１と同様の方法により、硬化性組成物２０を得た。 [Example 20: Preparation of curable composition 20]
The same method as in Example 1 except that the amount of fluororesin 1 used was 0 parts by mass, the amount of MegaFac RS-72-K was 0 parts by mass, and the amount of binder polymer used was 12.22 parts by mass. The curable composition 20 was obtained.
〔実施例２１：硬化性組成物２１の調製〕
　ｐ－メトキシフェノールの使用量を０質量部、バインダーポリマーの使用量を１１．１６質量部とした以外は実施例１と同様の方法により、硬化性組成物２１を得た。 [Example 21: Preparation of curable composition 21]
A curable composition 21 was obtained in the same manner as in Example 1 except that the amount of p-methoxyphenol used was 0 parts by mass and the amount of the binder polymer used was 11.16 parts by mass.
〔実施例２２：硬化性組成物２２の調製〕
　ジペンタエリスリトールヘキサアクリレートの使用量を３１．６４質量部、バインダーポリマーの使用量を０質量部とした以外は実施例１と同様の方法により、硬化性組成物２２を得た。 [Example 22: Preparation of curable composition 22]
A curable composition 22 was obtained in the same manner as in Example 1 except that the amount of dipentaerythritol hexaacrylate used was 31.64 parts by mass and the amount of the binder polymer used was 0 parts by mass.
〔実施例２３：硬化性組成物２３の調製〕
　ＴＢ分散液１に代えて、上述の方法により作製したＣＢ分散液を使用した以外は実施例１と同様の方法により、硬化性組成物２３を得た。 [Example 23: Preparation of curable composition 23]
A curable composition 23 was obtained in the same manner as in Example 1 except that the CB dispersion prepared by the above-described method was used in place of the TB dispersion 1.
〔実施例２４：硬化性組成物２４の調製〕
　ＴＢ分散液１に代えて、上述の方法により作製したＴＢ／ＣＢ分散液を使用した以外は実施例１と同様の方法により、硬化性組成物２４を得た。 [Example 24: Preparation of curable composition 24]
Instead of the TB dispersion 1, a 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.
〔実施例２５：硬化性組成物２５の調製〕
　ＴＢ分散液１に代えて、上述の方法により作製したＴＢ／ＰＹ分散液を使用した以外は実施例１と同様の方法により、硬化性組成物２５を得た。 [Example 25: Preparation of curable composition 25]
Instead of the TB dispersion 1, a 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.
〔実施例２６：硬化性組成物２６の調製〕
　有機溶剤として、プロピレングリコールモノメチルエーテルアセテートおよびシクロペンタノンを用い、硬化性組成物中におけるシクロペンタノンの含有量が１０質量％となり、かつ硬化性組成物の固形分が３０％となるよう希釈した以外は実施例１と同様の方法により、硬化性組成物２６を得た。 [Example 26: Preparation of curable composition 26]
As an organic solvent, propylene glycol monomethyl ether acetate and cyclopentanone were used and 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%. Except for the above, a curable composition 26 was obtained in the same manner as in Example 1.
〔実施例２７：硬化性組成物２７の調製〕
　ＴＢ分散液１に代えて、上述の方法により作製したＴＢ分散液２を使用した以外は実施例１と同様の方法により、硬化性組成物２７を得た。 [Example 27: Preparation of curable composition 27]
A curable composition 27 was obtained in the same manner as in Example 1 except that the TB dispersion 2 produced by the above-described method was used in place of the TB dispersion 1.
〔実施例２８：硬化性組成物２８の調製〕
　ＴＢ分散液１に代えて、上述の方法により作製したＴＢ分散液３を使用した以外は実施例１と同様の方法により、硬化性組成物２８を得た。 [Example 28: Preparation of curable composition 28]
A curable composition 28 was obtained in the same manner as in Example 1 except that the TB dispersion 3 produced by the above-described method was used in place of the TB dispersion 1.
〔実施例２９：硬化性組成物２９の調製〕
　ジペンタエリスリトールヘキサアクリレートに代えて、ペンタエリスリトールテトラアクリレート（重合性化合物に該当する。表１中では、「重合性化合物２」と表記する。）を使用した以外は実施例１と同様の方法により、硬化性組成物２９を得た。 [Example 29: Preparation of curable composition 29]
Instead of dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate (corresponding to a polymerizable compound. In Table 1, indicated as “polymerizable compound 2”) was used in the same manner as in Example 1. A curable composition 29 was obtained.
