WO2020066871A1 - 硬化性組成物、硬化膜、パターンの形成方法、光学フィルタおよび光センサ - Google Patents

硬化性組成物、硬化膜、パターンの形成方法、光学フィルタおよび光センサ Download PDF

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Publication number
WO2020066871A1
WO2020066871A1 PCT/JP2019/036905 JP2019036905W WO2020066871A1 WO 2020066871 A1 WO2020066871 A1 WO 2020066871A1 JP 2019036905 W JP2019036905 W JP 2019036905W WO 2020066871 A1 WO2020066871 A1 WO 2020066871A1
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Prior art keywords
compound
curable composition
group
mass
photopolymerization initiator
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PCT/JP2019/036905
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English (en)
French (fr)
Japanese (ja)
Inventor
全弘 森
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富士フイルム株式会社
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Priority to JP2020549105A priority Critical patent/JP7059387B2/ja
Priority to KR1020217004975A priority patent/KR102527570B1/ko
Publication of WO2020066871A1 publication Critical patent/WO2020066871A1/ja

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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
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/0325—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polysaccharides, e.g. cellulose
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Definitions

  • the present invention relates to a curable composition, a cured film, a method for forming a pattern, an optical filter, and an optical sensor.
  • Patent Literature 1 discloses a color filter array having a semiconductor substrate, a color filter array having two or more color filter layers, and a separation wall separating at least a color filter layer of a different color between the semiconductor substrate and the color filter array. And a light-collecting unit disposed in the solid-state imaging device.
  • optical sensors that sense near infrared rays have been studied. Near-infrared rays have a longer wavelength than visible rays, so they are not easily scattered, and can be used for distance measurement, three-dimensional measurement, and the like. In addition, since near-infrared light is invisible to humans and animals, even when illuminating the subject with near-infrared light at night, the subject is not noticed, and it stimulates the opponent as an application for shooting nocturnal wildlife and security. It can also be used to shoot without. As described above, the optical sensor that senses near-infrared rays can be developed for various uses. In such an optical sensor, a filter having a transmission band in a near-infrared region such as a near-infrared transmission filter is used (for example, see Patent Documents 2 and 3).
  • the above-described color filter and near-infrared transmission filter form a film using a curable composition containing a coloring material, a polymerizable compound, and a photopolymerization initiator, and cure the film by heating or the like. It is manufactured by doing.
  • Patent Document 4 discloses that a color filter is manufactured using a curable composition using an oxime ester-based photopolymerization initiator containing a fluorine atom as a photopolymerization initiator.
  • non-Si-based materials such as organic materials, quantum dots, and InGaAs (indium gallium arsenide) have been used in solid-state imaging devices in place of Si-based materials from the viewpoints of high resolution, high sensitivity, power saving and miniaturization. It has been studied to carry out photoelectric conversion using. Since the non-Si-based material as described above is weaker to heat than the Si-based material, it is desired that the heating temperature at the time of curing the curable composition be less than 200 ° C.
  • the present invention has been made in view of the above demands, and has as its object to provide a curable composition capable of forming a cured film having excellent adhesion at a low temperature.
  • the above problem was solved by using two types of photopolymerization initiators having predetermined light absorption characteristics different from each other in a curable composition having a low transmittance for light having a wavelength of 365 nm. Specifically, the above problem was solved by the following means ⁇ 1>, preferably by ⁇ 2> to ⁇ 20>.
  • the photopolymerization initiator A1 has an extinction coefficient of 1.0 ⁇ 10 3 mL / gcm or more in methanol at a wavelength of 365 nm, and the photopolymerization initiator A1 has an extinction coefficient of 1.0 ⁇ 10 3 in methanol at a wavelength of 365 nm.
  • the photopolymerization initiator A1 is an oxime compound, The curable composition according to ⁇ 1>.
  • the oxime compound is a compound containing a fluorine atom, The curable composition according to ⁇ 2>.
  • the photopolymerization initiator A2 is a hydroxyalkylphenone compound, The curable composition according to any one of ⁇ 1> to ⁇ 3>.
  • the photopolymerization initiator A2 is a compound represented by the following formula (A2-1): The curable composition according to any one of ⁇ 1> to ⁇ 3>; Formula (A2-1): In the formula, Rv 1 represents a substituent, Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent, and Rv 2 and Rv 3 may combine with each other to form a ring. , M represents an integer of 0 to 5.
  • the photopolymerization initiator A2 contains 50 to 200 parts by mass with respect to 100 parts by mass of the photopolymerization initiator A1.
  • the total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the curable composition is 5 to 15% by mass;
  • the polymerizable compound is a compound containing three or more ethylenically unsaturated groups, The curable composition according to any one of ⁇ 1> to ⁇ 7>.
  • the polymerizable compound is a compound containing an ethylenically unsaturated group and an alkyleneoxy group
  • the polymerizable compound is contained in an amount of 170 to 345 parts by mass based on 100 parts by mass of the photopolymerization initiator A1 and the photopolymerization initiator A2 in total.
  • the content of the polymerizable compound in the total solid content of the curable composition is 17.5 to 27.5% by mass;
  • the coloring material is a black coloring material containing at least one of a bisbenzofuranone compound, a perylene compound, and an azo compound.
  • the colorant comprises at least three compounds, The curable composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 14> Further, a compound having a cyclic ether structure, and a curing accelerator for a compound having a cyclic ether structure, The curable composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> Further containing resin, The curable composition according to any one of ⁇ 1> to ⁇ 14>.
  • ⁇ 16> A cured film obtained by curing the curable composition according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 17> Forming a curable composition layer on a support using the curable composition according to any one of ⁇ 1> to ⁇ 15>; A first exposure step of irradiating the curable composition layer with light having a wavelength of more than 350 nm and not more than 380 nm, and exposing in a pattern; A developing step of developing the curable composition layer, A second exposure step of irradiating the curable composition layer with light having a wavelength of 254 to 350 nm after the development step.
  • ⁇ 18> A step of heating the curable composition layer at a temperature of less than 200 ° C.
  • the curable composition of the present invention enables a cured film having excellent adhesion to be formed at a low temperature.
  • the curable composition of the present invention can provide the cured film, the pattern forming method, the optical filter, and the optical sensor of the present invention.
  • the numerical range represented by the symbol “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit, respectively.
  • step is meant to include not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended operation of the step can be achieved.
  • the notation of not indicating substituted or unsubstituted includes not only those having no substituent but also those having a substituent.
  • alkyl group when the term “alkyl group” is simply used, this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Meaning.
  • (meth) acrylate means both or “acrylate” and “methacrylate”
  • (meth) acryl means both “acryl” and “methacryl”
  • (Meth) acryloyl” means both or both “acryloyl” and “methacryloyl”.
  • the concentration of the total solids in a composition is represented by the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
  • the temperature is 23 ° C. unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are determined, for example, using HLC-8220 (manufactured by Tosoh Corporation) and using a guard column HZ-L, TSKgel @ Super @ HZM-M, TSKgel @ Super @ HZ4000, TSKgel. It can be determined by using Super @ HZ3000 and TSKgel @ Super @ HZ2000 (manufactured by Tosoh Corporation).
  • each layer constituting the laminate when the positional relationship of each layer constituting the laminate is described as “up” or “down”, other layers may be placed above or below a reference layer among a plurality of layers of interest. If there is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer.
  • the direction in which the layers are stacked on the substrate is referred to as “up”, or, if there is a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as “up”.
  • the opposite direction is referred to as "down”. Note that such setting in the vertical direction is for convenience in the present specification, and in an actual embodiment, the “up” direction in the present specification may be different from the vertical upward.
  • the curable composition of the present invention contains a coloring material, a polymerizable compound, and a photopolymerization initiator. And in the curable composition of this invention, content of a coloring material is 30 mass% or more with respect to the total solid content of a composition. Furthermore, the photopolymerization initiator A1 has an extinction coefficient of 1.0 ⁇ 10 3 mL / gcm or more in methanol at 365 nm in wavelength, and the photopolymerization initiator has an extinction coefficient of 1.0 nm in methanol at 365 nm in wavelength.
  • a photopolymerization initiator A2 having an absorption coefficient of not more than ⁇ 10 2 mL / gcm and an absorption coefficient at a wavelength of 254 nm of not less than 1.0 ⁇ 10 3 mL / gcm. Further, the ratio A / B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more.
  • the curable composition of the present invention has spectral characteristics that easily absorb visible light and easily transmit near infrared rays. Therefore, for example, it is used for manufacturing a near-infrared transmission filter.
  • near infrared refers to the vicinity of a wavelength range of 700 to 2500 nm.
  • the transmittance for light having a wavelength of 365 nm is relatively low due to the influence of the bottom of the absorption characteristics in the visible light region.
  • a cured film having excellent adhesion can be formed at a low temperature.
  • the effect is considered as follows.
  • the curable composition contains the photopolymerization initiator A1 and the photopolymerization initiator A2, exposure using light having a wavelength of more than 350 nm and not more than 380 nm (for example, 365 nm) (first exposure) ) And exposure using light having a wavelength of 254 to 350 nm (for example, 254 nm) (second exposure) is performed to achieve sufficient curing at a low temperature of less than 200 ° C.
  • the term "light” is used for convenience for electromagnetic waves other than the visible region, and the meaning of "light” is the same as “electromagnetic wave” for electromagnetic waves other than the visible region.
  • the second exposure is performed.
  • the composition can be sufficiently cured by heat treatment. That is, the curable composition of the present invention can be used in a method in which exposure is performed in one step, in addition to a method in which exposure is performed in two steps.
  • a photopolymerization initiator that has absorbed light generates active species, and the polymerization of the polymerizable compound is promoted by the active action of the active species.
  • components other than the photopolymerization initiator In particular, the coloring material
  • the coloring material has a property of easily absorbing visible light, and accordingly, light having a wavelength of 365 nm close to the visible light region is also easily absorbed by components other than the photopolymerization initiator.
  • exposure using light having a wavelength of 365 nm (first exposure) is regarded as a step of imparting sufficient strength to the curable composition to withstand development, and after the first exposure and development, The second exposure using the photopolymerization initiator A2 is performed.
  • the pattern has already been cut, and the influence of the diffusion of the excessively generated active species on the pattern size is small, so that the exposure energy can be increased. Therefore, sufficient light can reach the photopolymerization initiator A2 to the deep layer of the curable composition, and the curing of the deep layer can be sufficiently promoted.
  • the present invention since the absorption coefficient of the photopolymerization initiator A2 at a wavelength of 365 nm is relatively low and the consumption of the photopolymerization initiator A2 in the first exposure can be suppressed, the polymerization can be efficiently performed in the second exposure.
  • the polymerization of the hydrophilic compound is promoted.
  • the present invention relates to a composition used in such an application. Especially useful for:
  • the deep portion of the curable composition is sufficiently cured by the second exposure, and By improving the mechanical strength of the deep portion, the adhesion to the base can be improved.
  • the A / B is preferably 5 or more, more preferably 7.5 or more, further preferably 15 or more, and particularly preferably 30 or more. Further, the A / B is preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less.
  • the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
  • a ⁇ ⁇ log (T ⁇ / 100) (1)
  • a ⁇ is the absorbance at the wavelength ⁇
  • T ⁇ is the transmittance (%) at the wavelength ⁇ .
  • the value of the absorbance may be a value measured in a state of a solution, or a value of a film formed using a curable composition.
