WO2020075568A1 - Coloring composition, film, method for producing color filter, color filter, solid state imaging device and image display device - Google Patents

Coloring composition, film, method for producing color filter, color filter, solid state imaging device and image display device Download PDF

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Publication number
WO2020075568A1
WO2020075568A1 PCT/JP2019/038684 JP2019038684W WO2020075568A1 WO 2020075568 A1 WO2020075568 A1 WO 2020075568A1 JP 2019038684 W JP2019038684 W JP 2019038684W WO 2020075568 A1 WO2020075568 A1 WO 2020075568A1
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WIPO (PCT)
Prior art keywords
pigment
mass
coloring composition
resin
axis length
Prior art date
Application number
PCT/JP2019/038684
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French (fr)
Japanese (ja)
Inventor
昂広 大河原
Original Assignee
富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2020550438A priority Critical patent/JP7284184B2/en
Publication of WO2020075568A1 publication Critical patent/WO2020075568A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to a coloring composition containing a pigment.
  • the present invention also relates to a film using the coloring composition, a method for producing a color filter, a color filter, a solid-state image sensor, and an image display device.
  • Color filters are used as key devices for displays and optical elements.
  • the color filter is manufactured using a coloring composition containing a coloring agent such as a pigment.
  • Patent Document 1 contains a pigment and a binder component as essential components, and when the pigment has a minor axis of the primary particle as a and a major axis as b, the content of the primary particles satisfying the formula (1) is 70.
  • Patent Document 2 is an invention relating to a pigment ink composition used for inks for inkjet printers, which contains pigment particles containing at least needle pigment particles, a dispersant, and a solvent, Has a needle-like shape with an aspect ratio of 3 or more, an average aspect ratio of 5 or more and 7 or less, an average minor axis of 20 nm or more and 30 nm or less, and a standard deviation of the minor axis of 2.0 nm or less, and An invention is described for a pigment ink composition in which acicular pigment particles are coated with a dispersant.
  • voids are likely to occur between adjacent members.
  • a pixel of a color filter is formed using a coloring composition containing a pigment
  • the pixel contracts and the line width of the pixel decreases a void occurs between adjacent pixels and the sensitivity of the device changes. It may happen.
  • an object of the present invention is to provide a coloring composition capable of forming a film in which film shrinkage is suppressed.
  • the present invention also provides a film, a color filter manufacturing method, a color filter, a solid-state imaging device, and an image display device using the coloring composition.
  • the present invention provides the following.
  • a coloring composition containing a coloring agent, a resin, and an organic solvent, Containing 50% by mass or more of a colorant in the total solid content of the coloring composition contains 40% by mass or more of pigment A having a major axis length / minor axis length value of 1.4 or more, which is a ratio of the minor axis length to the major axis length.
  • the coloring composition according to ⁇ 1> which contains 60% by mass or more of a colorant in the total solid content of the coloring composition.
  • the pigment A is the coloring composition according to ⁇ 1> or ⁇ 2>, wherein the major axis length / minor axis length value is 1.4 or more and 3.0 or less.
  • ⁇ 5> The coloring composition according to any one of ⁇ 1> to ⁇ 4>, wherein the pigment A has an average minor axis length of 10 to 100 nm.
  • ⁇ 6> The coloring composition according to any one of ⁇ 1> to ⁇ 5>, in which the pigment A is a red pigment.
  • ⁇ 7> The coloring composition according to ⁇ 6>, wherein the red pigment is at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272.
  • the red pigment is at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272.
  • ⁇ 8> The coloring composition according to any one of ⁇ 1> to ⁇ 7>, which contains a photopolymerization initiator and a polymerizable compound.
  • ⁇ 9> The coloring composition according to any one of ⁇ 1> to ⁇ 8>, in which the resin contains an alkali-soluble resin.
  • the coloring composition according to any one of ⁇ 1> to ⁇ 9> which is for forming a pattern by a photolithography method.
  • ⁇ 11> The coloring composition according to any one of ⁇ 1> to ⁇ 10>, which is for a solid-state imaging device.
  • ⁇ 12> The coloring composition according to any one of ⁇ 1> to ⁇ 10>, which is for a color filter.
  • ⁇ 13> The coloring composition according to ⁇ 12>, which is for forming red pixels.
  • ⁇ 14> A film obtained from the coloring composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> A step of forming a coloring composition layer on a support using the coloring composition according to any one of ⁇ 1> to ⁇ 13>, and a pattern for the coloring composition layer by a photolithography method. Forming a color filter.
  • ⁇ 16> A color filter having the film according to ⁇ 14>.
  • ⁇ 17> A solid-state image sensor having the film according to ⁇ 14>.
  • ⁇ 18> An image display device having the film according to ⁇ 14>.
  • a colored composition capable of forming a film in which film shrinkage is suppressed, a film, a method for producing a color filter, a color filter, a solid-state image sensor, and an image display device.
  • substitution and non-substitution are not included as a lower limit value and an upper limit value.
  • the notation in which substitution and non-substitution are not included includes a group (atomic group) having no substituent and a group (atomic group) having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the term "exposure” includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified.
  • Examples of the light used for exposure include a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron rays, or radiation.
  • EUV light extreme ultraviolet rays
  • active rays such as X-rays and electron rays
  • radiation or radiation.
  • (meth) acrylate” represents both acrylate and methacrylate, or either
  • “(meth) acrylic” represents both acrylic and methacrylic
  • “Acryloyl” means both acryloyl and methacryloyl, or either.
  • the weight average molecular weight and the number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography) method.
  • the total solid content refers to the total mass of the components of the composition excluding the solvent.
  • the pigment means a compound that is difficult to dissolve in a solvent.
  • the pigment preferably has a solubility of 0.1 g or less in 100 g of water at 23 ° C.
  • step is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
  • the coloring composition of the present invention is a coloring composition containing a colorant, a resin and an organic solvent, Containing 50% by mass or more of a colorant in the total solid content of the coloring composition,
  • the colorant is characterized by containing 40% by mass or more of pigment A having a value of major axis length / minor axis length, which is a ratio of minor axis length to major axis length, of 1.4 or more.
  • the coloring composition of the present invention by containing 50% by mass or more of the above-described coloring agent containing 40% by mass or more of pigment A in the total solid content of the coloring composition, it is possible to suppress shrinkage of the obtained film. It is speculated that the pigment A is densely spread in the obtained film, and as a result, it is speculated that the shrinkage of the obtained film could be suppressed. In particular, even when the film is exposed to a high humidity environment for a long time, the film shrinkage can be effectively suppressed. Further, since the coloring composition of the present invention contains the coloring agent in an amount of 50% by mass or more, it is possible to form a film having a high color value. Therefore, thinning can be achieved while maintaining desired spectral characteristics.
  • the value of the major axis length / minor axis length of the pigment A is preferably 1.4 or more and 3.0 or less. According to this aspect, when a pattern is formed by the photolithography method using the coloring composition of the present invention, it is possible to suppress the occurrence of a development residual and to form a pattern having good rectangularity.
  • the pigment A is preferably a red pigment.
  • Red pigments generally tend to have a low color value, but by using a red pigment having a major axis length / minor axis length value of 1.4 or more, the red pigment is formed in the film. It can be densely spread and can form a film with a high red color value.
  • the colored composition of the present invention can be preferably used as a colored composition for a solid-state imaging device.
  • the coloring composition of the present invention can be preferably used as a coloring composition for a color filter. Specifically, it can be preferably used as a coloring composition for forming a pixel of a color filter, and more preferably used as a coloring composition for forming a pixel of a color filter used in a solid-state imaging device.
  • the pixels of the color filter include colored pixels such as red pixels, blue pixels, green pixels, yellow pixels, cyan color pixels, and magenta color pixels.
  • the coloring composition of the present invention is preferably used as a coloring composition for forming red pixels.
  • the colored composition of the present invention can be preferably used for pattern formation by a photolithography method.
  • the coloring composition of the present invention preferably contains a photopolymerization initiator and a polymerizable compound.
  • the resin contained in the coloring composition preferably contains an alkali-soluble resin.
  • the colored composition of the present invention can also be used as a composition for forming a color microlens.
  • Examples of the method for manufacturing a color microlens include the method described in JP-A-2018-010162.
  • the coloring composition of the present invention contains a coloring agent.
  • the colorant include chromatic colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant and an orange colorant.
  • the colorant include pigments and dyes, and those containing a pigment are used.
  • the pigment may be either an inorganic pigment or an organic pigment.
  • a material in which a part of an inorganic pigment or an organic-inorganic pigment is replaced with an organic chromophore can also be used. By substituting an inorganic pigment or an organic-inorganic pigment with an organic chromophore, hue design can be facilitated.
  • the colorant used in the present invention has a mass ratio of the major axis length / minor axis length, which is the ratio of the minor axis length to the major axis length, of pigment A having a value of 1.4 or more (hereinafter, also simply referred to as pigment A) of 40 mass. % Or more.
  • the value of major axis length / minor axis length of the pigment A is preferably 1.4 or more and 3.0 or less.
  • the value of the major axis length / minor axis length of the pigment A is within the above range, it is easy to obtain a film having high color value and suppressed film shrinkage.
  • a pattern is formed by the photolithography method using the colored composition of the present invention, it is possible to suppress the occurrence of a development residual and form a pattern having a good rectangularity.
  • the upper limit of the value of the major axis length / the minor axis length of the pigment A is preferably 2.7 or less, and is 2.4 or less because it is easy to obtain a film with high brightness by suppressing light scattering. Is more preferable.
  • the lower limit of the value of the major axis length / minor axis length of the pigment A is preferably 1.6 or more, and is preferably 1.8 or more because the pigment can be more densely spread in the film. Is more preferable, and 2.0 or more is more preferable.
  • the average minor axis length of Pigment A is preferably 10 to 100 nm.
  • the lower limit is preferably 15 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more from the viewpoint of reliability such as heat resistance, moisture resistance and weather resistance of the obtained film.
  • the upper limit is preferably 70 nm or less, more preferably 50 nm or less, further preferably 40 nm or less.
  • the average major axis length of Pigment A is preferably 15 to 150 nm.
  • the lower limit is preferably 20 nm or more, more preferably 30 nm or more.
  • the upper limit is preferably 100 nm or less, more preferably 70 nm or less, further preferably 50 nm or less.
  • the major axis length and the minor axis length are values measured by the following method. That is, by using a scanning electron microscope, an image taken at an accelerating voltage of 5 kV and an imaging magnification of 100,000 is digitized, and image luminance data in the major axis direction and minor axis direction of particles (coordinates in major axis direction, minor axis direction). Is composed of three components, namely, the coordinates of, and the luminance). In the digitization, an image is divided into 1280 in the width direction and processed with 8-bit luminance to obtain data of 256 gradations, and the image luminance of each divided coordinate point is converted into a predetermined gradation value.
  • the horizontal axis represents the coordinate in the direction of the long axis of the particle, and the average value of the brightness at each coordinate point in the long axis direction (that is, the average value of the brightness at each of the 1280 divided coordinate points).
  • Is the vertical axis and a brightness curve is created.
  • the created brightness curve is differentiated to create a differential curve, and the coordinate of the boundary of the particle is specified from the peak position of the created differential curve.
  • the operation of setting the coordinate in the direction corresponding to the long axis of the particle as the horizontal axis is repeated three times, and the longest axis length is set as the long axis length.
  • the operation of setting the coordinate on the horizontal axis is repeated three times, and the shortest axis length is set as the short axis length.
  • the major axis length is determined by defining the axis (straight line) that can maximize the length of the particle as the major axis, and using the major axis length.
  • the minor axis is determined as the axis that has the longest length when the particle length is taken on a straight line orthogonal to the major axis, and the length of this axis is defined as the minor axis length.
  • the average value of the short axis length of the pigment A and the average value of the long axis length of the pigment A are the arithmetic average values of the short axis length and the long axis length of 100 pigments A.
  • the major axis length / minor axis length value of the pigment can be adjusted by adjusting the milling conditions of the pigment to adjust the major axis length / minor axis length values, and the type and amount of the particle growth inhibitor.
  • the particle growth inhibitor include the compounds described in paragraph Nos. 0041 to 0050 of JP-A-2009-212266.
  • the types of pigments used in the present invention include those shown below.
  • Pigment C. I. Pigment Orange 2, 5, 13, 16, 17, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Above, orange pigment), C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63 etc. (above, green pigment), C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane type), 61 (xanthene type), etc. (above, purple pigment), C. I.
  • Pigment Blue 1 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo system), 88 (methine / polymethine type), etc. (above, blue pigment), C. I.
  • a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12 and an average number of chlorine atoms of 2 to 5 Can also be used. Specific examples thereof include the compounds described in International Publication WO2015 / 118720. Further, the compound described in CN1069009027A, a phthalocyanine compound having a phosphoric acid ester as a ligand, or the like can be used as a green pigment.
  • an aluminum phthalocyanine compound having a phosphorus atom may be used as the blue pigment.
  • Specific examples thereof include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraph 0047 of JP2011-157478A.
  • the pigments described in JP-A-2017-201003, the pigments described in JP-A-2017-197719, and paragraph numbers 0011 to 0062 and 0137 to JP-A-2017-171912 are disclosed.