〔実施例３０：硬化性組成物３０の調製〕
　ジペンタエリスリトールヘキサアクリレートに代えて、ジペンタエリスリトールヘキサアクリレート１０．００質量部およびペンタエリスリトールテトラアクリレート１０．４９質量部を使用した以外は実施例１と同様の方法により、硬化性組成物３０を得た。 [Example 30: Preparation of curable composition 30]
In place of dipentaerythritol hexaacrylate, a curable composition 30 was obtained in the same manner as in Example 1, except that 100.00 parts by mass of dipentaerythritol hexaacrylate and 10.49 parts by mass of pentaerythritol tetraacrylate were used. It was.
〔実施例３１：硬化性組成物３１の調製〕
　ＯＸＥ－０２に代えて、ＯＸＥ－０１（ＢＡＳＦ社製、オキシム系開始剤に該当する。表１中では、「光ラジカル重合開始剤３」と表記する。）を使用した以外は実施例１と同様の方法により、硬化性組成物３１を得た。 [Example 31: Preparation of curable composition 31]
In place of OXE-02, Example 1 was used except that OXE-01 (manufactured by BASF, corresponding to an oxime initiator. In Table 1, referred to as “photo radical polymerization initiator 3”) was used. The curable composition 31 was obtained by the same method.
〔実施例３２：硬化性組成物３２の調製〕
　ＯＸＥ－０２に代えて、下記式（Ｉ－１）で表される化合物（オキシム系開始剤に該当する。表１中では、「光ラジカル開始剤４」と表記する。）を使用した以外は実施例１と同様の方法により、硬化性組成物３３を得た。なお、下記式（Ｉ－１）は特表２０１４－５００８５２号公報の段落０３４４～０３４５に記載されている方法を参考にして合成した。 [Example 32: Preparation of curable composition 32]
Instead of OXE-02, a compound represented by the following formula (I-1) (corresponding to an oxime initiator, represented as “photoradical initiator 4” in Table 1) was used. A curable composition 33 was obtained in the same manner as in Example 1. The following formula (I-1) was synthesized with reference to the method described in paragraphs 0344 to 0345 of JP-T-2014-500852.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
〔実施例３３：硬化性組成物３３の調製〕
　ＰＢＧ１に代えて、ＰＥＧ１３を使用した以外は実施例１と同様の方法により、硬化性組成物３４を得た。 [Example 33: Preparation of curable composition 33]
A curable composition 34 was obtained in the same manner as in Example 1 except that PEG13 was used instead of PBG1.
〔比較例１〕
　ＰＥＧ１に代えて、バインダーポリマーを使用した（バインダーポリマーを合計１４．１０質量部）使用した以外は実施例１と同様の方法により、比較硬化性組成物を得た。 [Comparative Example 1]
A comparative curable composition was obtained in the same manner as in Example 1 except that a binder polymer was used in place of PEG1 (a total of 14.10 parts by mass of binder polymer).
〔評価方法〕
＜硬化膜の作製＞
　厚さ０．７ｍｍ、大きさ１００ｍｍ×１００ｍｍガラス板（コーニング１７３７、コーニング社製）上に乾燥膜厚が２．０μｍとなるよう、各硬化性組成物をスピンコート法により塗布した。その後、硬化性組成物が塗布されたガラス板に対して、１００℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行い、塗膜を形成した。次いで、高圧水銀灯にて１０００ｍＪ／ｃｍ２の露光量で塗膜に対して全面露光した。その後、全面露光された塗膜を有するガラス板をホットプレート上にて２００℃で３００秒間加熱し、硬化膜を得た。 〔Evaluation methods〕
<Production of cured film>
Each curable composition was applied by spin coating so that the dry film thickness was 2.0 μm on a glass plate having a thickness of 0.7 mm and a size of 100 mm × 100 mm (Corning 1737, manufactured by Corning). Thereafter, the glass plate coated with the curable composition was subjected to heat treatment (pre-baking) 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 with an exposure amount of 1000 mJ / cm 2 with a high-pressure mercury lamp. Then, the glass plate which has the coating film by which the whole surface exposure was carried out was heated at 200 degreeC for 300 second on the hotplate, and the cured film was obtained.