  • a method such as spin coating on a glass substrate
  • Apply the curable composition so that the thickness of the film after drying becomes a predetermined thickness, and use a hot plate.
  • the measurement is preferably performed using a film prepared by drying at 100 ° C. for 120 seconds.
  • the thickness of the film can be measured for the substrate having the film by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC).
  • the absorbance can be measured using a conventionally known spectrophotometer. It is preferable to measure the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm under the condition that the minimum value A of the absorbance in the wavelength range of 400 to 600 nm is adjusted to be 0.1 to 3.0. By measuring the absorbance under such conditions, the measurement error can be reduced. There is no particular limitation on the method for adjusting the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to be 0.1 to 3.0. For example, when measuring the absorbance in the state of a solution, a method of adjusting the optical path length of the sample cell may be used.
  • the absorbance When the absorbance is measured in the state of the film, a method of adjusting the film thickness may be used.
  • the absorbance can be measured using, for example, an ultraviolet-visible-near-infrared spectrophotometer.
  • an ultraviolet-visible-near-infrared spectrophotometer As such an apparatus, for example, U-4100 (manufactured by Hitachi High-Tech) can be used.
  • the curable composition more preferably satisfies any of the following spectral characteristics (1) to (4).
  • Amin1 / Bmax1 which is the ratio of the minimum absorbance Amin1 in the wavelength range of 400 to 640 nm to the maximum absorbance Bmax1 in the wavelength range of 800 to 1300 nm, is 5 or more and 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin1 / Bmax1 is preferably 500 or less, more preferably 400 or less, and still more preferably 300 or less. According to this aspect, it is possible to form a film capable of transmitting near-infrared light having a wavelength of 750 nm or less while blocking light having a wavelength in the range of 400 to 640 nm. Such a film preferably has, for example, spectral characteristics in which the maximum value of the transmittance at a wavelength of 400 to 640 nm is 20% and the transmittance at a wavelength of 750 nm is 70% or more.
  • Amin2 / Bmax2 which is the ratio of the minimum absorbance Amin2 in the wavelength range of 400 to 750 nm to the maximum absorbance Bmax2 in the wavelength range of 900 to 1300 nm, is 5 or more and 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin2 / Bmax2 is preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less. According to this aspect, it is possible to form a film capable of transmitting near-infrared light having a wavelength of 850 nm or less while blocking light having a wavelength of 400 to 750 nm. Such a film preferably has, for example, spectral characteristics in which the maximum value of the transmittance at a wavelength of 400 to 750 nm is 20% and the transmittance at a wavelength of 850 nm is 70% or more.
  • Amin3 / Bmax3 which is the ratio of the minimum absorbance Amin3 in the wavelength range of 400 to 850 nm to the maximum absorbance Bmax3 in the wavelength range of 1000 to 1300 nm, is 5 or more, and is 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin3 / Bmax3 is preferably equal to or less than 500, more preferably equal to or less than 400, and still more preferably equal to or less than 300. According to this aspect, it is possible to form a film capable of transmitting near-infrared light having a wavelength of 940 nm or less while blocking light having a wavelength of 400 to 830 nm. Such a film preferably has, for example, spectral characteristics such that the maximum value of the transmittance at a wavelength of 400 to 830 nm is 20% and the transmittance at a wavelength of 940 nm is 70% or more.
  • Amin4 / Bmax4 which is the ratio of the minimum absorbance Amin4 in the wavelength range of 400 to 950 nm to the maximum absorbance Bmax4 in the wavelength range of 1100 to 1300 nm, is 5 or more, and is 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin4 / Bmax4 is preferably equal to or less than 500, more preferably equal to or less than 400, and still more preferably equal to or less than 300. According to this aspect, it is possible to form a film that shields light in the wavelength range of 400 to 950 nm and transmits near infrared rays having a wavelength of 1040 nm or less. For example, such a film preferably has spectral characteristics such that the maximum value of the transmittance at a wavelength of 400 to 950 nm is 20% and the transmittance at a wavelength of 1040 nm is 70% or more.
  • the curable composition of the present invention contains a coloring material.
  • the coloring material is preferably a material that transmits at least a part of light in a near-infrared region and absorbs light in a visible region.
  • the coloring material is preferably a material that absorbs light in a violet to red wavelength region.
  • the coloring material is preferably a material that absorbs light in a wavelength region of 400 to 600 nm.
  • the coloring material is preferably a material that transmits light having a wavelength of 1000 to 1300 nm.
  • the coloring material preferably satisfies at least one of the following requirements (A) and (B).
  • A Two or more chromatic colorants are included, and black is formed by a combination of two or more chromatic colorants.
  • B Contains an organic black colorant.
  • the chromatic colorant means a colorant other than a white colorant and a black colorant.
  • the organic black colorant means a material that absorbs visible light but transmits at least a part of infrared light. Therefore, in the present invention, the organic black colorant does not include a black colorant that absorbs both visible light and infrared light, for example, carbon black and titanium black.
  • the organic black colorant is preferably a colorant having a maximum absorption wavelength in a wavelength range of 400 nm to 700 nm.
  • the color material is, for example, a material in which the ratio A / B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more. Is preferred.
  • the wavelength ⁇ p at which the absorbance (extinction coefficient) in the wavelength range of 400 to 600 nm is maximum is preferably larger than 365 nm by 20 nm or more, more preferably 30 nm or more. When the wavelength ⁇ p satisfies the above requirements, the irradiation light for exposure can be efficiently absorbed by the photopolymerization initiator described below.
  • the above-mentioned spectral characteristics may be satisfied with one kind of material, or may be satisfied with a combination of a plurality of materials.
  • the above-mentioned spectral characteristics are satisfied by combining a plurality of chromatic colorants.
  • the organic black colorant alone may satisfy the above-mentioned spectral characteristics.
  • the above spectral characteristics may be satisfied by a combination of an organic black colorant and a chromatic colorant.
  • the chromatic colorant is preferably a colorant selected from a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.
  • the chromatic colorant may be a pigment or a dye. Preferably, it is a pigment.
  • a material in which an inorganic pigment or an organic-inorganic pigment is partially replaced with an organic chromophore can be used. By partially replacing the inorganic pigment or the organic-inorganic pigment with an organic chromophore, the hue design can be facilitated.
  • the pigment preferably has an average particle size (r) of 20 nm ⁇ r ⁇ 300 nm, more preferably 25 nm ⁇ r ⁇ 250 nm, and still more preferably 30 nm ⁇ r ⁇ 200 nm.
  • the “average particle size” here means an average particle size of secondary particles in which primary particles of the pigment are aggregated.
  • the particle size distribution of the secondary particles of the pigment that can be used (hereinafter, also referred to simply as “particle size distribution”) is such that the secondary particles contained in the range of the average particle size ⁇ 100 nm are 70% by mass or more of the whole. Preferably, it is 80% by mass or more.
  • the particle size distribution of the secondary particles is measured using a scattering intensity distribution.
  • the chromatic colorant used in the present invention preferably contains a pigment. Further, the content of the pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and more preferably 90% by mass or more. Is particularly preferred.
  • the chromatic colorant may be a pigment alone. Examples of the pigment include the following.
  • Yellow pigment C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Or more, orange pigment), C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3.
  • a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule.
  • a compound described in CN106909097A, a phthalocyanine compound having a phosphate as a ligand, or the like can also be used.
  • an aluminum phthalocyanine compound having a phosphorus atom can be used as the blue pigment.
  • Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247593 and paragraph 0047 of JP-A-2011-157478.
  • yellow pigment a pigment described in JP-A-2017-201303 and a pigment described in JP-A-2017-197719 can be used.
  • a metal containing at least one anion, two or more metal ions, and a melamine compound selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof: Azo pigments can also be used.
  • the alkyl group represented by R 5 to R 7 preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, and still more preferably has 1 to 4 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.
  • the substituent is preferably a halogen atom, a hydroxyl group, an alkoxy group, a cyano group or an amino group.
  • yellow pigment a compound described in JP-A-2018-062644 can also be used. This compound can also be used as a pigment derivative.
  • red pigments diketopyrrolopyrrole-based pigments in which at least one bromine atom is substituted in the structure described in JP-A-2017-2013384, diketopyrrolopyrrole-based pigments described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 Etc. can also be used.
  • red pigment a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is introduced to a diketopyrrolopyrrole skeleton may be used. it can.
  • the dye is not particularly limited, and a known dye can be used.
  • a known dye can be used.
  • thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, azo compounds described in JP-A-2011-145540, and JP-A-2018-012863. Can also be preferably used.
  • yellow dye quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339, quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228, and the like can be used.
  • dyes described in WO 2012/128233 and JP-A-2017-201303 can be used.
  • red colorant dyes described in WO2012 / 102399, WO2012 / 117965 and JP-A-2012-229344 can be used.
  • green colorant a dye described in International Publication No. 2012/102395 can be used.
  • a salt-forming dye described in WO 2011/037195 can be used.
  • the coloring material preferably contains two or more selected from a red coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent and a green coloring agent. That is, it is preferable that the colorant forms black by a combination of two or more types of colorants selected from a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
  • Preferred combinations include, for example, the following. (1) A combination of a red colorant and a blue colorant. (2) A combination of a red colorant, a blue colorant and a yellow colorant. (3) A combination of a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
  • a combination of a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant (5) A combination of a red colorant, a blue colorant, a yellow colorant and a green colorant. (6) A combination of a red colorant, a blue colorant and a green colorant. (7) A combination of a yellow colorant and a purple colorant.
  • the mass ratio of the red colorant, the blue colorant, the yellow colorant, the purple colorant, and the green colorant is red colorant: blue colorant: yellow colorant: purple colorant: green colorant.
  • Agent 10 to 80:20 to 80: 5 to 40: 5 to 40: 5 to 40, preferably 10 to 60:30 to 80: 5 to 30: 5 to 30: 5 to 30.
  • the ratio is more preferably 10 to 40:40 to 80: 5 to 20: 5 to 20: 5 to 20.
  • C.I. I. Pigment Yellow 139, 150, and 185, and C.I. I. Pigment ⁇ Yellow ⁇ 139,150 is more preferable, and C.I. I. Pigment ⁇ Yellow ⁇ 139 is more preferable.
  • blue colorants include C.I. I. Pigment Blue 15: 6 is preferred.
  • purple colorant include C.I. I. Pigment Violet 23 is preferred.
  • Green colorants include C.I. I. Pigment Green 7, 36, 58, 59 are preferred.
  • the organic black colorant may be a pigment or a dye, and is preferably a pigment.
  • the organic black colorant include a bisbenzofuranone compound (also referred to as a benzodifuranone compound), an azomethine compound, a perylene compound, and an azo compound.
  • the organic black colorant preferably contains at least one of a bisbenzofuranone compound, a perylene compound and an azo compound.
  • the bisbenzofuranone compound include compounds described in JP-T-2010-534726, JP-T-2012-515233, JP-T-2012-515234, and the like. For example, as “Irgaphor Black” manufactured by BASF Available.
  • perylene compounds examples include C.I. I. Pigment Black 31, 32, and the compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821.
  • examples of the azomethine compound include those described in JP-A-01-170601 and JP-A-02-034664, and for example, it can be obtained as "Chromofine Black A1103" manufactured by Dainichi Seika.
  • the bisbenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent
  • R 3 and R 4 each independently represent a substituent
  • a and b each independently represent an integer of 0 to 4.