  • the pigments described, and the pigments described in paragraph Nos. 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915 can also be used.
  • JP-A-2018-62644 can be used as the yellow pigment.
  • This compound can also be used as a pigment derivative.
  • red pigment a diketopyrrolopyrrole pigment in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole described in paragraph Nos. 0016 to 0022 of Japanese Patent No. 6248838.
  • a pyrrole pigment or the like can also be used.
  • red pigment it is also possible to use a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is introduced is bound to a diketopyrrolopyrrole skeleton. it can.
  • the pigment A used in the present invention preferably contains a red pigment.
  • the red pigment is also preferably a diketopyrrolopyrrole compound.
  • the red pigment is preferably at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272, and more preferably Color Index Pigment Red 272.
  • Red pigments generally tend to have a low color value, but by using a red pigment having a major axis length / minor axis length value of 1.4 or more, a film having a high red color value can be obtained. Can be formed.
  • a dye may be used as the colorant.
  • the dye is not particularly limited, and known dyes can be used.
  • pyrazole azo type anilino azo type, triaryl methane type, anthraquinone type, anthrapyridone type, benzylidene type, oxonol type, pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type
  • Examples thereof include phthalocyanine-based dyes, benzopyran-based dyes, indigo-based dyes, and pyrromethene-based dyes.
  • the thiazole compound described in JP 2012-158649 A, the azo compound described in JP 2011-18449 A, and the azo compound described in JP 2011-145540 A can also be preferably used.
  • the yellow dye the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-054339A, the quinophthalone compounds described in paragraphs 0013 to 0058 of JP2014-026228A, and the like can be used.
  • a dye multimer may be used as the colorant.
  • the dye multimer is preferably a dye used by being dissolved in a solvent, but the dye multimer may form particles, and when the dye multimer is particles, it is usually in a state of being dispersed in a solvent. Used.
  • the dye multimer in the form of particles can be obtained, for example, by emulsion polymerization, and specific examples thereof include the compounds and production methods described in JP-A-2015-214682.
  • the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
  • the plurality of dye structures contained in one molecule may be the same dye structure or different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000.
  • the lower limit is more preferably 3,000 or more, still more preferably 6000 or more.
  • the upper limit is more preferably 30,000 or less, further preferably 20,000 or less.
  • Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, International Publication WO2016 / 031442, and the like. Compounds can also be used.
  • the content of the coloring agent is 50% by mass or more based on the total solid content of the coloring composition, preferably 53% by mass or more, more preferably 59% by mass or more, and further preferably 62% by mass or more.
  • the upper limit is preferably 85% by mass or less, and more preferably 80% by mass or less.
  • the coloring agent used in the coloring composition of the present invention has a pigment content of 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. Is more preferable, 80% by mass or more is more preferable, 90% by mass or more is still more preferable, and 95% by mass or more is particularly preferable.
  • the upper limit can be 100% by mass.
  • the coloring agent used in the coloring composition of the present invention is substantially only a pigment.
  • the case where the colorant is substantially only the pigment means that the content of the pigment is 99% by mass or more, preferably 99.5% by mass or more, and particularly preferably only the pigment. .
  • the colorant used in the coloring composition of the present invention contains two or more pigments, at least one of the two or more pigments may be the above-described pigment A, but all pigments contained in the colorant Is preferably the pigment A described above.
  • the colorant used in the coloring composition of the present invention contains the above-described pigment A (pigment having a major axis length / minor axis length value, which is a ratio of the minor axis length to the major axis length, of 1.4 or more). Is 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and further preferably 80% by mass or more. It is more preferably 90% by mass or more, still more preferably 95% by mass or more. The upper limit can be 100% by mass. It is also preferable that the coloring agent used in the coloring composition of the present invention is substantially only the pigment A.
  • the case where the colorant is substantially only the pigment A means that the content of the pigment A is 99% by mass or more, preferably 99.5% by mass or more, and only the pigment A is contained. Is particularly preferable.
  • the content of the pigment is preferably 50% by mass or more, more preferably 53% by mass or more, further preferably 59% by mass or more, and 62% by mass in the total solid content of the coloring composition. % Or more is particularly preferable.
  • the upper limit is preferably 85% by mass or less, and more preferably 80% by mass or less.
  • the coloring composition of the present invention contains a resin.
  • the resin is mixed, for example, for the purpose of dispersing the pigment in the coloring composition or the use of a binder.
  • the resin mainly used for dispersing the pigment is also referred to as a dispersant.
  • such an application of the resin is an example, and the resin can be used for purposes other than such an application.
  • the weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • the resin examples include (meth) acrylic resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin. , Polyolefin resins, cyclic olefin resins, polyester resins, styrene resins and the like. One of these resins may be used alone, or two or more thereof may be mixed and used. Further, the resins described in paragraphs 0041 to 0060 of JP-A-2017-206689 and the resins described in paragraphs 0022 to 0071 of JP-A-2018-010856 can also be used.
  • a resin having an acid group as the resin.
  • the developability of the colored composition can be improved, and pixels having excellent rectangularity can be easily formed.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group, and a carboxyl group is preferable.
  • the resin having an acid group can be used as, for example, an alkali-soluble resin.
  • the resin having an acid group preferably contains a repeating unit having an acid group as a side chain, and more preferably contains 5 to 70 mol% of a repeating unit having an acid group as a side chain in all repeating units of the resin.
  • the upper limit of the content of the repeating unit having an acid group in its side chain is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the lower limit of the content of the repeating unit having an acid group in its side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.
  • 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 dimers”). It is also preferable to include a repeating unit derived from the 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.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the resin used in the present invention preferably also contains 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 hydrogen atom or 1 to 20 carbon atoms which may include a benzene ring.
  • n represents an integer of 1 to 15.
  • the acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g.
  • the lower limit is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more.
  • the upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and further preferably 200 mgKOH / g or less.
  • the weight average molecular weight (Mw) of the resin having an acid group is preferably 5,000 to 100,000.
  • the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.
  • Examples of the resin having an acid group include resins having the following structures.
  • the coloring composition of the present invention may 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) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%, and the acid dispersant is substantially acid.
  • a resin consisting of only a group is more preferable.
  • the acid group contained in the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the acid value of the acidic dispersant is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and further preferably 60 to 105 mgKOH / g.
  • the basic dispersant represents a resin in which the amount of basic groups is larger than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%.
  • the basic group contained in the basic dispersant is preferably an amino group.
  • the resin used as the dispersant preferably contains a repeating unit having an acid group.
  • the resin used as the dispersant contains a repeating unit having an acid group, generation of a development residue can be further suppressed when forming a pattern by the photolithography method.
  • the resin used as the dispersant is also preferably a graft resin. Details of the graft resin can be referred to the descriptions in paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • the resin used as the dispersant is a polyimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
  • the polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom.
  • the resin having is preferable.
  • the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom that exhibits basicity.
  • the description in paragraph numbers 0102 to 0166 of JP 2012-255128 A can be referred to, and the contents thereof are incorporated in the present specification.
  • the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core part.
  • resins include dendrimers (including star polymers).
  • specific examples of the dendrimer include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A-2013-043962.
  • the above-mentioned resin having an acid group (alkali-soluble resin) can be used as a dispersant.
  • the resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond group in the side chain.
  • the content of the repeating unit having an ethylenically unsaturated bond group in its side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and more preferably 20 to 70 mol, based on all repeating units of the resin. % Is more preferable.
  • the dispersant is also available as a commercially available product, and specific examples thereof include the DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111 and 161, etc.), the Sols Perth series manufactured by Nippon Lubrizol Co., Ltd. For example, Solsperse 76500 etc.) and the like. Further, the pigment dispersant described in paragraph Nos. 0041 to 0130 of JP-A-2014-130338 can be used, and the contents thereof are incorporated in the present specification.
  • the resin described as the above dispersant can be used for purposes other than the dispersant. For example, it can also be used as a binder.
  • the content of the resin in the total solid content of the coloring composition is preferably 5 to 50% by mass.
  • the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
  • the content of the resin having an acid group (alkali-soluble resin) in the total solid content of the coloring composition is preferably 5 to 50% by mass.
  • the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
  • the content of the resin having an acid group (alkali-soluble resin) in the total amount of the resin is preferably 30% by mass or more, more preferably 50% by mass or more, and 70% by mass, because excellent developability is easily obtained.
  • the above is more preferable, and 80 mass% or more is particularly preferable.
  • the upper limit can be 100% by mass, 95% by mass, or 90% by mass or less.
  • the coloring composition of the present invention contains an organic solvent.
  • the organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like. For details of these, reference can be made to paragraph No. 0223 of International Publication WO 2015/166779, the contents of which 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 and methyl 3-methoxypropionate.
  • an organic solvent having a low metal content it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent having a mass ppt (parts per trilion) level may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
  • Examples of methods for removing impurities such as metals from organic solvents 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, still more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the organic solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, as for the isomer, only 1 type may be contained and 2 or more types may be contained.
  • the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
  • the content of the organic solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 30 to 90% by mass.
  • the coloring composition of the present invention does not substantially contain an environmentally controlled substance from the viewpoint of environmental regulation.
  • the phrase "substantially free of environmentally controlled substances” means that the content of the environmentally controlled substances in the colored composition is 50 mass ppm or less, preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
  • the environmentally controlled substance include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene.
  • REACH Registration Evaluation Authorization and Restriction of CHchemicals
  • PRTR Policy Release and Transfer Registor
  • VOC Volunteer Organics
  • the method is tightly regulated.
  • These compounds may be used as a solvent when producing each component used in the coloring composition of the present invention, and may be mixed in the coloring composition as a residual solvent. From the viewpoints of human safety and environmental consideration, it is preferable to reduce these substances as much as possible.
  • As a method for reducing the environmentally controlled substance there is a method in which the system is heated or decompressed to a temperature equal to or higher than the boiling point of the environmentally controlled substance and the environmentally controlled substance is distilled off from the system to reduce the amount.
  • distillation methods include the steps of the raw material, the step of the product obtained by reacting the raw material (for example, the resin solution or polyfunctional monomer solution after polymerization), or the step of the colored composition prepared by mixing these compounds. It is possible at any stage of.
  • the colored composition of the present invention preferably contains a polymerizable compound.
  • a polymerizable compound a known compound that can be crosslinked by a radical, an acid or heat can be used.
  • the polymerizable compound is preferably a compound having an ethylenically unsaturated bond group, for example. Examples of the ethylenically unsaturated bond group include a vinyl group, a (meth) allyl group and a (meth) acryloyl group.
  • the polymerizable compound used in the present invention is preferably a radical polymerizable compound.
  • the polymerizable compound may be in any chemical form such as a monomer, a prepolymer or an oligomer, but a monomer is preferable.
  • the molecular weight of the polymerizable compound is preferably 100 to 3000.
  • the upper limit is more preferably 2000 or less, still more preferably 1500 or less.
  • the lower limit is more preferably 150 or more, further preferably 250 or more.
  • the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond groups, and more preferably an ethylenically unsaturated bond group.
  • a compound containing 3 to 6 is more preferable.
  • the polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound.
  • polymerizable compound examples include paragraph numbers 0095 to 0108 of JP 2009-288705 A, paragraph 0227 of JP 2013-029760 A, paragraphs 0254 to 0257 of JP 2008-292970 A, and JP Compounds described in paragraphs 0034 to 0038 of 2013-253224, paragraphs 0477 of JP2012-208494A, JP2017-048367A, JP60557891A, and JP6031807A are disclosed. And their contents are incorporated herein.
  • dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku (stock) )
  • 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) Co., Ltd., NK ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues.
  • SR454, SR499 Compounds (eg, commercially available from Sartomer And are, SR454, SR499) is preferable.
  • trimethylolpropane tri (meth) acrylate trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate.
  • a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate.
  • Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • a compound having an acid group can also be used as the polymerizable compound.
  • the polymerizable compound having an acid group By using the polymerizable compound having an acid group, the polymerizable compound in the unexposed area can be easily removed during development, and the 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.
  • Examples of commercially available polymerizable compounds having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like.
  • the acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developing solution is good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling.
  • the polymerizable compound is 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, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
  • a polymerizable compound having an alkyleneoxy group can also be used.
  • the polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups.
  • Hexafunctional (meth) acrylate compounds are more preferred.
  • Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and trifunctional (meth) having three isobutyleneoxy groups. Examples include KAYARAD TPA-330, which is an acrylate.
  • the polymerizable compound may be a polymerizable compound having a fluorene skeleton.
  • Examples of commercially available polymerizable compounds having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (Osaka Gas Chemical Co., Ltd., (meth) acrylate monomer having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound that does not substantially contain an environmentally regulated substance such as toluene.
  • an environmentally regulated substance such as toluene.
  • Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12LT (manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of the polymerizable compound include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765.
  • Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable.
  • UA-7200 manufactured by Shin-Nakamura Chemical Co., Ltd.
  • DPHA-40H manufactured by Nippon Kayaku Co., Ltd.
  • UA-306H, UA-306T, UA-306I, AH-600. , T-600, AI-600, LINC-202UA manufactured by Kyoeisha Chemical Co., Ltd.
  • Kyoeisha Chemical Co., Ltd. and the like may be used.
  • the content of the polymerizable compound in the total solid content of the coloring composition is preferably 0.1 to 50% by mass.