＜反射率の測定＞
　上述の方法により形成したガラス板上の硬化膜に、入射角度５°で光を入射し、正反射測定を行った。測定は、日立ハイテクノロジー製分光光度計Ｕ－４１００を用いて実施、入射光の波長を、４００～１１００ｎｍ範囲で変化させて、最大反射率を確認した。 <Measurement of reflectance>
Light was incident on the cured film on the glass plate formed by the above-described method at an incident angle of 5 °, and specular reflection measurement was performed. The measurement was performed using a spectrophotometer U-4100 manufactured by Hitachi High Technology, and the maximum reflectance was confirmed by changing the wavelength of incident light in the range of 400 to 1100 nm.
　反射率の測定結果、および、各硬化性組成物の組成を以下の表１にまとめて示す。なお、表１中の各成分欄の数値は、質量部を表す。また、表１中、「発生塩基の分子量」とは、光塩基発生剤が分解して発生する塩基（第１級アミンまたは第２級アミン）の、構造式から算出した分子量を意味する。また、「量比」とは、光塩基発生剤と分散剤との質量比（光塩基発生剤の質量／分散剤の質量）を意味する。 The measurement results of reflectance and the composition of each curable composition are summarized in Table 1 below. In addition, the numerical value of each component column in Table 1 represents a mass part. In Table 1, “molecular weight of the generated base” means the molecular weight calculated from the structural formula of the base (primary amine or secondary amine) generated by decomposition of the photobase generator. The “quantity ratio” means a mass ratio of the photobase generator and the dispersant (the mass of the photobase generator / the mass of the dispersant).
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　表１に示すように、所定の成分を含有する硬化性組成物により形成される硬化膜は優れた低反射性を有していた。また、各硬化膜は優れた遮光性を有するため、遮光膜として用いることができることがわかった。
　一方、所定の光塩基発生剤を含有しない比較例１の硬化性組成物により形成される硬化膜は、所望の効果は得られなかった。 As shown in Table 1, the cured film formed of the curable composition containing the predetermined component had excellent low reflectivity. Moreover, since each cured film had the outstanding light-shielding property, it turned out that it can be used as a light-shielding film.
On the other hand, the cured film formed of the curable composition of Comparative Example 1 that does not contain the predetermined photobase generator did not achieve the desired effect.
　光塩基発生剤と分散剤の質量比（光塩基発生剤の質量／分散剤の質量）を０．０８１、０．０７９、０．４９、０．５１に変更した実施例１４～１７と実施例１とを比較すると、上記質量比が０．０８～０．５である硬化性組成物により形成される遮光膜は、より優れた低反射性を有していることがわかった。 Examples 14 to 17 and Examples in which the mass ratio of the photobase generator to the dispersant (the mass of the photobase generator / the mass of the dispersant) was changed to 0.081, 0.079, 0.49, and 0.51 1 was compared, it was found that the light-shielding film formed of the curable composition having the above mass ratio of 0.08 to 0.5 has more excellent low reflectivity.
　実施例６～８に対し、実施例１および実施例９～１２を比較すると、発生する第２級アミンの分子量が同じである場合には、一般式（ＰＢＧ）におけるＡｒａが縮環構造を有する光塩基発生剤を含有する硬化性組成物により形成される遮光膜の方が、より優れた低反射性を有していることがわかった。 When Examples 1 and 9 to 12 are compared with Examples 6 to 8, when the molecular weight of the generated secondary amine is the same, Ar a in the general formula (PBG) has a condensed ring structure. It turned out that the direction of the light shielding film formed with the curable composition containing the photobase generator which has has the more excellent low reflectivity.
　光塩基発生剤の一般式（ＰＢＧ）におけるＡｒａ基が式（ＣＲ１）である実施例１～５を比較すると、発生する塩基の分子量が小さい光塩基発生剤を含有する硬化性組成物により形成される遮光膜の方が、より優れた低反射性を有していることがわかった。
　また、実施例１と３３とを比較すると、一般式（ＰＢＧ）中、ＲａおよびＲｂがアルキル基である光塩基発生剤を含有する硬化性組成物により形成される遮光膜の方が、より優れた低反射性を有していることがわかった。 When Ar a group in the general formula (PBG) photobase generating agent Comparison of Examples 1-5 is of formula (CR1), forming a curable composition containing a low molecular weight photobase generator of bases that occur It was found that the light shielding film to be used has better low reflectivity.
Further, when Examples 1 and 33 are compared, the light-shielding film formed of the curable composition containing the photobase generator in which R a and R b are alkyl groups in the general formula (PBG) It has been found that it has better low reflectivity.