  • a plurality of R 3 may be the same or different, and a plurality of R 3 may combine to form a ring
  • a plurality of R 4 s may be the same or different, and a plurality of R 4 s may combine to form a ring.
  • the substituents represented by R 1 to R 4 are a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, —OR 301 , —COR 302 , and —COOR 303 , -OCOR 304 , -NR 305 R 306 , -NHCOR 307 , -CONR 308 R 309 , -NHCONR 310 R 311 , -NHCOOR 312 , -SR 313 , -SO 2 R 314 , -SO 2 OR 315 , -NHSO 2 R 316 or —SO 2 NR 317 represents R 318 , and R 301 to R 318 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroary
  • an organic black colorant when used as a coloring material, it is preferable to use it in combination with a chromatic colorant.
  • a chromatic colorant By using an organic black colorant and a chromatic colorant in combination, it is easy to obtain excellent spectral characteristics.
  • the chromatic colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a purple colorant, and a red colorant and a blue colorant are preferable. These may be used alone or in combination of two or more.
  • the mixing ratio of the chromatic colorant and the organic black colorant is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, per 100 parts by mass of the organic black colorant. preferable.
  • the content of the pigment in the coloring material is preferably 95% by mass or more, more preferably 97% by mass or more, and more preferably 99% by mass or more based on the total amount of the coloring material. preferable.
  • the content of the coloring material is 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and more preferably 45% by mass, based on the total solid content of the composition. % Or more is more preferable, and 50% by mass or more is particularly preferable. Further, the content of the coloring material is preferably not more than 80% by mass, more preferably not more than 75% by mass, more preferably not more than 70% by mass based on the total solid content of the composition.
  • the curable composition of the present invention can contain a near infrared absorbing agent.
  • the near-infrared absorbing agent has a role of limiting the light transmitted in the near-infrared region to a longer wavelength side in the spectral characteristics of the composition.
  • the near-infrared absorbing agent a compound having a maximum absorption wavelength in a near-infrared region (preferably, a wavelength exceeding 700 nm and 1,300 nm or less) can be preferably used.
  • the near-infrared absorbing agent may be a pigment or a dye.
  • a near-infrared absorbing compound having a ⁇ -conjugated plane containing a monocyclic or condensed aromatic ring can be preferably used as the near-infrared absorbing agent.
  • the number of atoms other than hydrogen constituting the ⁇ -conjugate plane of the near-infrared absorbing compound is preferably 14 or more, more preferably 20 or more, still more preferably 25 or more, and 30 or more. It is particularly preferable that the above is satisfied.
  • the upper limit is, for example, preferably 80 or less, and more preferably 50 or less.
  • the ⁇ -conjugate plane of the near-infrared absorbing compound preferably contains two or more monocyclic or condensed aromatic rings, more preferably contains three or more aromatic rings described above, More preferably, it contains four or more, particularly preferably five or more of the above-mentioned aromatic rings.
  • the upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less.
  • the near-infrared absorbing compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm.
  • “having a maximum absorption wavelength in a wavelength range of 700 to 1000 nm” means a wavelength showing a maximum absorbance in a wavelength range of 700 to 1000 nm in an absorption spectrum of a solution of a near-infrared absorbing compound. Means to have.
  • the measurement solvent used for measuring the absorption spectrum of the near-infrared absorbing compound in a solution includes chloroform, methanol, dimethyl sulfoxide, ethyl acetate, and tetrahydrofuran.
  • chloroform is used as a measuring solvent. If the compound does not dissolve in chloroform, use methanol. If it does not dissolve in either chloroform or methanol, use dimethyl sulfoxide.
  • the near-infrared absorbing compound is a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterylene compound, a merocyanine compound, a croconium compound, an oxonol compound, a diimonium compound, a dithiol compound, a triarylmethane compound, At least one selected from a pyrromethene compound, an azomethine compound, an anthraquinone compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound and a diimonium compound is more preferable. At least one selected from a pyrrolopyrrole compound, a cyanine compound, a
  • Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, compounds described in paragraphs 0011 to 0052 of JP-A-2011-068731, and WO 2015/166873. Examples include the compounds described in paragraphs 0010 to 0033, the contents of which are incorporated herein.
  • Examples of the squarylium compound include compounds described in paragraphs 0044 to 0049 of JP-A-2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, and paragraph 0040 of WO 2016/181987.
  • the compounds described in WO 2013/133030, the compounds described in WO 2014/088063, the compounds described in JP-A-2014-126642, and the compounds described in JP-A-2016-146619 Compounds, compounds described in JP-A-2015-176046, compounds described in JP-A-2017-025311, compounds described in International Publication No. WO2016 / 154772, compounds described in Patent No.
  • Patent 6036689 Compounds described in the gazette, No. 5,810,604, compounds described in JP-A-2017-068120, compounds described in JP-A-2017-197439, compounds described in paragraphs 0090 to 0107 of WO2017 / 213047, and the like. And their contents are incorporated herein.
  • Examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026 to 0030 of JP-A-2002-194040, and JP-A-2015-172004. And the compounds described in JP-A-2015-172102, the compounds described in JP-A-2008-088426, and the like, the contents of which are incorporated herein.
  • examples of the diimonium compound include the compounds described in JP-T-2008-528706, the contents of which are incorporated herein.
  • examples of the phthalocyanine compound include compounds described in paragraph 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraphs 0013 to 0029 of JP-A-2013-195480. And the contents of which are incorporated herein.
  • examples of the naphthalocyanine compound include the compounds described in paragraph 0093 of JP-A-2012-077153, the contents of which are incorporated herein.
  • the compounds described in paragraphs 0010 to 0081 of JP-A-2010-11117 may be used, the contents of which are incorporated herein. It is.
  • the cyanine compound for example, “Functional Dye, Shin Ogawara / Sen Matsuoka / Teijiro Kitao / Tsunaki Hirashima / Author, Kodansha Scientific” can be referred to, and the contents thereof are incorporated herein.
  • the near-infrared absorbing compound the compounds described in JP-A-2016-146519 can also be used, and the contents thereof are incorporated herein.
  • Examples of the near-infrared absorbing agent include a squarylium compound described in JP-A-2017-197439, a squarylium compound described in paragraphs 0090 to 0107 of WO2017 / 213047, and a paragraph 0019 to JP-A-2018-054760.
  • the near-infrared absorbing compound a commercial product may be used.
  • SDO-C33 manufactured by Arimoto Chemical Industry Co., Ltd.
  • EEX Color IR-14 EEX Color IR-10A
  • EEX Color TX-EX-801B EEX Color TX-EX-805K
  • Shigenox NIA-8041 Shigenox NIA-8042
  • Shigenox NIA-814 Shigenox NIA-820
  • Shigenox NIA-839 Manufactured by Hako Chemical Co., Ltd., Hako Chemical Co., Ltd.
  • Film Co., Ltd. NK-3027, NK-5060 (manufactured by Hayashibara), YKR-3070 (manufactured by Mitsui Chemicals, Inc.) and the like.
  • inorganic particles may be used as the near-infrared absorbing agent.
  • the shape of the inorganic particles is not particularly limited, and may be sheet-like, wire-like, or tube-like regardless of spherical or non-spherical shape.
  • metal oxide particles or metal particles are preferable. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped).
  • tungsten oxide-based compound can be used as the inorganic particles.
  • the tungsten oxide-based compound is preferably cesium tungsten oxide.
  • the content of the near-infrared absorbing agent is preferably 1 to 30% by mass based on the total solid content of the composition.
  • the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
  • the total amount of the near-infrared absorbing agent and the coloring material is preferably 10 to 70% by mass of the total solids of the composition.
  • the lower limit is preferably at least 20% by mass, more preferably at least 25% by mass.
  • the content of the near-infrared absorbing agent in the total amount of the near-infrared absorbing agent and the coloring material is preferably 5 to 40% by mass.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the lower limit is preferably at least 10% by mass, more preferably at least 15% by mass.
  • one kind of the near-infrared absorber may be used alone, or two or more kinds may be used in combination.
  • the total is preferably within the above range.
  • the near-infrared absorbing compound a commercial product may be used.
  • SDO-C33 manufactured by Arimoto Chemical Industry Co., Ltd.
  • EEX Color IR-14 EEX Color IR-10A
  • EEX Color TX-EX-801B EEX Color TX-EX-805K
  • ShigenoxNIA-8041 ShigenoxNIA-8042
  • ShigenoxNIA-814 ShigenoxNIA-820
  • ShigenoxNIA-839 Hakko Chemical Co., Ltd.
  • EpoliteV-63 Epolight3801, made Epolight3036 (EPOLIN, Inc.)
  • PRO-JET825LDI Fluji Film Co., Ltd.
  • NK-3027 NK-5060
  • YKR-3070 manufactured by Mitsui Chemicals, Inc.
  • the content of the near-infrared absorbing agent is preferably 1 to 30% by mass based on the total solid content of the curable composition.
  • the upper limit is preferably 25% by mass or less, and more preferably 20% by mass or less.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
  • the total amount of the near-infrared absorbing agent and the coloring material is preferably 35 to 80% by mass of the total solid of the curable composition.
  • the lower limit is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more.
  • the upper limit is preferably 75% by mass or less, more preferably 70% by mass or less. Further, the content of the near-infrared absorbing agent in the total amount of the near-infrared absorbing agent and the coloring material is preferably 5 to 40% by mass.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the lower limit is preferably at least 10% by mass, more preferably at least 15% by mass.
  • the near-infrared absorbing agent may be used alone or in combination of two or more.
  • the total is preferably within the above range.
  • the curable composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include a compound having an ethylenically unsaturated group.
  • the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound is preferably a compound polymerizable by a radical (radical polymerizable compound).
  • the molecular weight of the polymerizable compound is preferably from 100 to 2,000.
  • the upper limit is preferably 1500 or less, more preferably 1000 or less.
  • the lower limit is more preferably 150 or more, and further preferably 250 or more.
  • the lower limit is preferably at least 3 mmol / g, more preferably at least 4 mmol / g, even more preferably at least 5 mmol / g.
  • the upper limit is preferably at most 12 mmol / g, more preferably at most 10 mmol / g, even more preferably at most 8 mmol / g.
  • the polymerizable compound is preferably a compound containing three or more ethylenically unsaturated groups, and more preferably a compound containing four or more ethylenically unsaturated groups. According to this aspect, the curability of the curable composition upon exposure is good.
  • the upper limit of the number of ethylenically unsaturated groups is preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less from the viewpoint of the stability over time of the composition.
  • the polymerizable compound is preferably a trifunctional or higher functional (meth) acrylate compound, more preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 10 functional (meth) acrylate compound. More preferably, it is particularly preferably a tri- to hexafunctional (meth) acrylate compound.
  • the polymerizable compound is also preferably a compound containing an ethylenically unsaturated group and an alkyleneoxy group. Since such a polymerizable compound has high flexibility and the ethylenically unsaturated group is easily moved, the polymerizable compound easily reacts with each other at the time of exposure, and a cured film (pixel) having excellent adhesion to a support or the like. Can be formed. Further, when a hydroxyalkylphenone compound is used as the photopolymerization initiator, the polymerizable compound and the photopolymerization initiator approach each other to generate radicals in the vicinity of the polymerizable compound to more effectively convert the polymerizable compound. It is presumed that they can be reacted, and it is easy to form a cured film (pixel) having better adhesion and solvent resistance.