  • the lower limit is more preferably 0.5% by mass or more, still more preferably 1% by mass or more.
  • the upper limit is more preferably 45% by mass or less, further preferably 40% by mass or less.
  • the polymerizable compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total of them be in the above range.
  • the total content of the polymerizable compound and the resin in the total solid content of the coloring composition is preferably 10 to 65% by mass from the viewpoint of curability, developability and film forming property.
  • the lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more.
  • the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less. Further, it is preferable to contain 30 to 300 parts by mass of the resin with respect to 100 parts by mass of the polymerizable compound.
  • the lower limit is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more.
  • the upper limit is preferably 250 parts by mass or less, more preferably 200 parts by mass or less.
  • the coloring composition of the present invention preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light rays in the ultraviolet region to the visible region are preferable.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • photopolymerization initiator examples include halogenated hydrocarbon derivatives (eg, compounds having a triazine skeleton, compounds having an oxadiazole skeleton), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds. , Ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
  • the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole, from the viewpoint of exposure sensitivity.
  • a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl-substituted coumarin compound are preferable, and an oxime compound and an ⁇ -hydroxyketone compound are preferable. More preferably, it is a compound selected from an ⁇ -aminoketone compound and an acylphosphine compound, and even more preferably an oxime compound.
  • the descriptions in paragraphs 0065 to 0111 and JP 6301489 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated in the present specification.
  • Examples of commercially available ⁇ -hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF).
  • Commercially available ⁇ -aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF).
  • Examples of commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (above, manufactured by BASF).
  • Examples of the oxime compound include the compounds described in JP 2001-233842 A, the compounds described in JP 2000-080068 A, the compounds described in JP 2006-342166 A, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compound described in J. C. S. Compounds described in Perkin II (1979, pp.156-162), Compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in Japanese Patent Laid-Open No. 2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-0197766, compounds described in Patent No.
  • oxime compound examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-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 Examples thereof include imino-1-phenylpropan-1-one.
  • IRGACURE-OXE01 IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tengden Electronic New Materials Co., Ltd.), and ADEKA OPTOMER N-1919.
  • Photopolymerization initiator 2 described in JP 2012-14052 A manufactured by ADEKA Corporation can be used.
  • the oxime compound it is also preferable to use a compound having no coloring property or a compound having high transparency and being resistant to discoloration. Examples of commercially available products include ADEKA ARKUL'S NCI-730, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation).
  • an oxime compound having a fluorene ring can be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466. This content is incorporated herein.
  • an oxime compound having a fluorine atom can be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom are described in JP 2010-262028 A, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP 2013-164471 A. Compound (C-3) and the like. This content is incorporated herein.
  • an oxime compound having a nitro group can be used as the photopolymerization initiator.
  • 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 JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, The compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071 are ADEKA ARCRUZ NCI-831 (manufactured by ADEKA Corporation).
  • an oxime compound having a benzofuran skeleton can be used as the photopolymerization initiator.
  • Specific examples thereof include OE-01 to OE-75 described in International Publication WO2015 / 036910.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1,000 to 300,000, and more preferably 2,000 to 300,000. Is more preferable, and 5,000 to 200,000 is particularly preferable.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator.
  • two or more radicals are generated from one molecule of the photo-radical polymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity is lowered and the solubility in an organic solvent or the like is improved, it is difficult to deposit over time, and the stability over time of the coloring composition can be improved. it can.
  • bifunctional or trifunctional or more functional photoradical polymerization initiators include those disclosed in JP 2010-527339 A, JP 2011-524436 A, International Publication WO 2015/004565 and JP 2016-532675.
  • the content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 30% by mass.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
  • the photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention may contain a pigment derivative.
  • the storage stability of the colored composition can be further improved.
  • the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acid group, a basic group, a group having a salt structure or a phthalimidomethyl group.
  • a compound represented by the formula (B1) is preferable.
  • P represents a dye structure
  • L represents a single bond or a linking group
  • X represents an acid group, a basic group, a group having a salt structure or a phthalimidomethyl group
  • m is an integer of 1 or more.
  • n represents an integer of 1 or more, and when m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of X may be different from each other.
  • the dye structure represented by P is a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a quinacridone dye structure, an anthraquinone dye structure, a dianthraquinone dye structure, a benzoisoindole dye structure, a thiazineindigo dye structure, an azo dye structure, a quinophthalone.
  • Examples thereof include a dye structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, a dioxazine dye structure, a perylene dye structure, a perinone dye structure, a benzimidazolone dye structure, a benzothiazole dye structure, a benzimidazole dye structure and a benzoxazole dye structure.
  • linking group represented by L examples include a hydrocarbon group, a heterocyclic group, —NR—, —SO 2 —, —S—, —O—, —CO—, or a combination thereof.
  • R represents a hydrogen atom, an alkyl group or an aryl group.
  • Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imide acid group.
  • the carboxamide group is preferably a group represented by —NHCOR X1 .
  • the sulfonic acid amide group is preferably a group represented by —NHSO 2 R X2 .
  • the imido acid group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 .
  • R X1 to R X6 each independently represent a hydrocarbon group or a heterocyclic group.
  • the hydrocarbon group and heterocyclic group represented by R X1 to R X6 may further have a substituent.
  • the further substituent is preferably a halogen atom, and more preferably a fluorine atom.
  • Examples of the basic group represented by X include an amino group.
  • Examples of the salt structure represented by X include salts of the above-mentioned acid group or basic group.
  • Examples of the pigment derivative include compounds having the following structures. Further, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767 and JP-A-03-153780.
  • Japanese Patent Laid-Open No. 03-045662 Japanese Patent Laid-Open No. 04-285669, Japanese Patent Laid-Open No. 06-145546, Japanese Patent Laid-Open No. 06-212088, Japanese Patent Laid-Open No. 06-240158, Japanese Patent Laid-Open No.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more.
  • the upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15% by mass or less.
  • As the pigment derivative only one kind may be used, or two or more kinds may be used in combination. When two or more kinds are used in combination, the total amount thereof is preferably within the above range.
  • the colored composition of the present invention may contain a compound having a cyclic ether group.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • the compound having a cyclic ether group is preferably a compound having an epoxy group.
  • the compound having an epoxy group include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferable.
  • the upper limit of the number of epoxy groups may be, for example, 100 or less, 10 or less, or 5 or less.
  • the compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, further less than 1000), or a macromolecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight is 1000 or more).
  • the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, still more preferably 3000 or less.
  • An epoxy resin can be preferably used as the compound having an epoxy group.
  • the epoxy resin include an epoxy resin which is a glycidyl ether compound of a phenol compound, an epoxy resin which is a glycidyl ether compound of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester system.
  • the epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and further preferably 310 to 1000 g / eq.
  • Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (these are NOF Corporation's epoxy group-containing polymer).
  • the content of the compound having a cyclic ether group in the total solid content of the coloring composition is preferably 0.1 to 20% by mass.
  • the lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less.
  • the compound having a cyclic ether group may be only one kind or two or more kinds. When two or more kinds are used, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention may contain a silane coupling agent.
  • the silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that.
  • the hydrolyzable group means a substituent which is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable.
  • the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • functional groups other than hydrolyzable groups include vinyl group, (meth) allyl group, (meth) acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, and isocyanate group.
  • a phenyl group and the like, and an amino group, a (meth) acryloyl group and an epoxy group are preferable.
  • silane coupling agent examples include the compounds described in JP-A 2009-288703, paragraphs 0018 to 0036, and the compounds described in JP-A 2009-242604, paragraphs 0056 to 0066. Are incorporated herein by reference.
  • the content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.1 to 5% by mass.
  • the upper limit is preferably 3% by mass or less, more preferably 2% by mass or less.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the silane coupling agent may be only one kind or two or more kinds. When two or more kinds are used, the total amount is preferably within the above range.
  • the coloring composition of the present invention may contain a polymerization inhibitor.
  • a polymerization inhibitor hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, cerous salt, etc.) can be mentioned. Of these, p-methoxyphenol is preferable.
  • the content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass.
  • the coloring composition of the present invention may 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.
  • paragraph numbers 0238 to 0245 of International Publication WO 2015/166779 can be referred to, and the contents thereof are incorporated in the present specification.
  • the surfactant is preferably a fluorinated surfactant.
  • a fluorinated surfactant By including a fluorine-based surfactant in the coloring composition, liquid characteristics (particularly fluidity) can be further improved, and liquid saving can be further improved. It is also possible to form a film having a small thickness unevenness.
  • the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 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 the coating film and liquid saving, and also has good solubility in the coloring composition.
  • fluorinated surfactant examples include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-41318 (corresponding paragraphs 0060 to 0064 of WO 2014/017669) and JP-A-2011-2011. Examples thereof include the surfactants described in paragraph Nos. 0117 to 0132 of Japanese Patent No. 132503, the contents of which are incorporated herein. Examples of commercially available fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS.
  • Fluorine-based surfactants also have an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved to volatilize the fluorine atom. It can be preferably used.
  • a fluorinated surfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafac DS. -21 is included.
  • the fluorine-based surfactant it is also preferable to use 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.
  • a fluorine-based surfactant the description in JP-A-2016-216602 can be referred to, and the contents thereof are incorporated in the present specification.
  • 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 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (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 fluorine-based surfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of repeating units is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond group in its side chain can be used.
  • the compounds described in JP-A-2010-164965, paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation. , RS-72-K and the like.
  • the fluorine-based surfactant the compounds described in paragraph Nos. 0015 to 0158 of JP-A-2005-117327 can be used.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerolpropoxylate, glycerolethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS Company), Sols Perth 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries,
  • silicone-based surfactants 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 (above, Toray Dow Corning Co., Ltd. )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie) and the like. Further, as the silicon-based surfactant, a compound having the following structure can also be used.
  • the content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass.
  • the surfactant may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.
  • the coloring 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.
  • 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.
  • paragraphs 0052 to 0072 of JP2012-208374A paragraphs 0317 to 0334 of JP2013-068814A
  • paragraphs 0061 to 0080 of JP2016-162946A Reference may be made to these contents, which are incorporated herein.
  • Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.).
  • examples of the benzotriazole compound include MYUA series manufactured by Miyoshi Oil & Fats (Chemical Industry Daily, February 1, 2016).
  • the compounds described in paragraph Nos. 0049 to 0059 of Japanese Patent No. 6268967 can also be used as the ultraviolet absorber.
  • the content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
  • the ultraviolet absorber may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.
  • the coloring composition of the present invention may contain an antioxidant.
  • antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferable phenol compounds include hindered phenol compounds.
  • a compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group is preferred.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule.
  • a phosphorus-based antioxidant can also be preferably used.
  • phosphorus-based antioxidants include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphapin-2-yl ) Oxy] ethyl] amine, ethylbisphosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like.
  • antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80G. , ADEKA STAB AO-330 (above, ADEKA Corporation) and the like. Further, as the antioxidant, compounds described in paragraph Nos. 0023 to 0048 of Japanese Patent No. 6268967 can also be used.
  • the content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass.
  • the antioxidant only one kind may be used, or two or more kinds may be used. When two or more kinds are used, the total amount is preferably within the above range.
  • the coloring composition of the present invention if necessary, a sensitizer, a curing accelerator, a filler, a thermal curing accelerator, a plasticizer and other auxiliaries (for example, conductive particles, a filler, a defoaming agent, Flame retardant, leveling agent, peeling accelerator, perfume, surface tension adjusting agent, chain transfer agent, etc.) may be contained. Properties such as film physical properties can be adjusted by appropriately incorporating these components. These components are described, for example, in paragraph No. 0183 or later (corresponding U.S. Patent Application Publication No. 2013/0034812, paragraph No. 0237) of JP 2012-003225 A, or paragraphs of JP 2008-250074 A.
  • the coloring composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protecting group, and the compound is heated at 100 to 250 ° C or heated at 80 to 200 ° C in the presence of an acid / base catalyst.
  • Examples of the latent antioxidant include compounds described in International Publication WO2014 / 021023, International Publication WO2017 / 030005, and Japanese Patent Laid-Open No. 2017-008219.
  • Examples of commercially available products include ADEKA ARCRUZ GPA-5001 (manufactured by ADEKA).
  • the coloring composition of the present invention may contain a metal oxide in order to adjust the refractive index of the obtained film.
  • the metal oxide include TiO 2 , ZrO 2 , Al 2 O 3 , and SiO 2 .
  • the primary particle diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, most preferably 5 to 50 nm.
  • the metal oxide may have a core-shell structure, in which case the core part may be hollow.
  • the coloring composition of the present invention may contain a light resistance improver.
  • a light resistance improver compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, and JP-A-2017-129774 are disclosed.
  • the content of the free metal that is not bound or coordinated with the pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 10 ppm or less. In particular, it is particularly preferable not to contain substantially. According to this aspect, stabilization of pigment dispersibility (inhibition of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable component, and suppression of conductivity fluctuation due to elution of metal atom / metal ion, The display characteristics can be improved.
  • the effect is also obtained.
  • the types of the above-mentioned free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Ni, Cd, Pb, Bi etc.