　実施例１と実施例２０とを比較すると、含フッ素樹脂を含有する硬化性組成物により形成される遮光膜の方が、より優れた低反射性を有していることがわかった。 When comparing Example 1 and Example 20, it was found that the light-shielding film formed of the curable composition containing the fluorine-containing resin had better low reflectivity.
　実施例１、実施例１３、実施例３１、および、実施例３２を比較すると、ラジカル開始剤としてオキシム系開始剤を含有する硬化性組成物により形成される遮光膜の方が、より優れた低反射性を有していることがわかった。 When Example 1, Example 13, Example 31, and Example 32 are compared, the light-shielding film formed by the curable composition containing the oxime-based initiator as the radical initiator is more excellent. It was found to have reflectivity.
　実施例１と実施例２６とを比較すると、２種以上の有機溶剤を含有する硬化性組成物により形成される遮光膜の方が、より優れた低反射率を有していることがわかった。 Comparing Example 1 and Example 26, it was found that the light-shielding film formed from the curable composition containing two or more organic solvents had a better low reflectance. .
　実施例１と実施例２３とを比較すると、チタン化合物（チタンブラック）を含有する硬化性組成物により形成される遮光膜の方が、より優れた低反射率を有していることがわかった。
　実施例１、実施例２７、および、実施例２８を比較すると、一般式（１）で表される構造単位を有する高分子化合物を分散剤として含有する硬化性組成物により形成される遮光膜の方が、より優れた低反射率を有していることがわかった。
　実施例１と実施例２９とを比較すると、エチレン性不飽和基を５個以上有する重合性化合物を含有する硬化性組成物により形成される遮光膜の方が、より優れた低反射率を有していることがわかった。 When Example 1 was compared with Example 23, it was found that the light-shielding film formed of the curable composition containing the titanium compound (titanium black) had a better low reflectance. .
When Example 1, Example 27, and Example 28 are compared, 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 is shown. Was found to have better low reflectivity.
When Example 1 is compared with Example 29, the light-shielding film formed of the curable composition containing a polymerizable compound having 5 or more ethylenically unsaturated groups has a more excellent low reflectance. I found out.
〔ウェハレベルレンズ用遮光膜の作製および評価〕
　以下の操作により、レンズ膜を形成した。 [Production and evaluation of light shielding film for wafer level lens]
A lens film was formed by the following operation.
＜レンズ膜の形成＞
　脂環式エポキシ樹脂（ダイセル化学社製ＥＨＰＥ－３１５０）にアリールスルホニウム塩誘導体（ＡＤＥＫＡ社製ＳＰ－１７２）を１質量％添加したレンズ膜形成用組成物２ｍＬを５×５ｃｍのガラス基板（厚さ１ｍｍ、Ｓｃｈｏｔｔ社製、ＢＫ７）上に塗布し、塗膜を２００℃で１分間加熱して硬化させ、厚さ８０μｍのレンズ膜を形成した。 <Formation of lens film>
A glass substrate (thickness) of 2 mL of a composition for forming a lens film, in which 1% by mass of an arylsulfonium salt derivative (SP-172 manufactured by ADEKA) is added to an alicyclic epoxy resin (EHPE-3150 manufactured by Daicel Chemical Industries) 1 mm, manufactured by Schott, BK7), and the coating film was cured by heating at 200 ° C. for 1 minute to form a lens film having a thickness of 80 μm.
＜硬化性組成物層形成工程＞
　レンズ膜を形成したガラス基板（以下「支持体」という。）のレンズ膜上に、実施例１の硬化性組成物を塗布し、表面温度１２０℃のホットプレートにより硬化性組成物１が塗布された支持体を１２０秒間加熱した。このようにして、膜厚２．０μｍの塗膜（硬化性組成物層に該当する。）を得た。 <Curable composition layer forming step>
The curable composition of Example 1 was applied on a lens film of a glass substrate (hereinafter referred to as “support”) on which the lens film was formed, and the curable composition 1 was applied by a hot plate having a surface temperature of 120 ° C. The support was heated for 120 seconds. Thus, a coating film (corresponding to a curable composition layer) having a thickness of 2.0 μm was obtained.
＜露光工程＞
　次いで、高圧水銀灯を用い、１０ｍｍのホールパターンを有するフォトマスクを介して露光量５００ｍＪ／ｃｍ２で、得られた硬化性組成物層を露光した。 <Exposure process>
Subsequently, the obtained curable composition layer was exposed with the exposure amount of 500 mJ / cm < 2 > through the photomask which has a 10 mm hole pattern using the high pressure mercury lamp.