  • the number of alkyleneoxy groups contained in one molecule of the polymerizable compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
  • the upper limit is preferably 20 or less from the viewpoint of the stability over time of the composition.
  • the SP value (Solubility @Parameter) of the compound containing an ethylenically unsaturated group and an alkyleneoxy group is preferably from 9.0 to 11.0 from the viewpoint of compatibility with other components in the composition.
  • the upper limit is preferably 10.75 or less, more preferably 10.5 or less.
  • the lower limit is preferably 9.25 or more, and more preferably 9.5 or more.
  • the SP value used the calculated value based on the Fedors method.
  • Examples of the compound having an ethylenically unsaturated group and an alkyleneoxy group include a compound represented by the following formula (M-1).
  • a 1 represents an ethylenically unsaturated group
  • L 1 represents a single bond or a divalent linking group
  • R 1 represents an alkylene group
  • m represents an integer of 1 to 30
  • n represents 3
  • L 2 represents an n-valent linking group.
  • Examples of the ethylenically unsaturated group represented by A 1 include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
  • Examples of the divalent linking group represented by L 1 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, and a group combining two or more of these. .
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the carbon number of the alkylene group represented by R 1 is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, particularly preferably 2 or 3, and most preferably 2.
  • the alkylene group represented by R 1 is preferably linear or branched, and more preferably linear. Specific examples of the alkylene represented by R 1 include an ethylene group, a linear or branched propylene group, and an ethylene group is preferable.
  • n represents an integer of 3 or more, and preferably an integer of 4 or more.
  • the upper limit of n is preferably an integer of 15 or less, more preferably an integer of 10 or less, and even more preferably an integer of 6 or less.
  • Examples of the n-valent linking group represented by L 2 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group and a group formed by a combination thereof, and an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group. Examples include a group formed by combining at least one selected from a ring group and at least one selected from -O-, -CO-, -COO-, -OCO- and -NH-.
  • the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and is preferably linear or branched.
  • the carbon number of the aromatic hydrocarbon group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group.
  • the heterocyclic group is preferably a 5- or 6-membered ring. Examples of the types of hetero atoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the n-valent linking group represented by L 2 is also preferably a group derived from a polyfunctional alcohol.
  • a compound represented by the following formula (M-2) is more preferable.
  • R 2 represents a hydrogen atom or a methyl group
  • R 1 represents an alkylene group
  • m represents an integer of 1 to 30
  • n represents an integer of 3 or more
  • L 2 represents an n-valent linking group.
  • R 1, L 2, m, n of formula (M-2) is R 1, L 2, m, synonymous with n in formula (M-1), and preferred ranges are also the same.
  • polymerizable compounds having an ethylenically unsaturated group and an alkyleneoxy group include KAYARAD T-1420 (T), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like.
  • dipentaerythritol triacrylate (KAYARAD @ D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD @ D-320 as a commercial product; Nippon Kayaku Co., Ltd.) Nippon Kayaku), dipentaerythritol penta (meth) acrylate (commercially available KAYARAD @ D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD @ DPHA; Nippon Kayaku ( NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues.
  • SR commercially available from Sartomer It is may SR
  • ARONIX M-402 a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd.).
  • trimethylolpropane tri (meth) acrylate trimethylolpropanepropyleneoxy-modified tri (meth) acrylate, trimethylolpropaneethyleneoxy-modified tri (meth) acrylate, isocyanuric acid ethyleneoxy-modified tri (meth) acrylate
  • a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate.
  • trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • NK ester # A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD @ GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And the like.
  • a polymerizable compound having an acid group As the polymerizable compound.
  • the curable composition layer in an unexposed portion is easily removed at the time of development, and the generation of a development residue can be suppressed.
  • the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable.
  • the polymerizable compound having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate.
  • the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developer is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.
  • the polymerizable compound is also preferably a compound having a caprolactone structure.
  • the polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD @ DPCA series, for example, DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
  • Polymerizable compounds include compounds described in JP-A-2017-048367, JP-A-6057891, and JP-A-6031807, compounds described in JP-A-2017-194662, 8UH-1006, and 8UH. It is also preferable to use -1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like.
  • the content of the polymerizable compound is preferably 5.0 to 35% by mass based on the total solid content of the curable composition.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
  • the curable composition of the present invention contains a photopolymerization initiator.
  • the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole compounds, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoalkylphenone compounds, hydroxyalkylphenone compounds, phenylglyoxylate compounds, and the like.
  • paragraphs 0265 to 0268 of JP-A-2013-029760 and JP-A-6301489 can be referred to, and the contents thereof are incorporated herein.
  • Phenylglyoxylate compounds include phenylglyoxylic acid methyl ester and the like.
  • Commercially available products include DAROCUR-MBF (manufactured by BASF).
  • aminoalkylphenone compound examples include, for example, an aminoalkylphenone compound described in JP-A-10-291969. Further, as the aminoalkylphenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF) can also be used.
  • acylphosphine compound examples include the acylphosphine compounds described in Japanese Patent No. 422598. Specific examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • acylphosphine compound IRGACURE-819 and DAROCUR-TPO (both manufactured by BASF) can also be used.
  • hydroxyalkylphenone compound examples include a compound represented by the following formula (V).
  • Rv 1 represents a substituent
  • Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent
  • Rv 2 and Rv 3 may combine with each other to form a ring
  • m represents an integer of 0 to 5.
  • Examples of the substituent represented by Rv 1 include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms).
  • the alkyl group and the alkoxy group are preferably linear or branched, and more preferably linear.
  • the alkyl group and the alkoxy group represented by Rv 1 may be unsubstituted or may have a substituent.
  • Examples of the substituent include a hydroxyl group and a group having a hydroxyalkylphenone structure.
  • Examples of the group having a hydroxyalkylphenone structure include a benzene ring to which Rv 1 is bonded in Formula (V) or a group having a structure in which one hydrogen atom is removed from Rv 1 .
  • Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent.
  • an alkyl group preferably an alkyl group having 1 to 10 carbon atoms
  • Rv 2 and Rv 3 may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms).
  • the alkyl group is preferably linear or branched, and more preferably linear.
  • IRGACURE-184 As the hydroxyalkylphenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can also be used.
  • Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, and J.I. C. S. Compounds described in Perkin II (1979, pp. 1653-1660); C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer, Science and and Technology (1995, pp.
  • oxime compound examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyimiminobtan-2-one, 3-propionyloxyimiminobtan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one.
  • IRGACURE-OXE01 IRGACURE-OXE02
  • IRGACURE-OXE03 IRGACURE-OXE04
  • TR-PBG-304 manufactured by Changzhou Strong Electronics New Materials Co., Ltd.
  • Adeka Optomer N-1919 (Photopolymerization initiator 2 manufactured by ADEKA Corporation and described in JP-A-2012-014052).
  • Examples of the oxime compound include compounds described in JP-A-2009-519904 in which an oxime is linked to the N-position of a carbazole ring, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds described in JP-A-2010-015025 and US Patent Application Publication No. 2009/0292039 in which a nitro group is introduced into a dye moiety, ketoxime compounds described in WO2009 / 131189, triazine skeletons and oximes A compound described in US Pat. No.
  • the oxime compound is preferably an oxime compound containing a fluorine atom.
  • the oxime compound containing a fluorine atom preferably has an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated alkyl group), and a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated group). .
  • fluorinated group examples include -OR F1 , -SR F1 , -COR F1 , -COOR F1 , -OCOR F1 , -NR F1 R F2 , -NHCOR F1 , -CONR F1 R F2 , -NHCONR F1 R F2 , -NHCOOR At least one group selected from F1 , —SO 2 R F1 , —SO 2 OR F1, and —NHSO 2 R F1 is preferable.
  • R F1 represents a fluorine-containing alkyl group
  • R F2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group or a heterocyclic group.
  • the fluorine-containing group is preferably -OR F1 .
  • the carbon number of the alkyl group and the fluorine-containing alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4.
  • the alkyl group and the fluorine-containing alkyl group may be linear, branched or cyclic, but are preferably linear or branched.
  • the substitution ratio of fluorine atoms is preferably from 40 to 100%, more preferably from 50 to 100%, even more preferably from 60 to 100%.
  • the substitution rate of a fluorine atom means the ratio (%) of the number of substitution with a fluorine atom to the total number of hydrogen atoms of the alkyl group.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the number of condensation is preferably 2 to 8, more preferably 2 to 6, still more preferably 3 to 5, and particularly preferably 3 to 4.
  • the number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and more preferably 3 to 20.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a nitrogen atom.
  • the group containing a fluorine atom preferably has a terminal structure represented by the formula (1) or (2). -CHF 2 (1) -CF 3 (2)
  • the total number of fluorine atoms in the fluorine-containing oxime compound is preferably 3 or more, more preferably 4 to 10.
  • the oxime compound containing a fluorine atom is preferably a compound represented by the formula (OX-1). (OX-1)
  • Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent, and R 1 represents an aryl group having a group containing a fluorine atom. And R 2 and R 3 each independently represent an alkyl group or an aryl group.
  • Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent.
  • the aromatic hydrocarbon ring may be a single ring or a condensed ring.
  • the number of carbon atoms constituting the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10.
  • a benzene ring and a naphthalene ring are preferable.
  • at least one of Ar 1 and Ar 2 is preferably a benzene ring, and more preferably Ar 1 is a benzene ring.
  • Ar 2 is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.
  • Examples of the substituent which Ar 1 and Ar 2 may have include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, —OR X1 , —SR X1 , —COR X1 , and —COOR X1. , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 , -NHSO 2 R X1 No. R X1 and R X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group as a substituent and the alkyl group represented by R X1 and R X2 preferably have 1 to 30 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • some or all of the hydrogen atoms may be substituted with halogen atoms (preferably, fluorine atoms).
  • part or all of the hydrogen atoms may be substituted with the above substituents.
  • the carbon number of the aryl group as a substituent and the aryl group represented by R X1 and R X2 is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aryl group may be a single ring or a condensed ring. Further, in the aryl group, part or all of the hydrogen atoms may be substituted with the above substituents.
  • the heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably a 5- or 6-membered ring.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the number of carbon atoms constituting the heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, and even more preferably from 3 to 12.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, part or all of the hydrogen atoms may be substituted with the above substituents.
  • the aromatic hydrocarbon ring represented by Ar 1 is preferably unsubstituted.
  • the aromatic hydrocarbon ring represented by Ar 2 may be unsubstituted or may have a substituent. It preferably has a substituent.
  • —COR X1 is preferable.
  • R X1 is preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an aryl group.
  • the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.
  • R 1 represents an aryl group having a group containing a fluorine atom.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • the group containing a fluorine atom an alkyl group having a fluorine atom (fluorine-containing alkyl group) and a group containing a fluorine atom-containing alkyl group (fluorine-containing group) are preferable.
  • the group containing a fluorine atom has the same meaning as the above-mentioned range, and the preferred range is also the same.
  • R 2 represents an alkyl group or an aryl group, and is preferably an alkyl group.
  • the alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have.
  • the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • R 3 represents an alkyl group or an aryl group, and is preferably an alkyl group.
  • the alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have.
  • the number of carbon atoms of the alkyl group represented by R 3 is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • the aryl group represented by R 3 preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms, and still more preferably has 6 to 10 carbon atoms.
  • oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471.
  • Compound (C-3) examples include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471.
  • an oxime compound having a fluorene ring can be used as the oxime compound.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.
  • an oxime compound having a benzofuran skeleton can be used as the oxime compound.