  • the coloring composition of the present invention preferably has a content of free halogen that is not bound or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, and further preferably 10 ppm or less. It is more preferable, and it is particularly preferable not to contain substantially.
  • Halogen includes F, Cl, Br, I and their anions. Examples of methods for reducing free metals and halogens in the coloring composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
  • the coloring composition of the present invention does not contain a terephthalic acid ester.
  • the viscosity (25 ° C.) of the colored composition of the present invention is preferably 1 to 100 mPa ⁇ s when forming a film by coating, for example.
  • the lower limit is more preferably 2 mPa ⁇ s or more, further preferably 3 mPa ⁇ s or more.
  • the upper limit is more preferably 50 mPa ⁇ s or less, further preferably 30 mPa ⁇ s or less, and particularly preferably 15 mPa ⁇ s or less.
  • the container for the colored composition of the present invention is not particularly limited, and a known container can be used.
  • a container for the purpose of suppressing the mixing of impurities into the raw materials and the coloring composition, a multi-layer bottle in which the inner wall of the container is made of resin of 6 types and 6 layers, or a bottle having a structure of 7 types of 6 types of resin It is also preferred to use as such a container, for example, the container described in JP-A-2015-123351 can be mentioned.
  • the coloring composition of the present invention can be produced by mixing the above-mentioned components. In the production of the coloring composition, all components may be dissolved and / or dispersed in an organic solvent at the same time to produce the coloring composition. If necessary, each component may be appropriately used in two or more solutions or dispersions. As described above, these may be mixed at the time of use (at the time of application) to produce a coloring composition.
  • the mechanical force used to disperse the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
  • Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion.
  • the pulverization of the pigment in the sand mill (bead mill) it is preferable to use the beads having a small diameter, and to increase the filling rate of the beads to perform the treatment under the condition that the pulverization efficiency is increased. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment.
  • the process and disperser for dispersing the pigments are described in "Dispersion Technology Taizen, Information Technology Co., Ltd., July 15, 2005” and "Dispersion technology centering on suspension (solid / liquid dispersion system) and industrial application. In fact, the process and disperser described in Paragraph No.
  • JP-A-2015-157893 "Comprehensive reference materials, published by the Management Development Center Publishing Department, October 10, 1978" can be suitably used.
  • the particles may be refined in the salt milling step.
  • the materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629.
  • the filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration and the like.
  • fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight).
  • PTFE polytetrafluoroethylene
  • nylon eg nylon-6, nylon-6,6)
  • polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight).
  • PP polypropylene
  • the pore size of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, still more preferably 0.05 to 0.5 ⁇ m. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably.
  • 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., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.
  • a fibrous filter medium as the filter.
  • the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like.
  • examples of commercially available products include SBP type series (SBP008 etc.), TPR type series (TPR002, TPR005 etc.) and SHPX type series (SHPX003 etc.) manufactured by Loki Techno.
  • filters When using filters, different filters (eg, first filter and second filter) may be combined. At that time, the filtration by each filter may be performed only once or may be performed twice or more. Further, filters having different hole diameters may be combined within the above-described range. Further, 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 film of the present invention is a film obtained from the coloring composition of the present invention described above.
  • the film of the present invention can be used for a color filter or the like. Specifically, it can be preferably used as a colored layer (pixel) of a color filter, and more preferably used as a red colored layer (red pixel) of a color filter.
  • the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
  • the color filter of the present invention has the above-mentioned film of the present invention. More preferably, the pixel of the color filter has the film of the present invention.
  • the color filter of the present invention can be used for a solid-state imaging device such as CCD (charge coupled device) or CMOS (complementary metal oxide semiconductor), an image display device, or the like.
  • the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
  • the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
  • the pixel width of the color filter of the present invention is preferably 0.5 to 20.0 ⁇ m.
  • the lower limit is preferably 1.0 ⁇ m or more, and more preferably 2.0 ⁇ m or more.
  • the upper limit is preferably 15.0 ⁇ m or less, more preferably 10.0 ⁇ m or less.
  • the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
  • Each pixel included in the color filter of the present invention preferably has high flatness.
  • the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example.
  • the surface roughness of a pixel can be measured using, for example, AFM (atomic force microscope) Dimension 3100 manufactured by Veeco.
  • the contact angle of water on the pixel can be set to a suitable value as appropriate, but is typically in the range of 50 to 110 °.
  • the contact angle can be measured using, for example, a contact angle meter CV-DT • A type (manufactured by Kyowa Interface Science Co., Ltd.).
  • the volume resistance value of the pixel is high.
  • the volume resistance value of the pixel is preferably 10 9 ⁇ ⁇ cm or more, and more preferably 10 11 ⁇ ⁇ cm or more.
  • the upper limit is not specified, but it is preferably 10 14 ⁇ ⁇ cm or less, for example.
  • the volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest).
  • the color filter of the present invention may be provided with a protective layer on the surface of the film of the present invention.
  • a protective layer By providing the protective layer, various functions such as oxygen blocking, low reflection, hydrophilicity / hydrophobicity, and blocking of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted.
  • the thickness of the protective layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • Examples of the method of forming the protective layer include a method of applying a resin composition dissolved in an organic solvent to form the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive.
  • the protective layer for the purpose of blocking oxygen, it is preferable that the protective layer contains a polyol resin, SiO 2 , and Si 2 N 4 . Further, in the case of the protective layer aiming at low reflection, the protective layer preferably contains a (meth) acrylic resin or a fluororesin.
  • the resin composition When the resin composition is applied to form the protective layer, known methods such as a spin coating method, a casting method, a screen printing method, and an inkjet method can be used as a method for applying the resin composition.
  • a known organic solvent eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.
  • the protective layer is formed by the chemical vapor deposition method, known chemical vapor deposition methods (thermochemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) are known as the chemical vapor deposition method. Can be used.
  • the protective layer contains additives such as organic / inorganic fine particles, an absorber of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjusting agent, an antioxidant, an adhesive agent, a surfactant, etc., if necessary.
  • organic / inorganic particles include polymer particles (eg, silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , Magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate and the like.
  • a known absorber can be used as the absorber having a specific wavelength.
  • the ultraviolet absorber and the near infrared absorber include the materials described above.
  • the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total weight of the protective layer.
  • the protective layer described in paragraph Nos. 0073 to 0092 of JP-A-2017-151176 may be used.
  • the color filter may have a structure in which each color pixel (coloring layer) is embedded in a region partitioned by a partition wall.
  • the partition wall preferably has a low refractive index for each pixel.
  • the partition wall may be formed with the configuration described in US2018 / 0040656.
  • the color filter of the present invention a step of forming a coloring composition layer on a support using the coloring composition of the present invention described above, a step of forming a pattern for the coloring composition layer by photolithography, Can be manufactured through.
  • the pattern formation by the photolithography method preferably includes a step of exposing the coloring composition layer in a pattern, and a step of developing and removing an unexposed portion of the coloring composition layer to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-bake step) and a step of baking the developed pattern (pixel) may be provided (post-bake step).
  • pre-bake step pre-bake step
  • a step of baking the developed pattern (pixel) may be provided (post-bake step).
  • the coloring composition layer of the present invention is used to form a coloring composition layer on a support.
  • the support is not particularly limited and can be appropriately selected depending on the application.
  • a glass substrate, a silicon substrate, etc. are mentioned, and a silicon substrate is preferable.
  • a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film and the like may be formed on the silicon substrate.
  • CMOS complementary metal oxide semiconductor
  • a black matrix that isolates each pixel may be formed on the silicon substrate.
  • the silicon substrate may be provided with an undercoat layer for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the substrate surface.
  • a known method can be used as a method for applying the coloring 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 cast coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395A).
  • Methods described in the publication inkjet (for example, on-demand method, piezo method, thermal method), ejection-type printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprint methods and the like.
  • the method for applying the inkjet method is not particularly limited, and for example, the method described in “Expanding and Usable Inkjet-Infinite Possibilities Seen in Patents”, issued by Sumi Betechno Research, February 2005 (especially from page 115) (See page 133), Japanese Patent Application Laid-Open No. 2003-262716, Japanese Patent Application Laid-Open No. 2003-185831, Japanese Patent Application Laid-Open No. 2003-261827, Japanese Patent Application Laid-Open No. 2012-126830, Japanese Patent Application Laid-Open No. 2006-169325, and the like. Can be mentioned.
  • the descriptions in International Publication WO2017 / 030174 and International Publication WO2017 / 018419 can be referred to, and the contents thereof are incorporated in the present specification.
  • the colored composition layer formed on the support may be dried (prebaked). If the film is produced by a low temperature process, prebaking may not be performed.
  • the prebaking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and further preferably 110 ° C or lower.
  • the lower limit may be, for example, 50 ° C. or higher, and may be 80 ° C. or higher.
  • the prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Prebaking can be performed with a hot plate, an oven, or the like.
  • the colored composition layer is exposed in a pattern (exposure step).
  • the colored composition layer can be exposed in a pattern by using a stepper exposure device, a scanner exposure device, or the like through a mask having a predetermined mask pattern. Thereby, the exposed portion can be cured.
  • Radiation (light) that can be used at the time of exposure includes g rays, i rays, and the like. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm) are preferable. Also, a long-wavelength light source of 300 nm or more can be used.
  • pulse exposure is an exposure method of a type in which light irradiation and rest are repeated in a short-time (for example, millisecond level or less) cycle.
  • the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and further preferably 30 nanoseconds or less.
  • the lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, and may be 10 femtoseconds or more.
  • the frequency is preferably 1 kHz or higher, more preferably 2 kHz or higher, even more preferably 4 kHz or higher.
  • the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and further preferably 10 kHz or less.
  • Maximum instantaneous intensity is preferably at 50000000W / m 2 or more, more preferably 100000000W / m 2 or more, more preferably 200000000W / m 2 or more.
  • the upper limit of the maximum instantaneous intensity is preferably at 1000000000W / m 2 or less, more preferably 800000000W / m 2 or less, further preferably 500000000W / m 2 or less.
  • the pulse width is the time during which light is emitted in the pulse cycle.
  • the frequency is the number of pulse cycles per second.
  • the maximum instantaneous illuminance is the average illuminance within the time during which light is emitted in the pulse cycle.
  • the pulse cycle is a cycle in which light irradiation and rest in pulse exposure are one cycle.
  • Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
  • the oxygen concentration at the time of exposure can be appropriately selected.
  • the exposure may be carried out under oxygen-free conditions or under a high oxygen atmosphere in which the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume or 50% by volume).
  • the exposure illuminance can be set appropriately and is usually selected from the range of 1000 W / m 2 to 100000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , or 35000 W / m 2 ).
  • You can 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 unexposed portion of the colored composition layer is developed and removed to form a pattern (pixel).
  • the development removal of the unexposed part of the coloring composition layer can be performed using a developing solution.
  • the unexposed portion of the colored composition layer in the exposure step is eluted into the developing solution, and only the photocured portion remains.
  • the temperature of the developer is preferably 20 to 30 ° C., for example.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the process of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.
  • the alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water.
  • alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide.
  • Organic compounds such as, 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 hydrogen carbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate.
  • the alkaline 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 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
  • the developing solution may further contain a surfactant.
  • the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable.
  • the developer may be produced once as a concentrated solution and diluted to a required concentration at the time of use, from the viewpoint of convenience of transportation and storage. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. Further, it is also preferable to wash (rinse) with pure water after the development.
  • the rinsing is preferably performed by supplying a rinse liquid to the colored composition layer after development while rotating the support on which the colored composition layer after development is formed. It is also preferable that the nozzle for discharging the rinse liquid is moved from the central portion of the support to the peripheral portion of the support. At this time, when moving from the central portion of the support body of the nozzle to the peripheral edge portion, the movement speed of the nozzle may be gradually reduced. By performing the rinse in this manner, it is possible to suppress the in-plane variation of the rinse. Further, the same effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the peripheral portion.
  • the additional exposure process and the post-baking are curing processes after development to complete the curing.
  • the heating temperature in the post-baking is preferably 100 to 240 ° C, more preferably 200 to 240 ° C.
  • Post-baking can be performed in a continuous or batch manner by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the film after development can meet the above conditions.
  • the additional exposure process is performed, the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in KR1020170122130A.
  • the solid-state image sensor of the present invention has the above-mentioned film of the present invention.
  • the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations.
  • a plurality of photodiodes forming a light receiving area of a solid-state image pickup device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and transfer electrodes made of polysilicon or the like.
  • CCD charge coupled device
  • CMOS complementary metal oxide semiconductor
  • a device protection film made of silicon nitride or the like which has a light-shielding film that is opened only on the photodiode and the light-receiving portion of the photodiode on the transfer electrode and covers the entire light-shielding film and the photodiode light-receiving portion on the light-shielding film. And has a color filter on the device protective film.
  • a structure having a light collecting means for example, a microlens or the like; hereinafter the same) on the device protective film and below the color filter (on the side close to the substrate), or a structure having a light collecting means on the color filter is used. It may be.
  • the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each colored pixel. Examples of the imaging device having such a structure include the devices described in JP2012-227478A, JP2014-179577A, and International Publication WO2018 / 043654.
  • the image pickup apparatus provided with the solid-state image pickup element of the present invention can be used not only for digital cameras and electronic devices (such as mobile phones) having an image pickup function, but also for vehicle-mounted cameras and surveillance cameras.