＜現像工程＞
　上記露光後の硬化性組成物層に対し、現像液としてテトラメチルアンモニウムハイドロオキサイド０．３％水溶液を用い、２３℃の温度で６０秒間パドル現像を行った。その後、現像処理が施された硬化性組成物層のリンス処理をスピンシャワーにて行い、更に、リンス処理が施された組成物層を純水にて洗浄し、パターン状の遮光膜を得た。 <Development process>
The curable composition layer after the exposure was subjected to paddle development for 60 seconds at a temperature of 23 ° C. using a 0.3% aqueous solution of tetramethylammonium hydroxide as a developer. Thereafter, the curable composition layer subjected to the development treatment was rinsed with a spin shower, and the rinsed composition layer was washed with pure water to obtain a patterned light-shielding film. .
＜固体撮像装置の作製＞
　上述の方法により作製したパターン状の遮光膜上に、上述のレンズ膜形成用組成物を用いて、塗膜を形成した。その後、レンズ形状を持つ石英モールドで形状を転写して高圧水銀ランプにより４００ｍＪ／ｃｍ２の露光量で塗膜を硬化させることにより、ウェハレベルレンズを複数有するウェハレベルレンズアレイを作製した。
　作製されたウェハレベルレンズアレイを切断し、得られたウェハレベルレンズを用いてレンズモジュールを作製した後に、撮像素子およびセンサ基板を取り付け、撮像ユニット（固体撮像装置に該当する。）を作製した。 <Production of solid-state imaging device>
A coating film was formed on the patterned light-shielding film produced by the above-described method using the above-described lens film-forming composition. Thereafter, the shape was transferred with a quartz mold having a lens shape, and the coating film was cured with a high pressure mercury lamp at an exposure amount of 400 mJ / cm 2 , thereby producing a wafer level lens array having a plurality of wafer level lenses.
The produced wafer level lens array was cut and a lens module was produced using the obtained wafer level lens, and then an imaging device and a sensor substrate were attached to produce an imaging unit (corresponding to a solid-state imaging device).
＜評価＞
　得られたウェハレベルレンズは、レンズ開口部に残渣物が無く良好な透過性を有していた。また、遮光層は、低反射であり、塗布面の均一性が高く、遮光性が高いものであった。 <Evaluation>
The obtained wafer level lens was free from residue at the lens opening and had good transparency. Further, the light shielding layer had low reflection, high uniformity of the coated surface, and high light shielding properties.
〔ブラックマトリクスを有するカラーフィルタの作製および評価〕
　以下の操作によりブラックマトリクスを有するカラーフィルタを作製した。 [Production and evaluation of color filter having black matrix]
A color filter having a black matrix was produced by the following operation.
＜ブラックマトリクスの形成＞
　実施例１の硬化性組成物をガラスウエハにスピンコート法で塗布し、その後ホットプレート上にて、硬化性組成物が塗布されたガラスウエハを１２０℃で２分加熱して、塗膜（硬化性組成物層に該当する）を得た。得られた塗膜の膜厚は２．０μｍであった。
　次いで、ｉ線ステッパーを用い、パターンが０．１ｍｍのＩｓｌａｎｄパターンを有するフォトマスクを通して５００ｍＪ／ｃｍ２の露光量で、硬化性組成物層を露光した。
　上記露光後の硬化性組成物層に対し、現像液としてテトラメチルアンモニウムハイドロオキサイド０．３％水溶液を用い、２３℃６０秒間パドル現像を行った。その後、現像処理が施された硬化性組成物層のリンス処理をスピンシャワーにて行い、更にリンス処理が施された硬化性組成物層を純水にて洗浄し、パターン状の遮光膜（ブラックマトリクス）を得た。 <Formation of black matrix>
The curable composition of Example 1 was applied to a glass wafer by spin coating, and then the glass wafer on which the curable composition was applied was heated on a hot plate at 120 ° C. for 2 minutes to form a coating film (cured). Corresponded to the composition layer). The film thickness of the obtained coating film was 2.0 μm.
Next, using an i-line stepper, the curable composition layer was exposed at a dose of 500 mJ / cm 2 through a photomask having an Island pattern with a pattern of 0.1 mm.