  • Specific examples include compounds OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can be used.
  • Specific examples of such oxime compounds include the compounds described in WO2013 / 083505.
  • an oxime compound having a nitro group can be used.
  • the oxime compound having a nitro group is preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012 of JP-A-2014-137466, and 0070 to 0079, and JP-A-4223071. And the like.
  • a photopolymerization initiator A1 having an absorption coefficient of 1.0 ⁇ 10 3 mL / gcm or more in methanol at a wavelength of 365 nm, and a wavelength of 365 nm in methanol.
  • a photopolymerization initiator A2 having an extinction coefficient of 1.0 ⁇ 10 2 mL / gcm or less and an extinction coefficient at a wavelength of 254 nm of 1.0 ⁇ 10 3 mL / gcm or more.
  • the composition is easily cured sufficiently by exposure, and has excellent adhesion in a low-temperature process (for example, at a temperature of less than 200 ° C., or 150 ° C. or less, and even 120 ° C. or less throughout the entire process), Furthermore, a cured film having excellent solvent resistance, flatness, and rectangularity of the pattern can be formed.
  • a compound having the above-mentioned extinction coefficient is preferably selected from the above-mentioned compounds and used.
  • the extinction coefficient of the photopolymerization initiator at the above-mentioned wavelength is a value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution, and measuring the absorbance of the measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Carry5000) manufactured by Agilent Technologies, and the wavelength was 365 nm and the wavelength was applied by applying the following formula. The extinction coefficient (mL / gcm) at 254 nm was calculated.
  • ⁇ represents the extinction coefficient (mL / gcm)
  • A represents the absorbance
  • c represents the concentration of the photopolymerization initiator (g / mL)
  • l represents the optical path length (cm).
  • the extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 365 nm is 1.0 ⁇ 10 3 mL / gcm or more, preferably 1.0 ⁇ 10 4 mL / gcm or more, and more preferably 1.1 ⁇ 10 4 mL / gcm. It is more preferably at least 10 4 mL / gcm, even more preferably 1.2 ⁇ 10 4 to 1.0 ⁇ 10 5 mL / gcm, and 1.3 ⁇ 10 4 to 5.0 ⁇ 10 4 mL. / Gcm, more preferably 1.5 ⁇ 10 4 to 3.0 ⁇ 10 4 mL / gcm.
  • the extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 254 nm in methanol is preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 5 mL / gcm, and 1.5 ⁇ 10 4 to 1.5 ⁇ 10 4 mL / gcm. It is more preferably 9.5 ⁇ 10 4 mL / gcm, and still more preferably 3.0 ⁇ 10 4 to 8.0 ⁇ 10 4 mL / gcm.
  • the photopolymerization initiator A1 is preferably an oxime compound, an aminoalkylphenone compound or an acylphosphine compound, more preferably an oxime compound or an acylphosphine compound, further preferably an oxime compound, and has compatibility with other components contained in the composition.
  • an oxime compound containing a fluorine atom is particularly preferred.
  • a compound represented by the above formula (OX-1) is preferable.
  • photopolymerization initiator A1 examples include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (as commercial products, for example, IRGACURE-OXE01, BASF , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (commercially available, for example, IRGACURE- OXE02, manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercially available, for example, IRGACURE-819, manufactured by BASF), and specific examples of the above oxime compounds ( C-13) and (C-14).
  • the extinction coefficient of the photopolymerization initiator A2 for light having a wavelength of 365 nm in methanol is 1.0 ⁇ 10 2 mL / gcm or less, preferably 10 to 1.0 ⁇ 10 2 mL / gcm. More preferably, it is about 1.0 ⁇ 10 2 mL / gcm.
  • the difference between the extinction coefficient of photopolymerization initiator A1 at 365 nm in methanol and the extinction coefficient of photopolymerization initiator A2 at 365 nm in methanol is 9.0 ⁇ 10 2 mL.
  • the extinction coefficient of the photopolymerization initiator A2 in methanol at a wavelength of 254 nm in methanol is 1.0 ⁇ 10 3 mL / gcm or more, and 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6 mL / gcm. And more preferably from 5.0 ⁇ 10 3 to 1.0 ⁇ 10 5 mL / gcm.
  • the photopolymerization initiator A2 is preferably a hydroxyalkylphenone compound, a phenylglyoxylate compound, an aminoalkylphenone compound, an acylphosphine compound, more preferably a hydroxyalkylphenone compound and a phenylglyoxylate compound, and further preferably a hydroxyalkylphenone compound.
  • a compound represented by the above formula (V) is preferable.
  • photopolymerization initiator A2 examples include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available, for example, IRGACURE-184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl 2-hydroxy-2-methyl-1-propan-1-one (commercially available, for example, IRGACURE-2959, manufactured by BASF).
  • the photopolymerization initiator A1 As a combination of the photopolymerization initiator A1 and the photopolymerization initiator A2, a combination in which the photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a hydroxyalkylphenone compound is preferable, and the photopolymerization initiator A1 is preferably More preferably, the combination is an oxime compound, wherein the photopolymerization initiator A2 is a compound represented by the above formula (V), wherein the photopolymerization initiator A1 is an oxime compound containing a fluorine atom, and the photopolymerization initiator A2 is Combinations of the compounds of formula (V) described above are particularly preferred.
  • the content of the photopolymerization initiator A1 is preferably 1.0 to 20.0% by mass based on the total solid content of the curable composition of the present invention.
  • the lower limit of the content of the photopolymerization initiator A1 is preferably 2.0% by mass or more, and more preferably 3.0% by mass or more. More preferably, it is more preferably 4.0% by mass or more.
  • the upper limit of the content of the photopolymerization initiator A1 is preferably 15.0% by mass or less, more preferably 12.5% by mass or less, and 10.0% or less. It is more preferable that the content be not more than mass%.
  • the content of the photopolymerization initiator A2 is preferably 0.5 to 15.0% by mass based on the total solid content of the curable composition of the present invention.
  • the lower limit of the content of the photopolymerization initiator A2 is preferably 1.0% by mass or more, more preferably 1.5% by mass or more. More preferably, it is 0% by mass or more.
  • the upper limit of the content of the photopolymerization initiator A2 is preferably 12.5% by mass or less, more preferably 10.0% by mass or less, and 7.5. It is more preferable that the content be not more than mass%.
  • the curable composition of the present invention preferably contains 50 to 200 parts by mass of the photopolymerization initiator A2 based on 100 parts by mass of the photopolymerization initiator A1.
  • the upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less, from the viewpoint of miniaturization of the pattern after development.
  • the lower limit is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, from the viewpoint of the solvent resistance of the obtained cured film.
  • the total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the curable composition of the present invention is preferably 5 to 15% by mass or more.
  • the lower limit is preferably 6% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more.
  • the upper limit is preferably 14.5% by mass or less, more preferably 14.0% by mass or less, and still more preferably 13.0% by mass or less, from the viewpoint of miniaturization of the pattern after development. .
  • the curable composition of the present invention can contain a photopolymerization initiator other than the photopolymerization initiator A1 and the photopolymerization initiator A2 (hereinafter, also referred to as another photopolymerization initiator) as a photopolymerization initiator. It is preferable that other photopolymerization initiators are not substantially contained.
  • the case where the other photopolymerization initiator is not substantially contained means that the content of the other photopolymerization initiator is 1 part by mass with respect to 100 parts by mass in total of the photopolymerization initiator A1 and the photopolymerization initiator A2. It is preferably at most 0.5 part by mass, more preferably at most 0.5 part by mass, even more preferably at most 0.1 part by mass, and even more preferably not containing other photopolymerization initiator.
  • the composition of the present invention can contain a resin.
  • the resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition or for the purpose of a binder.
  • a resin mainly used for dispersing particles such as a pigment is also referred to as a dispersant.
  • a use of the resin is an example, and the resin may be used for a purpose other than the use.
  • the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 3,000 or more, more preferably 5,000 or more.
  • cyclic olefin resin a norbornene resin can be preferably used from the viewpoint of improving heat resistance.
  • Examples of commercially available norbornene resin include ARTON series (for example, ARTON @ F4520) manufactured by JSR Corporation.
  • Examples of the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester resin.
  • Epoxy resin glycidylamine-based epoxy resin, epoxy resin obtained by glycidylation of halogenated phenols, condensate of silicon compound with epoxy group and other silicon compound, polymerizable unsaturated compound with epoxy group and other Copolymers with other polymerizable unsaturated compounds and the like can be mentioned. Also, Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation) , An epoxy group-containing polymer) and the like.
  • resins described in Examples of International Publication WO 2016/088865, resins described in JP-A-2017-057265, resins described in JP-A-2017-032685, A resin described in JP-A-0-75248 and a resin described in JP-A-2017-066240 can also be used, and the contents thereof are incorporated herein.
  • a resin having a fluorene skeleton can be preferably used.
  • examples of the resin having a fluorene skeleton include a resin having the following structure.
  • A is a residue of a carboxylic acid dianhydride selected from pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and diphenyl ether tetracarboxylic dianhydride.
  • M is a phenyl or benzyl group.
  • the resin used in the present invention may have an acid group.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxyl group, and a carboxyl group is preferable. These acid groups may be used alone or in combination of two or more.
  • the resin having an acid group can be used as an alkali-soluble resin.
  • a polymer having a carboxyl group in a side chain is preferable.
  • alkali-soluble polymers such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins.
  • examples thereof include phenol resins, acidic cellulose derivatives having a carboxyl group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxyl group.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
  • Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds.
  • alkyl (meth) acrylate and the aryl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
  • vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, and cyclohexyl (meth) acrylate include styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydr
  • N-substituted maleimide monomers described in JP-A-10-300922 for example, N-phenylmaleimide, N-cyclohexylmaleimide and the like can also be used.
  • the other monomer copolymerizable with the (meth) acrylic acid may be only one kind or two or more kinds.
  • the resin having a diacid group may further have a polymerizable group.
  • the polymerizable group include an allyl group, a methallyl group, and a (meth) acryloyl group.
  • Commercial products include Dianar NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, and KS Resist 106 (all of Osaka Organic Chemicals, Inc.) Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel @ CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), Accrecur RD-F8 (Co., Ltd.) Nippon Shokubai).
  • Resins having an acid group include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate.
  • a multi-component copolymer composed of acrylate / (meth) acrylic acid / other monomer can be preferably used.
  • copolymers of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-07-140654.
  • the resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimer”). It is also preferable that the polymer contains a repeating unit derived from a component.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • RIn the formula (ED2) R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP-A-2010-168538 can be referred to.
  • ether dimer for example, paragraph 0317 of JP-A-2013-029760 can be referred to, and the contents thereof are incorporated herein.
  • the ether dimer may be only one kind or two or more kinds.
  • the resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a carbon atom having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring.
  • n represents an integer of 1 to 15.
  • the resin having an acid group is described in paragraphs 0558 to 0571 of JP-A-2012-208494 (paragraphs 0885 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099) and JP-A-2012-198408. Can be referred to, and the contents thereof are incorporated in the present specification.
  • a commercially available resin can be used as the resin having an acid group.
  • Acrybase FF-426 manufactured by Fujikura Kasei Co., Ltd.
  • the like can be mentioned.
  • the acid value of the resin having an acid group is preferably from 30 to 200 mgKOH / g.
  • the lower limit is preferably at least 50 mgKOH / g, more preferably at least 70 mgKOH / g.