  • the image display device of the present invention has the above-mentioned film of the present invention.
  • the image display device include a liquid crystal display device and an organic electroluminescence display device.
  • the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Institute Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, liquid crystal display devices of various systems described in the above-mentioned “next-generation liquid crystal display technology”.
  • Image brightness data (long-axis direction coordinates, short-axis direction coordinates) of the pigment in the long-axis direction and the short-axis direction are digitized using a scanning electron microscope at an accelerating voltage of 5 kV and an imaging magnification of 100,000 times. , And the luminance).
  • the image was divided into 1280 in the width direction, processed with 8-bit luminance to obtain data of 256 gradations, and the image luminance of each divided coordinate point was converted into a predetermined gradation value.
  • the horizontal axis represents the coordinate in the direction of the long axis of the particle, and the average value of the brightness at each coordinate point in the long axis direction (that is, the average value of the brightness at each of the 1280 divided coordinate points). ) was plotted on the vertical axis to create a luminance curve.
  • the created brightness curve was differentiated to create a differential curve, and the coordinates of the boundary of the pigment were specified from the peak position of the created differential curve.
  • the operation of setting the coordinate in the direction corresponding to the long axis of the pigment as the horizontal axis was repeated 3 times, and the longest axis length was defined as the long axis length.
  • the major axis length is determined by defining the axis (straight line) that can maximize the length of the particle as the major axis, and using the major axis length.
  • the minor axis is determined as the axis that has the longest length when the particle length is taken on a straight line orthogonal to the major axis, and the length of this axis is defined as the minor axis length. Further, the arithmetic mean values of the minor axis length and the major axis length of 100 pigments were calculated, and the average value of the minor axis length of the pigment and the average value of the major axis length of the pigment were calculated.
  • Pigment dispersion A1-1 to A1-7 C. I. Pigment Green 58 9 parts by mass, C.I. I. Pigment Yellow 185 (6 parts by mass), pigment derivative Y1 (2.5 parts by mass), dispersant D1 (5 parts by mass), and propylene glycol monomethyl ether acetate (PGMEA) (77.5 parts by mass). 230 parts by mass of 0.3 mm zirconia beads were added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersion liquids 1-1 to A1-7.
  • the major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table.
  • Pigment 1 and Pigment 2 were adjusted to the values shown in the following table by changing the dispersion time. These pigment dispersions had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
  • Pigment derivative Y1 a compound having the following structure.
  • Pigment dispersion A2-1 to A2-7) C. I. Pigment Green 36 9 parts by mass, C.I. I. Pigment Yellow 150 (6 parts by mass), pigment derivative Y1 (2.5 parts by mass), dispersant D1 (5 parts by mass), and PGMEA (77.5 parts by mass) are mixed in a mixed solution and zirconia beads 230 having a diameter of 0.3 mm are mixed. After adding parts by mass and performing a dispersion treatment using a paint shaker, the beads were separated by filtration to prepare pigment dispersions A2-1 to A2-7.
  • the major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table.
  • Pigment 1 and Pigment 2 were adjusted to the values shown in the following table by changing the dispersion time. These pigment dispersions had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
  • Pigment dispersion A3 C. I. Pigment Green 58 9 parts by mass, C.I. I. Pigment Yellow 139 (6 parts by mass), Pigment Derivative Y1 (2.5 parts by mass), Dispersant D1 (5 parts by mass), and PGMEA (77.5 parts by mass) in a mixed solution. After adding a mass part and performing a dispersion process using a paint shaker, the beads were separated by filtration to prepare a pigment dispersion A3. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
  • Pigment dispersion A4 C. I. Pigment Red 254, 10.5 parts by mass, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y1 (2.0 parts by mass), Dispersant D1 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed to prepare a mixed solution having a diameter of 0.3 mm. 230 parts by mass of the zirconia beads of was added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare a pigment dispersion A4. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
  • Pigment dispersion A5-1, A5-2 C. I. Pigment Red 177, 10.5 parts by mass, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y2 (2.0 parts by mass), Dispersant D2 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed in a mixed solution having a diameter of 0.3 mm. 230 parts by mass of the zirconia beads of was added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersions A5-1 and A5-2.
  • the major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table.
  • Pigment 1 and Pigment 2 were adjusted to the values shown in the following table by changing the dispersion time. These pigment dispersions had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
  • Pigment derivative Y2 compound having the following structure
  • Dispersant D2 compound having the following structure
  • Pigment dispersion A6 C. I. Pigment Red 264, 10.5 parts by mass, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y1 (2.0 parts by mass), Dispersant D1 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed to prepare a mixed solution having a diameter of 0.3 mm. After adding 230 parts by mass of zirconia beads of Example 1 and performing a dispersion treatment using a paint shaker, the beads were separated by filtration to prepare a pigment dispersion A6. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
  • Pigment dispersion A7 C. I. Pigment Red 272, 10.5 parts by mass, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y1 (2.0 parts by mass), Dispersant D1 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed to prepare a mixed solution having a diameter of 0.3 mm. After adding 230 parts by mass of zirconia beads of Example 1 and performing a dispersion treatment using a paint shaker, the beads were separated by filtration to prepare a pigment dispersion A7. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
  • Pigment dispersion A8 10.5 parts by mass of red pigment 1, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y1 (2.0 parts by mass), Dispersant D1 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed to prepare a mixed solution having a diameter of 0.3 mm. 230 parts by mass of zirconia beads were added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare a pigment dispersion A8. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass. Red pigment 1: compound with the following structure
  • Pigment dispersion A9-1, A9-2) C. I. Pigment Blue 15: 6 12 parts by mass, C.I. I. Pigment Violet 23, 2.7 parts by mass of the pigment derivative Y1, 4.8 parts by mass of the dispersant D1, and 77.5 parts by mass of PGMEA. 230 parts by mass of beads were added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersions A9-1 and A9-2.
  • the major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table.
  • Pigment 1 and Pigment 2 were adjusted to the values shown in the following table by changing the dispersion time. These pigment dispersions had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
  • Pigment dispersion A10 C. I. Pigment Blue 15: 6, 12 parts by mass, 3 parts by mass of V dye 1 described in paragraph No. 0292 of JP-A-2005-041058, 2.7 parts by mass of pigment derivative Y1, 4.8 parts by mass of dispersant D1. Parts, and 77.5 parts by mass of PGMEA, 230 parts by mass of zirconia beads having a diameter of 0.3 mm was added to the mixed solution, and dispersion treatment was performed using a paint shaker, and then the beads were separated by filtration. To prepare Pigment Dispersion Liquid A10. The major axis length and the minor axis length of Pigment 1 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a coloring material content (total amount of pigment and dye) of 15% by mass.
  • a coloring composition was prepared by filtering with a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 ⁇ m.
  • the compositions 101 to 118 and C101 to C103 were green coloring compositions
  • the compositions 201 to 205 and C201 were red coloring compositions
  • the compositions 301, 302 and C301 were blue coloring compositions.
  • T1 EHPE3150 (manufactured by Daicel Corporation, epoxy resin)
  • T2 Compound having the following structure (silane coupling agent)
  • CT-4000 manufactured by FUJIFILM Electronic Materials Co., Ltd.
  • CT-4000 manufactured by FUJIFILM Electronic Materials Co., Ltd.
  • Each coloring composition was applied onto this glass substrate with an underlayer by spin coating so that the film thickness after post-baking would be the film thickness shown in the table below, and then at 100 ° C. using a hot plate. Heated for 2 minutes.
  • the entire surface of the glass substrate was exposed to i-line through a mask of an open frame at an exposure dose of 1000 mJ / cm 2 .
  • the film was formed by heating at 200 ° C. for 5 minutes.
  • the film thickness of the obtained film was measured using a palpation-type profiling system DektakXT (manufactured by BRUKER).
  • the film produced above was allowed to stand for 100 hours under a constant temperature and humidity of 110 ° C. and 85% humidity.
  • Shrinkage rate (%) of film ⁇ (film thickness before humidity resistance test ⁇ film thickness after humidity resistance test) / film thickness before humidity resistance test ⁇ ⁇ 100 (Evaluation criteria)
  • D Shrinkage of the film is 20 % Or more
  • the coloring composition described in the following table was applied onto a glass substrate by spin coating. Then, using a hot plate, heating was performed at 100 ° C. for 2 minutes to form a film having a film thickness shown in the following table. Light having wavelengths shown in the table below is incident on the obtained film, and its transmittance is measured by a spectroscope (UV4100, manufactured by Hitachi High-Technologies Corporation) to measure an optical density (OD value). did. The obtained optical density was normalized by the film thickness to obtain the relative value of color value. Note that the film formed using the green coloring composition was irradiated with light having a wavelength of 660 nm. In addition, light having a wavelength of 530 nm was incident on the film formed by using the red coloring composition. In addition, light having a wavelength of 610 nm was incident on the film formed using the blue coloring composition.
  • CT-4000L manufactured by FUJIFILM Electronic Materials Co., Ltd.
  • FUJIFILM Electronic Materials Co., Ltd. was applied to an 8-inch (20.32 cm) silicon wafer by a spin coater to a thickness of 0.1 ⁇ m after post-baking, and a hot plate was applied. It was heated at 220 ° C. for 300 seconds to form an undercoat layer, and a silicon wafer with an undercoat layer was obtained.
  • each coloring composition was applied by spin coating so that the film thickness after post-baking would be the film thickness described in the following table. Then, it was post-baked at 100 ° C. for 2 minutes using a hot plate.
  • i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
  • an exposure amount of 200 mJ / cm 2 was applied through a mask having a Bayer pattern formed with a pixel (pattern) size of 1 ⁇ m square. Exposed with lines.
  • paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with a spin shower and further washed with pure water. Next, by using a hot plate and heating at 200 ° C. for 5 minutes, pixels (pattern) were formed.
  • TMAH tetramethylammonium hydroxide
  • a pattern having a target line width was formed without distortion, and the difference between the line width at the center of the pattern and the line width at the end was less than 5%.
  • D Other than A to C, or the pattern could not be formed.
  • Test Example 1001 The Green composition was applied onto a silicon wafer by spin coating so that the film thickness after post-baking would be 1.0 ⁇ m. Then, using a hot plate, it heated at 100 degreeC for 2 minutes. Then, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm was exposed through a mask having a dot pattern of 2 ⁇ m square at an exposure dose of 1000 mJ / cm 2 . Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • the Green composition was patterned by heating (post-baking) at 200 ° C. for 5 minutes using a hot plate.
  • the Red composition and the Blue composition were sequentially patterned to form red, green, and blue colored patterns (Bayer patterns).
  • Composition 101 was used as the Green composition.
  • Composition 201 was used as the Red composition.
  • Composition 301 was used as the Blue composition.
  • the Bayer pattern is, as disclosed in U.S. Pat. No. 3,971,065, one red element, two green elements, and one blue element. ) Element and a 2 ⁇ 2 array of color filter elements are repeated.
  • the obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had a suitable image recognition ability.

Abstract

Provided is a coloring composition which contains a coloring agent, a resin and an organic solvent. The coloring agent is contained at a quantity of 50 mass% or more relative to the total solid content in the coloring composition. The coloring agent contains 40 mass% or more of a pigment A for which the major axis length/minor axis length ratio is 1.4 or more. Also provided are a film which uses the coloring composition; a method for producing a color filter; a color filter; a solid state imaging device; and an image display device.

Description

着色組成物、膜、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子及び画像表示装置Coloring composition, film, method for producing color filter, color filter, solid-state imaging device, and image display device
　本発明は、顔料を含む着色組成物に関する。また、本発明は、着色組成物を用いた膜、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子および画像表示装置に関する。 The present invention relates to a coloring composition containing a pigment. The present invention also relates to a film using the coloring composition, a method for producing a color filter, a color filter, a solid-state image sensor, and an image display device.
　近年、デジタルカメラ、カメラ付き携帯電話等の普及から、電荷結合素子（ＣＣＤ）イメージセンサなどの固体撮像素子の需要が大きく伸びている。ディスプレイや光学素子のキーデバイスとしてカラーフィルタが使用されている。カラーフィルタは、顔料などの着色剤を含む着色組成物を用いて製造されている。 Demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has grown significantly with the recent spread of digital cameras and camera-equipped mobile phones. Color filters are used as key devices for displays and optical elements. The color filter is manufactured using a coloring composition containing a coloring agent such as a pigment.