The curable composition layer after the exposure was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide as a developer. Thereafter, the curable composition layer that has been subjected to the development treatment is rinsed by a spin shower, and the curable composition layer that has been further rinsed is washed with pure water to form a patterned light-shielding film (black Matrix).
＜有彩色硬化性組成物の調製＞
　実施例１の硬化性組成物において、チタンブラックを、下記有彩色系顔料に替えたほかは同様にして、それぞれ赤色（Ｒ）用着色硬化性組成物Ｒ－１、緑色（Ｇ）用着色硬化性組成物Ｇ－１、および青色（Ｂ）用着色硬化性組成物Ｂ－１を調製した。
　～ＲＧＢ各色着色画素形成用の有彩色系顔料～
・赤色（Ｒ）用顔料
　Ｃ．Ｉ．ピグメント・レッド２５４
・緑色（Ｇ）用顔料
　Ｃ．Ｉ．ピグメント・グリーン３６とＣ．Ｉ．ピグメント・イエロー２１９との３０／７０〔質量比〕混合物
・青色（Ｂ）用顔料
　Ｃ．Ｉ．ピグメント・ブルー１５：６とＣ．Ｉ．ピグメント・バイオレット２３との３０／７０〔質量比〕混合物 <Preparation of chromatic color curable composition>
In the same manner as in Example 1, except that the titanium black was replaced with the following chromatic pigments, red (R) colored curable composition R-1 and green (G) colored cured, respectively. Composition G-1 and a colored curable composition B-1 for blue (B) were prepared.
-Chromatic pigments for forming colored pixels for each color of RGB-
-Red (R) pigment C.I. I. Pigment Red 254
-Green (G) pigment C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 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
＜カラーフィルタの作製＞
　上記で作製したブラックマトリクス内に、上記赤色（Ｒ）用着色硬化性組成物Ｒ－１を用いて、上記で作製したブラックマトリクスの作製方法と同じ要領で８０×８０μｍの赤色（Ｒ）の着色パターンを形成した。更に、同様にして緑色（Ｇ）用着色硬化性組成物Ｇ－１を用いて緑色（Ｇ）の有彩色着色パターンを、および青色（Ｂ）用着色硬化性組成物Ｂ－１を用いて青色（Ｂ）の有彩色着色パターンを順次形成して液晶表示装置用のブラックマトリクスを有するカラーフィルタを作製した。 <Production of color filter>
The red (R) colored curable composition R-1 is used in the black matrix produced above, and the red (R) is colored 80 × 80 μm in the same manner as the black matrix produced above. A pattern was formed. Further, in the same manner, a green (G) chromatic coloring pattern is obtained using the green (G) colored curable composition G-1, and a blue color using the blue (B) colored curable composition B-1. A chromatic color pattern of (B) was sequentially formed to produce a color filter having a black matrix for a liquid crystal display device.
＜評価＞
　得られたカラーフィルタを搭載した液晶表示装置は高コントラストで鮮明な画像が得られ、外光下でも視認性に極めて優れることが分かった。
　遮光層は、光学濃度が高く、バックライトの光を通さないための十分な遮光性が実現できるため、高コントラストで鮮明な画像が得られるばかりでなく、反射率が低いために外光下でも視認性に極めて優れることが推定される。 <Evaluation>
It was found that a liquid crystal display device equipped with the obtained color filter can obtain a clear image with high contrast and is extremely excellent in visibility even under external light.
The light-shielding layer has a high optical density and can achieve a sufficient light-shielding property to prevent the light from passing through the backlight. It is estimated that the visibility is extremely excellent.
　２，２０，３０，４０　固体撮像装置
　３　ＣＭＯＳセンサ
　４　回路基板
　５　セラミック基板
　５ａ　開口
　５ｂ　内壁面
　６　ＩＲカットフィルタ
　６ａ　入射面
　７　撮影レンズ
　８　レンズホルダ
　９　保持筒
　１０，１１，２１，３１，４１　遮光膜（遮光層） 2, 20, 30, 40 Solid-state imaging device 3 CMOS sensor 4 Circuit board 5 Ceramic substrate 5a Opening 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 Light shielding Film (light shielding layer)

Claims (13)

  1. 　着色剤と、光ラジカル重合開始剤と、重合性化合物と、塩基発生剤と、分散剤と、を含有する硬化性組成物。 A curable composition containing a colorant, a radical photopolymerization initiator, a polymerizable compound, a base generator, and a dispersant.