  • the upper limit is preferably equal to or less than 150 mgKOH / g, and more preferably equal to or less than 120 mgKOH / g.
  • Examples of the resin having an acid group include a resin having the following structure.
  • Me represents a methyl group.
  • the composition of the present invention can also contain a resin as a dispersant.
  • the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) refers to a resin in which the amount of an acid group is larger than the amount of a basic group.
  • the acid dispersant (acidic resin) is preferably a resin in which the amount of the acid group accounts for 70 mol% or more when the total amount of the acid group and the basic group is 100 mol%. More preferred are resins consisting only of groups.
  • the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the acid value of the acidic dispersant is preferably from 40 to 105 mgKOH / g, more preferably from 50 to 105 mgKOH / g, even more preferably from 60 to 105 mgKOH / g.
  • the basic dispersant (basic resin) refers to a resin in which the amount of the basic group is larger than the amount of the acid group.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of the basic group exceeds 50 mol% when the total amount of the acid group and the amount of the basic group is 100 mol%.
  • the basic group of the basic dispersant is preferably an amino group.
  • the resin used as the dispersant preferably contains a repeating unit having an acid group.
  • residues generated on the base of the pixel can be further reduced when a pattern is formed by a photolithography method.
  • the resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity for a solvent due to the graft chain, the dispersibility of the pigment and the dispersion stability after aging are excellent.
  • the details of the graft copolymer can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • specific examples of the graft copolymer include the following resins.
  • the following resins are also resins having an acid group (alkali-soluble resins).
  • examples of the graft copolymer include resins described in paragraphs 0072 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain as the resin (dispersant).
  • the oligoimine-based dispersant includes a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain including a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain. Resins having a basic nitrogen atom on at least one side are preferred.
  • the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
  • oligoimine-based dispersant the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
  • a resin having the following structure or a resin described in paragraphs 0168 to 0174 of JP-A-2012-255128 can be used.
  • the dispersant is also available as a commercial product, and specific examples of such a dispersant include Disperbyk-111 (manufactured by BYK Chemie), Solsperse 76500 (manufactured by Nippon Lubrizol Co., Ltd.), and the like. Further, pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the contents thereof are incorporated herein. Further, the above-mentioned resin having an acid group can be used as a dispersant.
  • the content of the resin is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit is more preferably 40% by mass or less, and still more preferably 30% by mass or less.
  • the content of the resin having an acid group is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit is more preferably 40% by mass or less, and still more preferably 30% by mass or less.
  • the composition of the present invention may include only one type of resin, or may include two or more types of resins. When two or more kinds are contained, the total amount thereof is preferably within the above range.
  • the curable composition of the present invention preferably contains a compound containing a furyl group (hereinafter, also referred to as a furyl group-containing compound).
  • a furyl group-containing compound a compound containing a furyl group
  • the furyl group and the ethylenically unsaturated group of the polymerizable compound form a bond by the Diels-Alder reaction even at a low temperature of less than 200 ° C., and thus are excellent in low-temperature curing.
  • the structure of the furyl group-containing compound is not particularly limited as long as it contains a furyl group (a group obtained by removing one hydrogen atom from furan).
  • a furyl group a group obtained by removing one hydrogen atom from furan.
  • the furyl group-containing compound the compounds described in paragraphs 0049 to 0089 of JP-A-2017-194662 can be used.
  • the difuryl group-containing compound may be a monomer, an oligomer, or a polymer.
  • the polymer is preferably used because it is easy to improve the durability of the obtained film.
  • the weight average molecular weight is preferably from 2000 to 70000.
  • the upper limit is preferably 60,000 or less, more preferably 50,000 or less.
  • the lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more.
  • the weight average molecular weight is preferably less than 2000.
  • the polymer type furyl group-containing compound is a component corresponding to the resin in the curable composition of the present invention, and the monomer type furyl group-containing compound is also a polymerizable compound in the curable composition of the present invention.
  • the corresponding component is a component corresponding to the resin in the curable composition of the present invention, and the monomer type furyl group-containing compound is also a polymerizable compound in the curable composition of the present invention.
  • Examples of the monomer type furyl group-containing compound include compounds represented by the following formula (fur-1). This compound has a polymerizable group in addition to the furyl group.
  • Rf 1 represents a hydrogen atom or a methyl group
  • Rf 2 represents a divalent linking group
  • Examples of the divalent linking group represented by Rf 2 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups.
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group.
  • the furyl group-containing monomer is preferably a compound represented by the following formula (fur-2).
  • Rf 1 represents a hydrogen atom or a methyl group
  • Rf 11 represents —O— or —NH—
  • Rf 12 represents a single bond or a divalent linking group.
  • Examples of the divalent linking group represented by Rf 12 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups.
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group.
  • furyl group-containing monomer examples include a compound having the following structure.
  • Rf 1 represents a hydrogen atom or a methyl group.
  • the polymer type furyl group-containing compound (hereinafter also referred to as a furyl group-containing polymer) is preferably a resin containing a repeating unit containing a furyl group, and is preferably a resin derived from the compound represented by the above formula (fur-1). More preferably, the resin contains units.
  • the concentration of the furyl group in the furyl group-containing polymer is preferably 0.5 to 6.0 mmol, more preferably 1.0 to 4.0 mmol, per 1 g of the furyl group-containing polymer. When the concentration of the furyl group is 0.5 mmol or more, preferably 1.0 mmol or more, it is easy to form a pixel having excellent solvent resistance and the like. If the concentration of the furyl group is 6.0 mmol or less, preferably 4.0 mmol or less, the curable composition has better stability over time.
  • the furyl group-containing polymer may contain a repeating unit having an acid group and / or a repeating unit having a polymerizable group in addition to the repeating unit having a furyl group.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxyl group.
  • the polymerizable group include an ethylenically unsaturated group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • its acid value is preferably from 10 to 200 mgKOH / g, more preferably from 40 to 130 mgKOH / g.
  • the furyl group-containing polymer contains a repeating unit having a polymerizable group, it is easy to form a pixel having more excellent solvent resistance and the like.
  • the furyl group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of JP-A-2017-194662.
  • the content of the furyl group-containing compound is preferably 0.1 to 70% by mass based on the total solid content of the curable composition.
  • the lower limit is preferably 2.5% by mass or more, more preferably 5.0% by mass or more, and even more preferably 7.5% by mass or more.
  • the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the content of the furyl group-containing polymer in the resin contained in the curable composition is preferably 0.1 to 100% by mass.
  • the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.
  • the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.
  • the curable composition of the present invention can further contain a compound having a cyclic ether group.
  • the curable composition of the present invention preferably contains a curing accelerator for the compound having a cyclic ether group.
  • the cyclic ether group is, for example, an epoxy group and an oxetane group, and an epoxy group is preferable.
  • the compound having an epoxy group a compound having two or more epoxy groups in one molecule is preferable.
  • the epoxy group preferably has 2 to 100 epoxy groups in one molecule.
  • the upper limit can be, for example, 10 or less, or 5 or less.
  • the compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (a macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more).
  • the molecular weight (weight average molecular weight in the case of a polymer) of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 50,000.
  • the upper limit of the molecular weight (weight average molecular weight in the case of a polymer) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.
  • EHPE3150 manufactured by Daicel Corporation
  • EPICLON @ N-695 manufactured by DIC Corporation
  • Marproof G-0150M Marproof G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (both manufactured by NOF Corporation, epoxy group-containing polymer) and the like.
  • the content of the compound is preferably 0.1 to 20% by mass based on the total solid content of the composition.
  • the lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more.
  • the upper limit is more preferably equal to or less than 15% by mass, and still more preferably equal to or less than 10% by mass.
  • the compound having a cyclic ether group may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
  • a compound generally used as a curing accelerator for an epoxy compound can be used, for example, acid anhydride, Amines, carboxylic acids and alcohols are preferred.
  • Acid anhydrides as curing accelerators include, for example, methyl tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, 2,4-diethyl glutaric anhydride, butane tetra Carboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3 4-Tricarboxylic acid-3,4-anhydride and the like are preferred from the viewpoints of light resistance, transparency and workability.
  • the carboxylic acid as a curing accelerator is preferably a di- to hexa-functional carboxylic acid.
  • Such carboxylic acids include, for example, alkyltricarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid and citric acid; Aliphatic cyclic polycarboxylic acids such as phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid and methylnadic acid; linolenic acid and oleic acid Dimer acids which are multimers of unsaturated fatty acids and their reduced products; linear alkyl diacids such as malic acid and the like are preferable, and hexane di
  • the amine as the curing accelerator is preferably a polyvalent amine, and more preferably a diamine.
  • Such amines are, for example, hexamethylenediamine, triethylenetetramine, polyethyleneimine and the like.
  • Alcohols as curing accelerators are preferably polyhydric alcohols, more preferably diols.
  • Such alcohols are, for example, polyether diol compounds, polyester diol compounds, polycarbonate diol compounds and the like.
  • the content of the curing accelerator is preferably 1 to 30 parts by mass, and more preferably 5 to 25 parts by mass based on 100 parts by mass of the compound having a cyclic ether group. Part by mass, more preferably 10 to 20 parts by mass.
  • the curing accelerators may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
  • the curable composition of the present invention preferably contains a solvent.
  • the solvent include an organic solvent.
  • the solvent is basically not particularly limited as long as the solubility of each component and the coatability of the curable composition are satisfied.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For details thereof, paragraph 0223 of WO 2015/166779 can be referred to, and the contents thereof are incorporated herein. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
  • organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropanamide and the like.
  • aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
  • aromatic hydrocarbons for environmental reasons or the like (for example, 50 ppm by mass (parts per part with respect to the total amount of the organic solvent). (million) or less, 10 mass ppm or less, or 1 mass ppm or less).
  • a solvent having a low metal content it is preferable to use a solvent having a low metal content, and it is preferable that the metal content of the solvent be, for example, 10 mass ppb (parts per per billion) or less. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one isomer may be contained, or a plurality of isomers may be contained.
  • the content of the peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide.
  • the content of the solvent in the curable composition is preferably from 60 to 95% by mass.
  • the upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and even more preferably 85% by mass or less.
  • the lower limit is preferably at least 65% by mass, more preferably at least 70% by mass, even more preferably at least 75% by mass.
  • the curable composition of the present invention does not substantially contain an environmental regulation substance from the viewpoint of environmental regulation.
  • the term "substantially not containing an environmental control substance” means that the content of the environmental control substance in the curable composition is 50 mass ppm or less, and 30 mass ppm or less. It is more preferably at most 10 ppm by mass, particularly preferably at most 1 ppm by mass.
  • environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • azeotrope When a small amount of environmentally regulated substances are distilled off, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency.
  • a polymerization inhibitor or the like When a compound having a radical polymerizability is contained, a polymerization inhibitor or the like is added in order to suppress the radical polymerization reaction from proceeding and crosslinking between molecules during the distillation under reduced pressure, followed by distillation under reduced pressure. You may.
  • These distillation methods include a raw material stage, a product obtained by reacting the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or a curable composition prepared by mixing these compounds. Either stage is possible.
  • the curable composition of the present invention can contain a pigment derivative.
  • the pigment derivative include a compound having a structure in which a part of a chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group.
  • the chromophore constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, and a perinone skeleton.