　特許文献１には、顔料及びバインダー成分を必須成分として含有し、顔料が、その一次粒子の短径をａ、長径をｂとするとき、式（１）を満足する一次粒子の含有量が７０体積％以上で、かつ、式（２）を満足する一次粒子の含有量が５体積％以下の形状分布を持つものである画像形成用着色組成物を用いてカラーフィルタの着色画素を形成することが記載されている。
　ｂ／ａ＜１．４　・・・（１）
　ｂ／ａ≧１．８　・・・（２） Patent Document 1 contains a pigment and a binder component as essential components, and when the pigment has a minor axis of the primary particle as a and a major axis as b, the content of the primary particles satisfying the formula (1) is 70. Forming a colored pixel of a color filter using a coloring composition for image formation which has a shape distribution in which the content of primary particles satisfying the formula (2) is 5% by volume or more by volume. Is listed.
b / a <1.4 (1)
b / a ≧ 1.8 (2)
　一方、特許文献２には、インクジェットプリンタ用インクなどに用いられる顔料インク組成物に関する発明であって、少なくとも針状顔料粒子を含む顔料粒子と、分散剤と、溶媒を含有し、針状顔料粒子がアスペクト比３以上の針状形状からなり、平均アスペクト比が５以上７以下で、かつ平均短径が２０ｎｍ以上３０ｎｍ以下で、短径の標準偏差が２．０ｎｍ以下の分布を有し、かつ針状顔料粒子が分散剤で被覆されている顔料インク組成物に関する発明が記載されている。 On the other hand, Patent Document 2 is an invention relating to a pigment ink composition used for inks for inkjet printers, which contains pigment particles containing at least needle pigment particles, a dispersant, and a solvent, Has a needle-like shape with an aspect ratio of 3 or more, an average aspect ratio of 5 or more and 7 or less, an average minor axis of 20 nm or more and 30 nm or less, and a standard deviation of the minor axis of 2.0 nm or less, and An invention is described for a pigment ink composition in which acicular pigment particles are coated with a dispersant.
特開平１０－２３９８３５号公報JP-A-10-239835 特開２００９－２２１２６６号公報JP, 2009-212266, A
　本発明者の検討によれば、顔料を含む着色組成物を用いて形成される膜は、膜収縮が生じやすいことが分かった。特に湿度の高い環境下では膜収縮が生じやすい傾向にあることが分かった。 According to the study by the present inventor, it was found that a film formed using a coloring composition containing a pigment is likely to cause film shrinkage. It was found that the film shrinkage tends to occur particularly in an environment with high humidity.
　膜収縮が生じると、隣接する部材との間にボイドが発生しやすい。例えば、顔料を含む着色組成物を用いてカラーフィルタの画素を形成した場合、画素が収縮して画素の線幅が減少すると、隣接する画素間などでボイドが発生してデバイスの感度が変化してしまうことがある。 When film shrinkage occurs, voids are likely to occur between adjacent members. For example, when a pixel of a color filter is formed using a coloring composition containing a pigment, when the pixel contracts and the line width of the pixel decreases, a void occurs between adjacent pixels and the sensitivity of the device changes. It may happen.
　よって、本発明の目的は、膜収縮が抑制された膜を形成できる着色組成物を提供することにある。また、本発明は、この着色組成物を用いた膜、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子および画像表示装置を提供することにある。 Therefore, an object of the present invention is to provide a coloring composition capable of forming a film in which film shrinkage is suppressed. The present invention also provides a film, a color filter manufacturing method, a color filter, a solid-state imaging device, and an image display device using the coloring composition.
　本発明者の検討によれば、以下の構成とすることにより上記目的を達成できることを見出し、本発明を完成するに至った。よって、本発明は以下を提供する。
　＜１＞　着色剤と樹脂と有機溶剤とを含む着色組成物であって、
　着色組成物の全固形分中に着色剤を５０質量％以上含有し、
　着色剤は、短軸長と長軸長との比率である長軸長／短軸長の値が１．４以上の顔料Ａを４０質量％以上含有する、着色組成物。
　＜２＞　着色組成物の全固形分中に着色剤を６０質量％以上含有する、＜１＞に記載の着色組成物。
　＜３＞　顔料Ａは、長軸長／短軸長の値が１．４以上３．０以下である、＜１＞または＜２＞に記載の着色組成物。
　＜４＞　顔料Ａの長軸長の平均値が１５～１５０ｎｍである、＜１＞～＜３＞のいずれか１つに記載の着色組成物。
　＜５＞　顔料Ａの短軸長の平均値が１０～１００ｎｍである、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
　＜６＞　顔料Ａは赤色顔料である、＜１＞～＜５＞のいずれか１つに記載の着色組成物。
　＜７＞　赤色顔料は、カラーインデックスピグメントレッド２５４、カラーインデックスピグメントレッド２６４、および、カラーインデックスピグメントレッド２７２から選ばれる少なくとも１種である、＜６＞に記載の着色組成物。
　＜８＞　光重合開始剤と重合性化合物とを含む、＜１＞～＜７＞のいずれか１つに記載の着色組成物。
　＜９＞　樹脂はアルカリ可溶性樹脂を含む、＜１＞～＜８＞のいずれか１つに記載の着色組成物。
　＜１０＞　フォトリソグラフィ法でのパターン形成用である、＜１＞～＜９＞のいずれか１つに記載の着色組成物。
　＜１１＞　固体撮像素子用である、＜１＞～＜１０＞のいずれか１つに記載の着色組成物。
　＜１２＞　カラーフィルタ用である、＜１＞～＜１０＞のいずれか１つに記載の着色組成物。
　＜１３＞　赤色の画素形成用である、＜１２＞に記載の着色組成物。
　＜１４＞　＜１＞～＜１３＞のいずれか１つに記載の着色組成物から得られる膜。
　＜１５＞　＜１＞～＜１３＞のいずれか１つに記載の着色組成物を用いて支持体上に着色組成物層を形成する工程と、フォトリソグラフィ法により着色組成物層に対してパターンを形成する工程と、を有するカラーフィルタの製造方法。
　＜１６＞　＜１４＞に記載の膜を有するカラーフィルタ。
　＜１７＞　＜１４＞に記載の膜を有する固体撮像素子。
　＜１８＞　＜１４＞に記載の膜を有する画像表示装置。 According to the study of the present inventor, it was found that the above-mentioned object can be achieved by the following constitution, and the present invention has been completed. Therefore, the present invention provides the following.
<1> A coloring composition containing a coloring agent, a resin, and an organic solvent,
Containing 50% by mass or more of a colorant in the total solid content of the coloring composition,
The coloring composition contains 40% by mass or more of pigment A having a major axis length / minor axis length value of 1.4 or more, which is a ratio of the minor axis length to the major axis length.
<2> The coloring composition according to <1>, which contains 60% by mass or more of a colorant in the total solid content of the coloring composition.
<3> The pigment A is the coloring composition according to <1> or <2>, wherein the major axis length / minor axis length value is 1.4 or more and 3.0 or less.
<4> The coloring composition according to any one of <1> to <3>, wherein the pigment A has an average major axis length of 15 to 150 nm.
<5> The coloring composition according to any one of <1> to <4>, wherein the pigment A has an average minor axis length of 10 to 100 nm.
<6> The coloring composition according to any one of <1> to <5>, in which the pigment A is a red pigment.
<7> The coloring composition according to <6>, wherein the red pigment is at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272.
<8> The coloring composition according to any one of <1> to <7>, which contains a photopolymerization initiator and a polymerizable compound.
<9> The coloring composition according to any one of <1> to <8>, in which the resin contains an alkali-soluble resin.
<10> The coloring composition according to any one of <1> to <9>, which is for forming a pattern by a photolithography method.
<11> The coloring composition according to any one of <1> to <10>, which is for a solid-state imaging device.
<12> The coloring composition according to any one of <1> to <10>, which is for a color filter.
<13> The coloring composition according to <12>, which is for forming red pixels.
<14> A film obtained from the coloring composition according to any one of <1> to <13>.
<15> A step of forming a coloring composition layer on a support using the coloring composition according to any one of <1> to <13>, and a pattern for the coloring composition layer by a photolithography method. Forming a color filter.
<16> A color filter having the film according to <14>.
<17> A solid-state image sensor having the film according to <14>.
<18> An image display device having the film according to <14>.
　本発明によれば、膜収縮が抑制された膜を形成できる着色組成物、膜、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子および画像表示装置を提供することができる。 According to the present invention, it is possible to provide a colored composition capable of forming a film in which film shrinkage is suppressed, a film, a method for producing a color filter, a color filter, a solid-state image sensor, and an image display device.
　以下において、本発明の内容について詳細に説明する。
　本明細書において、「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
　本明細書において、構造式中のＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。
　本明細書において、重量平均分子量および数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値である。
　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
　本明細書において、顔料とは、溶剤に対して溶解しにくい化合物を意味する。例えば、顔料は、２３℃の水１００ｇおよび２３℃のプロピレングリコールモノメチルエーテルアセテート１００ｇに対する溶解度がいずれも０．１ｇ以下であることが好ましく、０．０１ｇ以下であることがより好ましい。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。 Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used to mean that numerical values described before and after the “to” are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not included includes a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, the term "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified. Examples of the light used for exposure include a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron rays, or radiation.
In the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, "(meth) acrylic" represents both acrylic and methacrylic, or "(meth ) "Acryloyl" means both acryloyl and methacryloyl, or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography) method.
In the present specification, the total solid content refers to the total mass of the components of the composition excluding the solvent.
In the present specification, the pigment means a compound that is difficult to dissolve in a solvent. For example, the pigment preferably has a solubility of 0.1 g or less in 100 g of water at 23 ° C. and 100 g of propylene glycol monomethyl ether acetate at 23 ° C., and more preferably 0.01 g or less.
In the present specification, the term "step" is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
＜着色組成物＞
　本発明の着色組成物は、着色剤と樹脂と有機溶剤とを含む着色組成物であって、
　着色組成物の全固形分中に着色剤を５０質量％以上含有し、
　着色剤は、短軸長と長軸長との比率である長軸長／短軸長の値が１．４以上の顔料Ａを４０質量％以上含有することを特徴とする。 <Coloring composition>
The coloring composition of the present invention is a coloring composition containing a colorant, a resin and an organic solvent,
Containing 50% by mass or more of a colorant in the total solid content of the coloring composition,
The colorant is characterized by containing 40% by mass or more of pigment A having a value of major axis length / minor axis length, which is a ratio of minor axis length to major axis length, of 1.4 or more.
　本発明の着色組成物によれば、上述した顔料Ａを４０質量％以上含む着色剤を着色組成物の全固形分中に５０質量％以上含有することにより、得られる膜の収縮を抑制できる。得られる膜中で、顔料Ａが緻密に敷き詰められると推測され、その結果、得られる膜の収縮を抑制できたと推測される。特に、湿度の高い環境下に膜を長時間さらした場合であっても、膜収縮を効果的に抑制することもできる。また、本発明の着色組成物は着色剤を５０質量％以上含有するので、色価の高い膜を形成することができる。このため、所望の分光特性を維持しつつ、薄膜化を達成することができる。 According to the coloring composition of the present invention, by containing 50% by mass or more of the above-described coloring agent containing 40% by mass or more of pigment A in the total solid content of the coloring composition, it is possible to suppress shrinkage of the obtained film. It is speculated that the pigment A is densely spread in the obtained film, and as a result, it is speculated that the shrinkage of the obtained film could be suppressed. In particular, even when the film is exposed to a high humidity environment for a long time, the film shrinkage can be effectively suppressed. Further, since the coloring composition of the present invention contains the coloring agent in an amount of 50% by mass or more, it is possible to form a film having a high color value. Therefore, thinning can be achieved while maintaining desired spectral characteristics.
　本発明において、顔料Ａの長軸長／短軸長の値は１．４以上３．０以下であることが好ましい。この態様によれば、本発明の着色組成物を用いてフォトリソグラフィ法でパターン形成した場合において、現像残差の発生を抑制でき、かつ、矩形性の良いパターンを形成することができる。 In the present invention, the value of the major axis length / minor axis length of the pigment A is preferably 1.4 or more and 3.0 or less. According to this aspect, when a pattern is formed by the photolithography method using the coloring composition of the present invention, it is possible to suppress the occurrence of a development residual and to form a pattern having good rectangularity.
　本発明において、顔料Ａは、赤色顔料であることが好ましい。赤色顔料は一般的に色価の低いものが多い傾向にあるが、赤色顔料として、長軸長／短軸長の値が１．４以上であるものを用いることで、膜中で赤色顔料を緻密に敷き詰めることができ、赤色の色価の高い膜を形成することもできる。 In the present invention, the pigment A is preferably a red pigment. Red pigments generally tend to have a low color value, but by using a red pigment having a major axis length / minor axis length value of 1.4 or more, the red pigment is formed in the film. It can be densely spread and can form a film with a high red color value.
　本発明の着色組成物は、固体撮像素子用の着色組成物として好ましく用いることができる。また、本発明の着色組成物は、カラーフィルタ用の着色組成物として好ましく用いることができる。具体的には、カラーフィルタの画素形成用の着色組成物として好ましく用いることができ、固体撮像素子に用いられるカラーフィルタの画素形成用の着色組成物としてより好ましく用いることができる。カラーフィルタの画素としては、赤色画素、青色画素、緑色画素、黄色画素、シアン色画素およびマゼンタ色画素などの着色画素が挙げられる。本発明の着色組成物は、赤色の画素形成用の着色組成物として好ましく用いられる。 The colored composition of the present invention can be preferably used as a colored composition for a solid-state imaging device. Further, the coloring composition of the present invention can be preferably used as a coloring composition for a color filter. Specifically, it can be preferably used as a coloring composition for forming a pixel of a color filter, and more preferably used as a coloring composition for forming a pixel of a color filter used in a solid-state imaging device. Examples of the pixels of the color filter include colored pixels such as red pixels, blue pixels, green pixels, yellow pixels, cyan color pixels, and magenta color pixels. The coloring composition of the present invention is preferably used as a coloring composition for forming red pixels.