  2. 　前記塩基発生剤が光塩基発生剤を含有する、請求項１に記載の硬化性組成物。 The curable composition according to claim 1, wherein the base generator contains a photobase generator.
  3. 　前記分散剤に対する前記光塩基発生剤の質量比が、０．０８～０．５である、請求項２に記載の硬化性組成物。 The curable composition according to claim 2, wherein a mass ratio of the photobase generator to the dispersant is 0.08 to 0.5.
  4. 　前記光塩基発生剤が、下記の一般式（ＰＢＧ）で表される請求項２または３に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
    一般式（ＰＢＧ）中、ＲａおよびＲｂはそれぞれ独立に水素原子または１価の有機基を表し、ＲａおよびＲｂは互いに結合して環を形成してもよく、Ａｒａはアリール基またはヘテロアリール基を表す。     The curable composition according to claim 2 or 3, wherein the photobase generator is represented by the following general formula (PBG).
    Figure JPOXMLDOC01-appb-C000001
    In General Formula (PBG), R a and R b each independently represent a hydrogen atom or a monovalent organic group, R a and R b may be bonded to each other to form a ring, and Ar a is an aryl group Or represents a heteroaryl group.
  5. 　前記光塩基発生剤から発生する塩基がアミン化合物であって、前記アミン化合物の分子量が１５０以下である請求項２～４のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 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. 　前記光ラジカル重合開始剤が、オキシム系開始剤である請求項１～５のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 5, wherein the photo radical polymerization initiator is an oxime initiator.
  7. 　前記着色剤が、遮光性顔料である請求項１～６のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 6, wherein the colorant is a light-shielding pigment.
  8. 　前記遮光性顔料が、チタン化合物である請求項７に記載の硬化性組成物。 The curable composition according to claim 7, wherein the light-shielding pigment is a titanium compound.
  9. 　さらに、含フッ素樹脂を含有する請求項１～８のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 8, further comprising a fluorine-containing resin.
  10. 　さらに、２種以上の有機溶剤を含有する請求項１～９のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 9, further comprising two or more organic solvents.
  11. 　請求項１～１０のいずれか一項に記載の硬化性組成物を硬化して得られる遮光膜。 A light-shielding film obtained by curing the curable composition according to any one of claims 1 to 10.
  12. 　請求項１１に記載の遮光膜を有する、固体撮像装置。 A solid-state imaging device having the light-shielding film according to claim 11.
  13. 　請求項１２に記載の遮光膜を有する、カラーフィルタ。 A color filter having the light shielding film according to claim 12.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019168089A1 (en) * 2018-03-02 2019-09-06 日本化薬株式会社 Novel compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator
JP6885518B1 (en) * 2019-07-22 2021-06-16 三菱ケミカル株式会社 Photosensitive colored resin composition, cured product, partition wall and image display device
WO2022196450A1 (en) * 2021-03-19 2022-09-22 富士フイルム株式会社 Colored composition, method for producing film, method for producing color filter, method for producing solid imaging element, and method for producing image display device

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210052452A (en) * 2018-08-30 2021-05-10 닛산 가가쿠 가부시키가이샤 Negative photosensitive resin composition

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010143560A1 (en) * 2009-06-08 2010-12-16 三洋化成工業株式会社 Photosensitive composition
JP2011075691A (en) * 2009-09-29 2011-04-14 Dainippon Printing Co Ltd Color filter for organic electroluminescence display device
JP2012053465A (en) * 2010-08-06 2012-03-15 Sanyo Chem Ind Ltd Photosensitive composition
JP2013029709A (en) * 2011-07-29 2013-02-07 Fujifilm Corp Colored photosensitive resin composition, color filter, and liquid crystal display element having color filter
JP2013148857A (en) * 2011-12-22 2013-08-01 Tokyo Ohka Kogyo Co Ltd Photosensitive resin composition, color filter, and liquid crystal display device
US20140162178A1 (en) * 2012-12-10 2014-06-12 Lg Display Co., Ltd. Photosensitive composition for display device, black matrix having the composition, and method of forming black matrix using the composition
JP2015099313A (en) * 2013-11-20 2015-05-28 凸版印刷株式会社 Black photosensitive resin composition, black matrix, color filter, liquid crystal display device, and electroluminescence display device
JP2016156856A (en) * 2015-02-23 2016-09-01 三洋化成工業株式会社 Photosensitive composition for forming color filter
JP2016212347A (en) * 2015-05-13 2016-12-15 三洋化成工業株式会社 Manufacturing method of photosensitive composition for forming color filter