  • quinoline skeleton, benzimidazolone skeleton, diketo A pyrrolopyrrole-based skeleton, an azo-based skeleton, a quinophthalone-based skeleton, an isoindoline-based skeleton, and a phthalocyanine-based skeleton are preferred, and an azo-based skeleton and a benzimidazolone-based skeleton are more preferred.
  • a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable.
  • an amino group is preferable, and a tertiary amino group is more preferable.
  • the description in paragraphs 0162 to 0183 of JP-A-2011-252665 can be referred to, and the contents thereof are incorporated herein.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment.
  • One kind of the pigment derivative may be used alone, or two or more kinds thereof may be used in combination.
  • the curable composition of the present invention may contain a curing accelerator for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature.
  • the curing accelerator include a polyfunctional thiol compound having two or more mercapto groups in a molecule.
  • the polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
  • the polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably a compound represented by the formula (T1).
  • n represents an integer of 2 to 4
  • L represents a divalent to tetravalent linking group.
  • the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
  • the curing accelerator examples include a methylol-based compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of JP-A-2005-034963), amines, phosphonium salts, amidine salts, and amide compounds (for example, JP-A-2013-041165, a curing agent described in paragraph 0186), a base generator (for example, an ionic compound described in JP-A-2014-055114), and a cyanate compound (for example, JP-A-2012-150180)
  • Compounds exemplified as acid generators, JP Compounds described in JP-009-180949) or the like can be used.
  • the content of the curing accelerator is preferably 0.3 to 8.9% by mass based on the total solid content of the curable composition, and 0.8 to 6% by mass. 0.4 mass% is more preferred.
  • the curable composition of the present invention can contain a silane coupling agent.
  • a silane coupling agent a silane compound having at least two types of functional groups having different reactivities in one molecule is preferable.
  • the silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureide group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. Is preferred.
  • silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) and N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-603), 3-Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu) Chemical Industry Co., Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) And KBM-403).
  • the description in paragraphs 0155 to 0158 of JP-A-2013-254407 can be referred to, and the contents thereof are incorporated herein.
  • the content of the silane coupling agent is preferably 0.001 to 20% by mass based on the total solid content of the curable composition, and 0.01 to 10% by mass. % By mass is more preferable, and 0.1 to 5% by mass is particularly preferable.
  • the curable composition of the present invention may include only one type of silane coupling agent, or may include two or more types. When two or more kinds are contained, the total amount thereof is preferably within the above range.
  • the curable composition of the present invention can contain a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine salts (ammonium salts, cerous salts) and the like.
  • the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the curable composition.
  • the curable composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds are contained, the total amount thereof is preferably within the above range.
  • the curable composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used.
  • paragraphs 0052 to 0072 of JP-A-2012-208374, paragraphs 0317 to 0334 of JP-A-2013-068814, and paragraphs 0061 to 0080 of JP-A-2016-162946 can be referred to. These contents are incorporated herein.
  • UV absorbers include, for example, UV-503 (manufactured by Daito Chemical Co., Ltd.).
  • benzotriazole compound examples include MYUA series (manufactured by Miyoshi Oil & Fats, Chemical Daily, February 1, 2016).
  • compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as an ultraviolet absorber.
  • the content of the ultraviolet absorber is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the total solid content of the curable composition. Is more preferable, and 0.1 to 3% by mass is particularly preferable.
  • only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount is preferably within the above range.
  • the curable composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
  • paragraphs 0238 to 0245 of WO 2015/166779 can be referred to, and the contents thereof are incorporated herein.
  • the surfactant is preferably a fluorinated surfactant.
  • a fluorine-based surfactant in the curable composition, liquid properties (particularly, fluidity) are further improved, and liquid saving properties can be further improved.
  • a film with small thickness unevenness can be formed.
  • the fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of a coating film and liquid saving properties, and has good solubility in a curable composition.
  • fluorinated surfactant examples include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-041318 (paragraphs 0060 to 0064 of WO 2014/017669), and JP-A-2011-132503.
  • the surfactants described in paragraphs 0117 to 0132 of the gazette are exemplified, and the contents thereof are incorporated herein.
  • fluorine surfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PolyFox @ PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA) and the like. .
  • fluorine-based surfactants have a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off when heat is applied and the fluorine atom is volatilized. It can be suitably used.
  • fluorinated surfactant include Megafac DS series (manufactured by DIC Corporation, Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafac DS. -21.
  • a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant.
  • the description of JP-A-2016-216602 can be referred to for such a fluorine-based surfactant, and the contents thereof are incorporated herein.
  • a block polymer can also be used as the fluorine-based surfactant.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom, and has 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group and propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the following compounds are also exemplified as the fluorinated surfactant used in the present invention.
  • the above compound has a weight average molecular weight of preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of the repeating unit is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used.
  • Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, Megafac RS-101, RS-102, RS-718K, RS manufactured by DIC Corporation. -72-K and the like.
  • the fluorine-based surfactant compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Co., Ltd.), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS ), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fuji
  • silicone-based surfactant examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning Inc.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all made by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (all, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (all manufactured by Big Chemie).
  • the content of the surfactant in the total solid content of the curable composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass.
  • the surfactant may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount thereof is within the above range.
  • the curable composition of the present invention may optionally contain various additives, for example, a filler, an adhesion promoter, an antioxidant, and an anti-agglomeration agent.
  • additives include those described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated herein.
  • the antioxidant for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph 0042 of JP-A-2011-090147), a thioether compound, or the like can be used.
  • antioxidants described in (1) can also be used.
  • One type of antioxidant may be used, or two or more types may be used.
  • the curable composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst.
  • a compound in which a protecting group is eliminated to function as an antioxidant can be mentioned.
  • Specific examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP-A-2017-008219.
  • Commercially available products include Adeka Aquel's GPA-5001 (manufactured by ADEKA Corporation).
  • the curable composition of the present invention may be a sensitizer or a light stabilizer described in paragraph 0078 of JP-A-2004-295116, a thermal polymerization inhibitor described in paragraph 0081 of the same, or JP-A-2018-091940.
  • the storage stabilizer described in paragraph No. 0242 of JP-A No. 2-1980 can be contained.
  • the curable composition of the present invention preferably has a content of free metal not bound or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, further preferably 10 ppm or less. Preferably, it is particularly preferable that it is not substantially contained. According to this aspect, stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of a curable component, suppression of conductivity fluctuation due to elution of metal atoms and metal ions, Effects such as improvement of display characteristics can be expected.
  • the types of the above free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Fe, Co, Mg, Al, Ti, Sn, Zn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Bi, and the like.
  • the curable composition of the present invention preferably has a content of free halogen not bound or coordinated with a pigment or the like of 100 mass ppm or less, more preferably 50 mass ppm or less, and 10 mass ppm or less. The content is more preferably not more than ppm by mass, and particularly preferably substantially not contained.
  • Examples of a method for reducing free metals and halogens in the curable composition include methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
  • the curable composition of the present invention contains substantially no terephthalate.
  • substantially free means that the content of the terephthalic acid ester in the solid content of the composition is 1000 mass ppb or less, more preferably 500 mass ppb or less, Particularly preferred is zero.
  • the container for storing the curable composition of the present invention is not particularly limited, and a known container can be used. Further, as a container, for the purpose of suppressing the contamination of impurities into the raw material and the curable composition, a multilayer bottle in which the inner wall of the container is composed of six types of six layers of resin and a six types of resin having a seven layer structure. It is also preferred to use bottles. Examples of such a container include a container described in JP-A-2015-123351.
  • the inner wall of the container is preferably made of glass or stainless steel from the viewpoint of preventing metal elution from the inner wall of the container, increasing storage stability of the composition, and suppressing deterioration of components.
  • the curable composition of the present invention can be produced by mixing the above components.
  • the curable composition may be produced by dissolving and / or dispersing all the components in a solvent at the same time.
  • the composition may be manufactured by mixing these at the time of use (at the time of application) as a liquid.
  • the production of the curable composition may include a process of dispersing particles such as pigments.
  • examples of mechanical force used for dispersing the pigment include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion.
  • fine processing of particles may be performed in a salt milling step.
  • the materials, equipment, processing conditions and the like used in the salt milling step can be referred to, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high-density, ultra-high molecular weight (Including polyolefin resin).
  • PTFE polytetrafluoroethylene
  • nylon eg, nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (high-density, ultra-high molecular weight (Including polyolefin resin).
  • PP polypropylene
  • nylon high-density polypropylene
  • nylon are preferred.
  • the pore size of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m.
  • the nominal value of the filter manufacturer can be referred to.
  • various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.
  • a fibrous filter medium examples include a polypropylene fiber, a nylon fiber, and a glass fiber.
  • Commercially available products include SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno.
  • filters for example, a first filter and a second filter
  • the filtration by each filter may be performed only once or may be performed twice or more.
  • filters having different hole diameters may be combined within the above-described range.
  • the filtration with the first filter may be performed only on the dispersion liquid, and after the other components are mixed, the filtration with the second filter may be performed.
  • the cured film of the present invention can be produced by forming a film of the above-described curable composition of the present invention, drying and curing the film.
  • the cured film of the present invention can be preferably used as a near infrared transmitting filter.
  • the thickness of the cured film can be appropriately adjusted depending on the purpose, and is preferably 100 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the lower limit of the thickness is preferably at least 0.1 ⁇ m, more preferably at least 0.2 ⁇ m, even more preferably at least 0.3 ⁇ m.
  • the maximum value of light transmittance in the thickness direction of the film in a wavelength range of 400 to 600 nm is 20% or less; It is preferable to satisfy the spectral characteristic that the minimum value in the wavelength range of 1000 to 1300 nm is 70% or more.
  • the maximum value in the wavelength range of 400 to 600 nm is preferably 15% or less, more preferably 10% or less.
  • the minimum value in the wavelength range of 1000 to 1300 nm is preferably at least 75%, more preferably at least 80%.
  • the cured film of the present invention more preferably satisfies any of the following spectral characteristics (11) to (14).
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 640 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 950 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the optical filter of the present invention is, for example, a near-infrared transmitting filter and includes the cured film of the present invention.
  • the optical filter of the present invention may be provided with a protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 on the surface of the cured film.
  • the optical filter of the present invention may include an RGB color filter containing a chromatic colorant. Such a color filter is manufactured using a curable composition containing the same chromatic colorant as the chromatic colorant described in the description of the color material.
  • the pattern forming method of the present invention includes a step of forming a curable composition layer on a support using the curable composition of the present invention, and a step of forming a curable composition layer having a thickness of more than 350 nm to 380 nm or less.
  • a second exposure step of irradiating light having the following.
  • the treatment can be performed at a temperature of less than 200 ° C., preferably at a temperature of 150 ° C. or less throughout all the steps.
  • “the treatment is performed at a temperature of less than 200 ° C. throughout the entire process” means that all of the steps of forming a patterned cured film using the curable composition are performed at a temperature of less than 200 ° C. Means that.
  • a heating step may be further provided after the second exposure step. However, in this case, the heating temperature is lower than 200 ° C.
  • each step will be described in detail.
  • the curable composition of the present invention is applied on a support to form a curable composition layer.
  • the support is, for example, a glass substrate or a resin substrate.
  • the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate.
  • An organic light emitting layer or a photoelectric conversion layer may be formed on these substrates.
  • the substrate may be provided with an undercoat layer for improving adhesion to an upper layer, preventing diffusion of a substance, or planarizing the surface.
  • the undercoat layer may be formed, for example, by applying a curable composition obtained by removing a coloring material from the curable composition of the present invention.