　本発明の着色組成物は、フォトリソグラフィ法でのパターン形成用として好ましく用いることができる。この場合、本発明の着色組成物は、光重合開始剤と重合性化合物とを含むことが好ましい。また、着色組成物に含まれる樹脂は、アルカリ可溶性樹脂を含むものであることが好ましい。 The colored composition of the present invention can be preferably used for pattern formation by a photolithography method. In this case, the coloring composition of the present invention preferably contains a photopolymerization initiator and a polymerizable compound. The resin contained in the coloring composition preferably contains an alkali-soluble resin.
　また、本発明の着色組成物は、カラーマイクロレンズの形成用の組成物として用いることもできる。カラーマイクロレンズの製造方法としては、特開２０１８－０１０１６２号公報に記載された方法などが挙げられる。 The colored composition of the present invention can also be used as a composition for forming a color microlens. Examples of the method for manufacturing a color microlens include the method described in JP-A-2018-010162.
　以下、本発明の着色組成物に用いられる各成分について説明する。 Hereinafter, each component used in the coloring composition of the present invention will be described.
＜＜着色剤＞＞
　本発明の着色組成物は着色剤を含有する。着色剤としては、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤などの有彩色着色剤が挙げられる。着色剤としては、顔料および染料が挙げられ、顔料を含むものが用いられる。顔料は、無機顔料、有機顔料のいずれでもよい。また、顔料には、無機顔料または有機－無機顔料の一部を有機発色団で置換した材料を用いることもできる。無機顔料や有機－無機顔料を有機発色団で置換することで、色相設計をしやすくできる。 << Colorant >>
The coloring composition of the present invention contains a coloring agent. Examples of the colorant include chromatic colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant and an orange colorant. Examples of the colorant include pigments and dyes, and those containing a pigment are used. The pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, a material in which a part of an inorganic pigment or an organic-inorganic pigment is replaced with an organic chromophore can also be used. By substituting an inorganic pigment or an organic-inorganic pigment with an organic chromophore, hue design can be facilitated.
　本発明で用いられる着色剤は、短軸長と長軸長との比率である長軸長／短軸長の値が１．４以上の顔料Ａ（以下、単に顔料Ａともいう）を４０質量％以上含有する。顔料Ａの長軸長／短軸長の値は、１．４以上３．０以下であることが好ましい。顔料Ａの長軸長／短軸長の値が上記範囲であれば、色価が高く、膜収縮が抑制された膜が得られやすい。更には、本発明の着色組成物を用いてフォトリソグラフィ法でパターン形成した場合において、現像残差の発生を抑制でき、かつ、矩形性の良いパターンを形成することもできる。 The colorant used in the present invention has a mass ratio of the major axis length / minor axis length, which is the ratio of the minor axis length to the major axis length, of pigment A having a value of 1.4 or more (hereinafter, also simply referred to as pigment A) of 40 mass. % Or more. The value of major axis length / minor axis length of the pigment A is preferably 1.4 or more and 3.0 or less. When the value of the major axis length / minor axis length of the pigment A is within the above range, it is easy to obtain a film having high color value and suppressed film shrinkage. Furthermore, when a pattern is formed by the photolithography method using the colored composition of the present invention, it is possible to suppress the occurrence of a development residual and form a pattern having a good rectangularity.
　顔料Ａの長軸長／短軸長の値の上限は、光の散乱を抑制して輝度の高い膜が得られやすいという理由から２．７以下であることが好ましく、２．４以下であることがより好ましい。また、顔料Ａの長軸長／短軸長の値の下限は、膜中に顔料をより緻密に敷き詰められやすいという理由から、１．６以上であることが好ましく、１．８以上であることがより好ましく、２．０以上であることがより好ましい。 The upper limit of the value of the major axis length / the minor axis length of the pigment A is preferably 2.7 or less, and is 2.4 or less because it is easy to obtain a film with high brightness by suppressing light scattering. Is more preferable. Further, the lower limit of the value of the major axis length / minor axis length of the pigment A is preferably 1.6 or more, and is preferably 1.8 or more because the pigment can be more densely spread in the film. Is more preferable, and 2.0 or more is more preferable.
　顔料Ａの短軸長の平均値は１０～１００ｎｍであることが好ましい。下限は、得られる膜の耐熱性、耐湿性、耐候性などの信頼性の観点から１５ｎｍ以上が好ましく、２０ｎｍ以上がより好ましく、３０ｎｍ以上が更に好ましい。上限は、色価の観点から７０ｎｍ以下が好ましく、５０ｎｍ以下がより好ましく、４０ｎｍ以下が更に好ましい。 The average minor axis length of Pigment A is preferably 10 to 100 nm. The lower limit is preferably 15 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more from the viewpoint of reliability such as heat resistance, moisture resistance and weather resistance of the obtained film. From the viewpoint of color value, the upper limit is preferably 70 nm or less, more preferably 50 nm or less, further preferably 40 nm or less.
　顔料Ａの長軸長の平均値は１５～１５０ｎｍであることが好ましい。下限は、信頼性の観点から２０ｎｍ以上が好ましく、３０ｎｍ以上がより好ましい。上限は、色価の観点から１００ｎｍ以下が好ましく、７０ｎｍ以下がより好ましく、５０ｎｍ以下が更に好ましい。 The average major axis length of Pigment A is preferably 15 to 150 nm. From the viewpoint of reliability, the lower limit is preferably 20 nm or more, more preferably 30 nm or more. From the viewpoint of color value, the upper limit is preferably 100 nm or less, more preferably 70 nm or less, further preferably 50 nm or less.
　なお、本明細書において、長軸長および短軸長は次の方法で測定した値である。すなわち、走査型電子顕微鏡を用い、加速電圧５ｋＶ、撮像倍率１０万倍で撮影した画像をデジタル化して、粒子の長軸方向、短軸方向の画像輝度データ（長軸方向の座標、短軸方向の座標、および輝度の３成分からなる。）を作成する。デジタル化では、画像を幅方向に１２８０分割して、輝度８ビットで処理して２５６階調のデータを得て、分割した各座標ポイントの画像輝度を所定の階調値に変換する。次に、得られた画像輝度データにおいて、粒子の長軸にあたる方向の座標を横軸にとり、長軸方向の各座標ポイントにおける輝度の平均値（即ち、１２８０分割した各座標ポイントにおける輝度の平均値）を縦軸にとって輝度曲線を作成する。作成した輝度曲線を微分して微分曲線を作成し、作成した微分曲線のピーク位置から粒子の境界の座標を特定する。粒子の長軸にあたる方向の座標を横軸にとる操作を３回繰り返し、最も長い軸長を長軸長とする。短軸方向でも座標を横軸にとる操作を３回繰り返し、最も短い軸長を短軸長とする。詳しくは、長軸長とは、粒子の長さを最も長く取ることができる軸（直線）を長軸として決定し、この長軸の長さとする。一方、短軸とは、長軸と直交する直線で粒子長さを取ったときに最も長さが長くなる軸として決定し、この軸の長さを短軸長とする。 In this specification, the major axis length and the minor axis length are values measured by the following method. That is, by using a scanning electron microscope, an image taken at an accelerating voltage of 5 kV and an imaging magnification of 100,000 is digitized, and image luminance data in the major axis direction and minor axis direction of particles (coordinates in major axis direction, minor axis direction). Is composed of three components, namely, the coordinates of, and the luminance). In the digitization, an image is divided into 1280 in the width direction and processed with 8-bit luminance to obtain data of 256 gradations, and the image luminance of each divided coordinate point is converted into a predetermined gradation value. Next, in the obtained image brightness data, the horizontal axis represents the coordinate in the direction of the long axis of the particle, and the average value of the brightness at each coordinate point in the long axis direction (that is, the average value of the brightness at each of the 1280 divided coordinate points). ) Is the vertical axis, and a brightness curve is created. The created brightness curve is differentiated to create a differential curve, and the coordinate of the boundary of the particle is specified from the peak position of the created differential curve. The operation of setting the coordinate in the direction corresponding to the long axis of the particle as the horizontal axis is repeated three times, and the longest axis length is set as the long axis length. Even in the short axis direction, the operation of setting the coordinate on the horizontal axis is repeated three times, and the shortest axis length is set as the short axis length. Specifically, the major axis length is determined by defining the axis (straight line) that can maximize the length of the particle as the major axis, and using the major axis length. On the other hand, the minor axis is determined as the axis that has the longest length when the particle length is taken on a straight line orthogonal to the major axis, and the length of this axis is defined as the minor axis length.
　また、顔料Ａの短軸長の平均値および顔料Ａの長軸長の平均値は、１００個の顔料Ａの短軸長および長軸長の算術平均値である。 Further, the average value of the short axis length of the pigment A and the average value of the long axis length of the pigment A are the arithmetic average values of the short axis length and the long axis length of 100 pigments A.
　顔料の長軸長／短軸長の値を調整する方法としては、顔料のミリング条件を調整して長軸長／短軸長の値を調整する方法、粒子成長抑制剤の種類及び使用量を調整してミリング処理を行い長軸長／短軸長の値を調整する方法、顔料を加熱熟成して長軸長／短軸長の値を調整する方法などが挙げられる。粒子成長抑制剤としては、特開２００９－２２１２６６号公報の段落番号００４１～００５０に記載された化合物が挙げられる。 The major axis length / minor axis length value of the pigment can be adjusted by adjusting the milling conditions of the pigment to adjust the major axis length / minor axis length values, and the type and amount of the particle growth inhibitor. A method of adjusting the major axis length / minor axis length value by adjusting and milling, a method of adjusting the major axis length / minor axis length value by heating and aging the pigment, and the like. Examples of the particle growth inhibitor include the compounds described in paragraph Nos. 0041 to 0050 of JP-A-2009-212266.
　本発明で用いられる顔料の種類としては以下に示すものが挙げられる。 The types of pigments used in the present invention include those shown below.
　カラーインデックス（Ｃ．Ｉ．）ピグメントイエロー１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４，２３１，２３２（メチン／ポリメチン系）等（以上、黄色顔料）、
　Ｃ．Ｉ．ピグメントオレンジ２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等（以上、オレンジ色顔料）、
　Ｃ．Ｉ．ピグメントグリーン７，１０，３６，３７，５８，５９，６２，６３等（以上、緑色顔料）、
　Ｃ．Ｉ．ピグメントバイオレット１，１９，２３，２７，３２，３７，４２，６０（トリアリールメタン系），６１（キサンテン系）等（以上、紫色顔料）、
　Ｃ．Ｉ．ピグメントブルー１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，２９，６０，６４，６６，７９，８０，８７（モノアゾ系），８８（メチン／ポリメチン系）等（以上、青色顔料）、
　Ｃ．Ｉ．ピグメントレッド１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７９，２９４（キサンテン系、Ｏｒｇａｎｏ　Ｕｌｔｒａｍａｒｉｎｅ、Ｂｌｕｉｓｈ　Ｒｅｄ）等（以上、赤色顔料）。 Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 72,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,231,232 (methine / polymethine type) etc. Pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Above, orange pigment),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63 etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane type), 61 (xanthene type), etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo system), 88 (methine / polymethine type), etc. (above, blue 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 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184. 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 279, 294 (xanthene-based, Organ) Ultramarine, Bluish Red), etc. (or more, a red pigment).
　また、緑色顔料として、１分子中のハロゲン原子数が平均１０～１４個であり、臭素原子数が平均８～１２個であり、塩素原子数が平均２～５個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開ＷＯ２０１５／１１８７２０号公報に記載の化合物が挙げられる。また、緑色顔料としてＣＮ１０６９０９０２７Ａに記載の化合物、リン酸エステルを配位子として有するフタロシアニン化合物などを用いることもできる。 Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12 and an average number of chlorine atoms of 2 to 5 Can also be used. Specific examples thereof include the compounds described in International Publication WO2015 / 118720. Further, the compound described in CN1069009027A, a phthalocyanine compound having a phosphoric acid ester as a ligand, or the like can be used as a green pigment.
　また、青色顔料として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開２０１２－２４７５９１号公報の段落００２２～００３０、特開２０１１－１５７４７８号公報の段落００４７に記載の化合物が挙げられる。 Alternatively, an aluminum phthalocyanine compound having a phosphorus atom may be used as the blue pigment. Specific examples thereof include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraph 0047 of JP2011-157478A.
　また、黄色顔料として、特開２０１７－２０１００３号公報に記載されている顔料、特開２０１７－１９７７１９号公報に記載されている顔料、特開２０１７－１７１９１２号公報の段落番号００１１～００６２、０１３７～０２７６に記載されている顔料、特開２０１７－１７１９１３号公報の段落番号００１０～００６２、０１３８～０２９５に記載されている顔料、特開２０１７－１７１９１４号公報の段落番号００１１～００６２、０１３９～０１９０に記載されている顔料、特開２０１７－１７１９１５号公報の段落番号００１０～００６５、０１４２～０２２２に記載されている顔料を用いることもできる。 As yellow pigments, the pigments described in JP-A-2017-201003, the pigments described in JP-A-2017-197719, and paragraph numbers 0011 to 0062 and 0137 to JP-A-2017-171912 are disclosed. No. 0276 to the pigments described in JP-A-2017-171913, paragraphs 0010 to 0062 and 0138 to 0295 in JP-A No. 2017-171914, and paragraphs 0011 to 0062 and 0139 to 0190 in JP-A No. 2017-171914. The pigments described, and the pigments described in paragraph Nos. 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915 can also be used.