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5546734B2 (en) * 2007-03-29 2014-07-09 東京応化工業株式会社 Colored photosensitive resin composition, black matrix, color filter, and liquid crystal display
JP5223633B2 (en) * 2008-12-02 2013-06-26 大日本印刷株式会社 Photosensitive resin composition, article using the same, and negative pattern forming method
JP2011215316A (en) * 2010-03-31 2011-10-27 Dainippon Printing Co Ltd Color filter substrate and display device
JP5898985B2 (en) * 2011-05-11 2016-04-06 東京応化工業株式会社 Resist pattern forming method
US9244346B2 (en) * 2011-06-24 2016-01-26 Tokyo Ohka Kogyo Co., Ltd. Negative-type photosensitive resin composition, pattern forming method, cured film, insulating film, color filter, and display device
JP2015007770A (en) * 2013-05-29 2015-01-15 住友ベークライト株式会社 Photosensitive resin composition, and electronic device
CN110941142B (en) * 2014-03-17 2021-05-25 旭化成株式会社 Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device
TWI671343B (en) * 2014-06-27 2019-09-11 日商富士軟片股份有限公司 Thermosetting resin composition, cured film, method for producing cured film, and semiconductor device

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010143560A1 (en) * 2009-06-08 2010-12-16 三洋化成工業株式会社 Photosensitive composition
JP2011075691A (en) * 2009-09-29 2011-04-14 Dainippon Printing Co Ltd Color filter for organic electroluminescence display device
JP2012053465A (en) * 2010-08-06 2012-03-15 Sanyo Chem Ind Ltd Photosensitive composition
JP2013029709A (en) * 2011-07-29 2013-02-07 Fujifilm Corp Colored photosensitive resin composition, color filter, and liquid crystal display element having color filter
JP2013148857A (en) * 2011-12-22 2013-08-01 Tokyo Ohka Kogyo Co Ltd Photosensitive resin composition, color filter, and liquid crystal display device
US20140162178A1 (en) * 2012-12-10 2014-06-12 Lg Display Co., Ltd. Photosensitive composition for display device, black matrix having the composition, and method of forming black matrix using the composition
JP2015099313A (en) * 2013-11-20 2015-05-28 凸版印刷株式会社 Black photosensitive resin composition, black matrix, color filter, liquid crystal display device, and electroluminescence display device
JP2016156856A (en) * 2015-02-23 2016-09-01 三洋化成工業株式会社 Photosensitive composition for forming color filter
JP2016212347A (en) * 2015-05-13 2016-12-15 三洋化成工業株式会社 Manufacturing method of photosensitive composition for forming color filter

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MASAHIRO TSUNOOKA: "Recent Trends of Photocrosslinking Systems by the Use of Photoacid and Photobase Generators", NETWORK POLYMER, vol. 18, no. 1, 1997, pages 27 - 35 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019168089A1 (en) * 2018-03-02 2019-09-06 日本化薬株式会社 Novel compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator
JPWO2019168089A1 (en) * 2018-03-02 2021-04-01 日本化薬株式会社 A novel compound, a photopolymerization initiator containing the compound, and a photosensitive resin composition containing the photopolymerization initiator.
US11414382B2 (en) 2018-03-02 2022-08-16 Nippon Kayaku Kabushiki Kaisha Compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator
JP7218073B2 (en) 2018-03-02 2023-02-06 日本化薬株式会社 Novel compound, photopolymerization initiator comprising said compound, and photosensitive resin composition containing said photopolymerization initiator
JP6885518B1 (en) * 2019-07-22 2021-06-16 三菱ケミカル株式会社 Photosensitive colored resin composition, cured product, partition wall and image display device
JP2021120756A (en) * 2019-07-22 2021-08-19 三菱ケミカル株式会社 Photosensitive colored resin composition, cured product, partition wall and image display device
CN113993922A (en) * 2019-07-22 2022-01-28 三菱化学株式会社 Photosensitive colored resin composition, cured product, partition wall, and image display device
JP7201019B2 (en) 2019-07-22 2023-01-10 三菱ケミカル株式会社 Photosensitive colored resin composition, cured product, partition wall and image display device
WO2022196450A1 (en) * 2021-03-19 2022-09-22 富士フイルム株式会社 Colored composition, method for producing film, method for producing color filter, method for producing solid imaging element, and method for producing image display device

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