  • a known method can be used as a method for applying the composition.
  • a dropping method drop casting
  • a slit coating method for example, a spraying method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, JP-A-2009-145395).
  • Publications inkjet (eg, on-demand method, piezo method, thermal method), discharge printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • Various printing methods a transfer method using a mold or the like; a nanoimprint method, and the like.
  • the application method in the ink jet is not particularly limited, and for example, a method shown in “Spread and usable ink jets—infinite possibilities seen in patents”, published in February 2005, Sumibe Techno Research (especially from page 115). 133 page), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261828, JP-A-2012-126830, JP-A-2006-169325, and the like. No.
  • the descriptions in WO2017 / 030174 and WO2017 / 018419 can be referred to, and the contents thereof are incorporated in the present specification.
  • the cured composition layer formed on the support may be dried (prebaked).
  • the prebaking temperature is preferably 80 ° C or lower, more preferably 70 ° C or lower, still more preferably 60 ° C or lower, and particularly preferably 50 ° C or lower.
  • the lower limit can be, for example, 40 ° C. or higher.
  • the prebake time is preferably from 10 to 3600 seconds. Prebaking can be performed on a hot plate, an oven, or the like.
  • First exposure step light is applied to the curable composition layer in a pattern by irradiating light having a wavelength of more than 350 nm and not more than 380 nm.
  • the curable composition layer can be exposed in a pattern by using an exposure device such as a stepper through a mask having a predetermined mask pattern. Thereby, the exposed portion of the curable composition layer can be cured.
  • Light that can be used for exposure is light having a wavelength of more than 350 nm and not more than 380 nm, preferably light having a wavelength of 355 to 370 nm, and more preferably i-line (365 nm). This exposure processing may be performed while cutting light having a wavelength shorter than the i-line, as described in KR10201702122130A.
  • the irradiation dose for example, preferably 30 ⁇ 1500mJ / cm 2, more preferably 50 ⁇ 1000mJ / cm 2.
  • the oxygen concentration at the time of exposure can be appropriately selected.
  • a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free)
  • a high oxygen atmosphere having an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume).
  • the exposure illuminance can be appropriately set and can be selected from a range of usually 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , 35000 W / m 2 ). .
  • Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
  • the reaction rate of the polymerizable compound in the curable composition layer after exposure is preferably more than 30% and less than 80%. With such a reaction rate, the polymerizable compound can be in a state of being appropriately cured.
  • the reaction rate is preferably set to be higher. Further, in the present invention, the reaction rate is more preferably from 40 to 75%, further preferably from 50 to 70%.
  • the reaction rate of the polymerizable compound refers to a ratio of the reacted polymerizable group among the polymerizable groups included in the polymerizable compound before the first exposure step.
  • the reaction rate of the polymerizable compound can be determined as an average value in the thickness direction of the film by analyzing a peak area near 810 cm -1 by an infrared absorption spectrum method.
  • a pattern (pixel) is formed by developing and removing an unexposed portion of the curable composition layer.
  • the development removal of the unexposed portion of the curable composition layer can be performed using a developer.
  • the curable composition layer in the unexposed portion in the exposure step elutes into the developer, leaving only the photocured portion.
  • the developer include an organic solvent and an alkali developer, and an alkali developer is preferable.
  • the temperature of the developer is preferably, for example, 20 to 30 ° C.
  • the development time is preferably from 20 to 180 seconds. Further, in order to improve the residue removal property, the step of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
  • the alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water.
  • the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene
  • Alkaline compounds sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate.
  • the alkali agent a compound having a large molecular weight is preferable in terms of environment and safety.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass.
  • the developer may further contain a surfactant.
  • the surfactant include the surfactants described above, and a nonionic surfactant is preferable.
  • the developer may be once produced as a concentrated solution and diluted to a necessary concentration at the time of use, from the viewpoint of convenience of transportation and storage.
  • the dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times.
  • the rinsing is preferably performed by supplying a rinsing liquid to the curable composition layer after development while rotating the support on which the curable composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the center of the support to the peripheral edge of the support. At this time, when the nozzle is moved from the central portion to the peripheral portion of the support, the nozzle may be moved while gradually lowering the moving speed. By performing rinsing in this manner, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually lowering the rotation speed of the support while moving the nozzle from the center of the support to the peripheral portion.
  • Second exposure step the curable composition layer is exposed to light having a wavelength of 254 to 350 nm.
  • the light to be irradiated preferably contains light having a wavelength of 300 nm or less, and more preferably contains light having a wavelength of 254 nm.
  • the second exposure step can be performed using, for example, an ultraviolet photoresist curing device. From the ultraviolet photoresist curing device, for example, light having a wavelength of 254 to 350 nm and other light (for example, i-line) may be irradiated.
  • the difference between the wavelength of light used in the above-described exposure before development and the wavelength of light used in the exposure after development (post-exposure) is preferably 200 nm or less, and more preferably 100 to 150 nm.
  • Irradiation dose is preferably 30 ⁇ 4000mJ / cm 2, more preferably 50 ⁇ 3500mJ / cm 2.
  • the oxygen concentration at the time of exposure can be appropriately selected, similarly to the conditions at the time of the first exposure step.
  • the reaction rate of the polymerizable compound in the curable composition layer after exposure is preferably 60% or more.
  • the upper limit may be set to 100% or less, or may be set to 90% or less.
  • the curable composition layer can be appropriately cured by the first exposure (exposure before development).
  • Exposure 2 exposure after development
  • the curable composition layer is sufficiently cured to form a pattern-like cured film having excellent adhesiveness and excellent solvent resistance, flatness and rectangularity. be able to.
  • the curable composition layer is heated at a predetermined temperature between the developing step and the second exposure step, and at least one of the periods after the second exposure step.
  • a step (post bake) may be performed.
  • the heating temperature of post-baking is preferably lower than 200 ° C., more preferably 150 ° C. or lower, further preferably 120 ° C. or lower. Further, the heating temperature of the post-baking is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 80 ° C. or higher.
  • the heating temperature is preferably 50 to 120 ° C, more preferably 80 to 100 ° C, and 80 to 90 ° C. Is more preferred.
  • the heating time can be appropriately selected and is, for example, 1 to 10 minutes, preferably 2 to 8 minutes, and more preferably 3 to 6 minutes.
  • the post bake may be performed in the air or in a low oxygen atmosphere.
  • the post-baking is preferably performed in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less, and the oxygen concentration is preferably 15% by volume or less. It is more preferably at most 5% by volume, particularly preferably at most 1% by volume (substantially oxygen-free).
  • the post-bake can be performed continuously or batch-wise using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), a high frequency heater or the like.
  • a heating means such as a hot plate, a convection oven (hot air circulation type dryer), a high frequency heater or the like.
  • post-baking may not be performed.
  • the thickness of the patterned cured film after the second exposure step is preferably 0.1 to 5.0 ⁇ m.
  • the lower limit is preferably at least 0.2 ⁇ m, more preferably at least 0.5 ⁇ m.
  • the upper limit is preferably 4.0 ⁇ m or less, more preferably 2.5 ⁇ m or less.
  • the width of the pattern of the cured film is preferably 0.5 to 20.0 ⁇ m.
  • the lower limit is preferably at least 1.0 ⁇ m, more preferably at least 2.0 ⁇ m.
  • the upper limit is preferably 15.0 ⁇ m or less, more preferably 10.0 ⁇ m or less.
  • the patterned cured film preferably has a Young's modulus of 0.5 to 20 GPa, more preferably 2.5 to 15 GPa. The Young's modulus can be measured using, for example, a nanoindentation method.
  • the optical sensor of the present invention includes, for example, a solid-state imaging device constituting a light-receiving element, and a near-infrared transmission filter of the present invention installed on the light-receiving side of the solid-state imaging device. With such a configuration, near infrared rays in a desired wavelength range can be received by the light receiving element.
  • the optical sensor incorporating the near-infrared transmission filter of the present invention can be applied to a CCD (charge coupled device) image sensor, a CMOS (complementary metal oxide semiconductor) image sensor, and the like. It can be preferably used for mobile applications, automobile applications, agricultural applications, medical applications, distance measurement applications, gesture recognition applications, and the like.
  • composition (curable composition) was prepared by mixing the raw materials described in the following table.
  • the numerical values in the following table are parts by mass.
  • IB Irgaphor Black S 0100 CF (manufactured by BASF, compound having the following structure, lactam pigment)
  • PBk32 C.I. I. Pigment Black 32 (compound having the following structure, perylene pigment)
  • PR254 C.I. I. Pigment Red 254
  • PY139 C.I. I. Pigment Yellow 139
  • PB15 6: C.I. I. Pigment Blue 15: 6
  • PB16 C.I. I. Pigment Blue 16 PV23: C.I. I. Pigment Violet 23
  • D1 TMPEOTA (manufactured by Daicel Ornex)
  • D2 Monomer having the following structure.
  • D3 Monomer having the following structure.
  • D4 a mixture of compounds having the following structure (a mixture in which the molar ratio of the left compound (6-functional (meth) acrylate compound) to the right compound (pentafunctional (meth) acrylate compound) is 7: 3)
  • D5 Compound having the following structure (tetrafunctional (meth) acrylate compound having an alkyleneoxy group)
  • I-A1 IRGACURE-OXE02 (manufactured by BASF)
  • I-A2 IRGACURE-OXE03 (manufactured by BASF)
  • I-A3 IRGACURE379 (manufactured by BASF)
  • I-B1 IRGACURE2959 (manufactured by BASF)
  • I-B2 IRGACURE 1173 (manufactured by BASF)
  • Each composition was applied on a glass substrate by spin coating so that the film thickness after the post-baking had the film thickness described in the following table, and after heating and drying at 100 ° C. for 120 seconds using a hot plate, Further, a heat treatment (post-bake) was performed at 200 ° C. for 300 seconds to form a film.
  • the glass substrate on which the film was formed was measured using a UV-visible-near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Tech) to measure the minimum absorbance A in the wavelength range of 400 to 600 nm and the absorbance in the wavelength range of 1000 to 1300 nm.
  • the maximum value B was measured.
  • CT-4000L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied on an 8-inch (1 inch is approximately 2.54 cm) silicon wafer by spin coating to form a coating film.
  • the film was treated in an oven at 220 ° C. for 1 hour to cure the applied film and form an undercoat layer.
  • the spinning speed of spin coating was adjusted so that the thickness of the undercoat layer after the heat treatment was about 0.1 ⁇ m.
  • each composition obtained above is applied on an undercoat layer of the silicon wafer using a spin coater so that the film thickness after drying becomes a film thickness described in the following table, and using a hot plate. Dry at 100 ° C. for 120 seconds.
  • the entire glass wafer was irradiated with an exposure amount of 10,000 mJ / cm 2 by using an ultraviolet photoresist curing device (MMA-802-HC-552, manufactured by Ushio Electric Co., Ltd.) to perform a second exposure.
  • an ultraviolet photoresist curing device MMA-802-HC-552, manufactured by Ushio Electric Co., Ltd.
  • a cellophane tape is pressed using a pressure roller (2 kg) for a peeling test, and the tape is peeled off at a speed of 75 mm / sec while tilting the end of the tape at an angle of 45 °.
  • the numbers were evaluated as follows.
  • the adhesion was evaluated using an optical microscope according to the following criteria.
  • compositions of Examples were able to form patterns having excellent adhesion.

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