　また、黄色顔料として、特開２０１８－６２６４４に記載の化合物を用いることもできる。この化合物は顔料誘導体としても使用可能である。 Alternatively, the compounds described in JP-A-2018-62644 can be used as the yellow pigment. This compound can also be used as a pigment derivative.
　また、赤色顔料として、特開２０１７－２０１３８４号公報に記載の構造中に少なくとも１つ臭素原子が置換したジケトピロロピロール系顔料、特許第６２４８８３８号の段落番号００１６～００２２に記載のジケトピロロピロール系顔料などを用いることもできる。また、赤色顔料として、芳香族環に対して、酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。 Further, as a red pigment, a diketopyrrolopyrrole pigment in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole described in paragraph Nos. 0016 to 0022 of Japanese Patent No. 6248838. A pyrrole pigment or the like can also be used. As the red pigment, it is also possible to use a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is introduced is bound to a diketopyrrolopyrrole skeleton. it can.
　本発明で用いられる顔料Ａは、赤色顔料を含むものであることが好ましい。また、赤色顔料は、ジケトピロロピロール化合物であることも好ましい。赤色顔料は、カラーインデックスピグメントレッド２５４、カラーインデックスピグメントレッド２６４、および、カラーインデックスピグメントレッド２７２から選ばれる少なくとも１種であることが好ましく、カラーインデックスピグメントレッド２７２であることがより好ましい。赤色顔料は一般的に色価の低いものが多い傾向にあるが、赤色顔料として長軸長／短軸長の値が１．４以上であるものを用いることにより、赤色の色価の高い膜を形成することができる。 The pigment A used in the present invention preferably contains a red pigment. The red pigment is also preferably a diketopyrrolopyrrole compound. The red pigment is preferably at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272, and more preferably Color Index Pigment Red 272. Red pigments generally tend to have a low color value, but by using a red pigment having a major axis length / minor axis length value of 1.4 or more, a film having a high red color value can be obtained. Can be formed.
　本発明において、着色剤には染料を用いることもできる。染料としては特に制限はなく、公知の染料が使用できる。例えば、ピラゾールアゾ系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が挙げられる。また、特開２０１２－１５８６４９号公報に記載のチアゾール化合物、特開２０１１－１８４４９３号公報に記載のアゾ化合物、特開２０１１－１４５５４０号公報に記載のアゾ化合物も好ましく用いることができる。また、黄色染料として、特開２０１３－０５４３３９号公報の段落番号００１１～００３４に記載のキノフタロン化合物、特開２０１４－０２６２２８号公報の段落番号００１３～００５８に記載のキノフタロン化合物などを用いることもできる。 In the present invention, a dye may be used as the colorant. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo type, anilino azo type, triaryl methane type, anthraquinone type, anthrapyridone type, benzylidene type, oxonol type, pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, Examples thereof include phthalocyanine-based dyes, benzopyran-based dyes, indigo-based dyes, and pyrromethene-based dyes. Further, the thiazole compound described in JP 2012-158649 A, the azo compound described in JP 2011-18449 A, and the azo compound described in JP 2011-145540 A can also be preferably used. Further, as the yellow dye, the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-054339A, the quinophthalone compounds described in paragraphs 0013 to 0058 of JP2014-026228A, and the like can be used.
　本発明において、着色剤には色素多量体を用いることもできる。色素多量体は、溶剤に溶解して用いられる染料であることが好ましいが、色素多量体は、粒子を形成していてもよく、色素多量体が粒子である場合は通常溶剤に分散した状態で用いられる。粒子状態の色素多量体は、例えば乳化重合によって得ることができ、特開２０１５－２１４６８２号公報に記載されている化合物および製造方法が具体例として挙げられる。色素多量体は、一分子中に、色素構造を２以上有するものであり、色素構造を３以上有することが好ましい。上限は、特に限定はないが、１００以下とすることもできる。一分子中に有する複数の色素構造は、同一の色素構造であってもよく、異なる色素構造であってもよい。色素多量体の重量平均分子量（Ｍｗ）は、２０００～５００００が好ましい。下限は、３０００以上がより好ましく、６０００以上がさらに好ましい。上限は、３００００以下がより好ましく、２００００以下がさらに好ましい。色素多量体は、特開２０１１－２１３９２５号公報、特開２０１３－０４１０９７号公報、特開２０１５－０２８１４４号公報、特開２０１５－０３０７４２号公報、国際公開ＷＯ２０１６／０３１４４２号公報等に記載されている化合物を用いることもできる。 In the present invention, a dye multimer may be used as the colorant. The dye multimer is preferably a dye used by being dissolved in a solvent, but the dye multimer may form particles, and when the dye multimer is particles, it is usually in a state of being dispersed in a solvent. Used. The dye multimer in the form of particles can be obtained, for example, by emulsion polymerization, and specific examples thereof include the compounds and production methods described in JP-A-2015-214682. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures contained in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000. The lower limit is more preferably 3,000 or more, still more preferably 6000 or more. The upper limit is more preferably 30,000 or less, further preferably 20,000 or less. Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, International Publication WO2016 / 031442, and the like. Compounds can also be used.
　着色剤の含有量は、着色組成物の全固形分中５０質量％以上であり、５３質量％以上が好ましく、５９質量％以上がより好ましく、６２質量％以上が更に好ましい。上限は、８５質量％以下が好ましく、８０質量％以下がより好ましい。 The content of the coloring agent is 50% by mass or more based on the total solid content of the coloring composition, preferably 53% by mass or more, more preferably 59% by mass or more, and further preferably 62% by mass or more. The upper limit is preferably 85% by mass or less, and more preferably 80% by mass or less.
　本発明の着色組成物に用いられる着色剤は、顔料の含有量が４０質量％以上であり、５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましく、８０質量％以上であることがより一層好ましく、９０質量％以上であることが更に一層好ましく、９５質量％以上であることが特に好ましい。上限は、１００質量％とすることができる。また、本発明の着色組成物に用いられる着色剤は、実質的に顔料のみであることも好ましい。着色剤が実質的に顔料のみである場合とは、顔料の含有量が９９質量％以上であることを意味し、９９．５質量％以上であることが好ましく、顔料のみであることが特に好ましい。本発明の着色組成物に用いられる着色剤が２種以上の顔料を含む場合、２種以上の顔料のうち少なくとも１種が上述した顔料Ａであればよいが、着色剤に含まれるすべての顔料が上述した顔料Ａであることが好ましい。 The coloring agent used in the coloring composition of the present invention has a pigment content of 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. Is more preferable, 80% by mass or more is more preferable, 90% by mass or more is still more preferable, and 95% by mass or more is particularly preferable. The upper limit can be 100% by mass. It is also preferable that the coloring agent used in the coloring composition of the present invention is substantially only a pigment. The case where the colorant is substantially only the pigment means that the content of the pigment is 99% by mass or more, preferably 99.5% by mass or more, and particularly preferably only the pigment. . When the colorant used in the coloring composition of the present invention contains two or more pigments, at least one of the two or more pigments may be the above-described pigment A, but all pigments contained in the colorant Is preferably the pigment A described above.
　本発明の着色組成物に用いられる着色剤は、上述した顔料Ａ（短軸長と長軸長との比率である長軸長／短軸長の値が１．４以上の顔料）の含有量が４０質量％以上であり、５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましく、８０質量％以上であることがより一層好ましく、９０質量％以上であることが更に一層好ましく、９５質量％以上であることが特に好ましい。上限は、１００質量％とすることができる。また、本発明の着色組成物に用いられる着色剤は、実質的に顔料Ａのみであることも好ましい。着色剤が実質的に顔料Ａのみである場合とは、顔料Ａの含有量が９９質量％以上であることを意味し、９９．５質量％以上であることが好ましく、顔料Ａのみであることが特に好ましい。 The colorant used in the coloring composition of the present invention contains the above-described pigment A (pigment having a major axis length / minor axis length value, which is a ratio of the minor axis length to the major axis length, of 1.4 or more). Is 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and further preferably 80% by mass or more. It is more preferably 90% by mass or more, still more preferably 95% by mass or more. The upper limit can be 100% by mass. It is also preferable that the coloring agent used in the coloring composition of the present invention is substantially only the pigment A. The case where the colorant is substantially only the pigment A means that the content of the pigment A is 99% by mass or more, preferably 99.5% by mass or more, and only the pigment A is contained. Is particularly preferable.
　本発明の着色組成物において、顔料の含有量は、着色組成物の全固形分中５０質量％以上であることが好ましく、５３質量％以上がより好ましく、５９質量％以上が更に好ましく、６２質量％以上が特に好ましい。上限は、８５質量％以下が好ましく、８０質量％以下がより好ましい。 In the coloring composition of the present invention, the content of the pigment is preferably 50% by mass or more, more preferably 53% by mass or more, further preferably 59% by mass or more, and 62% by mass in the total solid content of the coloring composition. % Or more is particularly preferable. The upper limit is preferably 85% by mass or less, and more preferably 80% by mass or less.
＜＜樹脂＞＞
　本発明の着色組成物は、樹脂を含有する。樹脂は、例えば、顔料を着色組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で使用することもできる。 << resin >>
The coloring composition of the present invention contains a resin. The resin is mixed, for example, for the purpose of dispersing the pigment in the coloring composition or the use of a binder. The resin mainly used for dispersing the pigment is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for purposes other than such an application.
　樹脂の重量平均分子量（Ｍｗ）は、３０００～２００００００が好ましい。上限は、１００００００以下が好ましく、５０００００以下がより好ましい。下限は、４０００以上が好ましく、５０００以上がより好ましい。 The weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000. The upper limit is preferably 1,000,000 or less, more preferably 500000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.
　樹脂としては、（メタ）アクリル樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂などが挙げられる。これらの樹脂から１種を単独で使用してもよく、２種以上を混合して使用してもよい。また、特開２０１７－２０６６８９号公報の段落番号００４１～００６０に記載の樹脂、特開２０１８－０１０８５６号公報の段落番号００２２～００７１に記載の樹脂を用いることもできる。 Examples of the resin include (meth) acrylic resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin. , Polyolefin resins, cyclic olefin resins, polyester resins, styrene resins and the like. One of these resins may be used alone, or two or more thereof may be mixed and used. Further, the resins described in paragraphs 0041 to 0060 of JP-A-2017-206689 and the resins described in paragraphs 0022 to 0071 of JP-A-2018-010856 can also be used.
　本発明において、樹脂として酸基を有する樹脂を用いることが好ましい。この態様によれば、着色組成物の現像性を向上させることができ、矩形性に優れた画素を形成しやすい。酸基としては、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシル基が好ましい。酸基を有する樹脂は、例えば、アルカリ可溶性樹脂として用いることができる。 In the present invention, it is preferable to use a resin having an acid group as the resin. According to this aspect, the developability of the colored composition can be improved, and pixels having excellent rectangularity can be easily formed. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group, and a carboxyl group is preferable. The resin having an acid group can be used as, for example, an alkali-soluble resin.
　酸基を有する樹脂は、酸基を側鎖に有する繰り返し単位を含むことが好ましく、酸基を側鎖に有する繰り返し単位を樹脂の全繰り返し単位中５～７０モル％含むことがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の上限は、５０モル％以下であることが好ましく、３０モル％以下であることがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の下限は、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましい。 The resin having an acid group preferably contains a repeating unit having an acid group as a side chain, and more preferably contains 5 to 70 mol% of a repeating unit having an acid group as a side chain in all repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in its side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group in its side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.
　酸基を有する樹脂は、下記式（ＥＤ１）で示される化合物および／または下記式（ＥＤ２）で表される化合物（以下、これらの化合物を「エーテルダイマー」と称することもある。）を含むモノマー成分に由来する繰り返し単位を含むことも好ましい。 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 dimers”). It is also preferable to include a repeating unit derived from the component.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（ＥＤ１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。
Figure JPOXMLDOC01-appb-C000002
 　式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の詳細については、特開２０１０－１６８５３９号公報の記載を参酌でき、この内容は本明細書に組み込まれる。 In formula (ED1), 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.
Figure JPOXMLDOC01-appb-C000002
 In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of the formula (ED2), the description in JP 2010-168539 A can be referred to, and the contents thereof are incorporated in the present specification.
　エーテルダイマーの具体例としては、例えば、特開２０１３－０２９７６０号公報の段落番号０３１７の記載を参酌することができ、この内容は本明細書に組み込まれる。 As specific examples of the ether dimer, for example, the description in paragraph No. 0317 of JP2013-029760A can be referred to, and the contents thereof are incorporated in the present specification.
　本発明で用いられる樹脂は、下記式（Ｘ）で示される化合物に由来する繰り返し単位を含むことも好ましい。
Figure JPOXMLDOC01-appb-C000003
 　式（Ｘ）中、Ｒ１は、水素原子またはメチル基を表し、Ｒ２は炭素数２～１０のアルキレン基を表し、Ｒ３は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。 The resin used in the present invention preferably also contains a repeating unit derived from a compound represented by the following formula (X).
Figure JPOXMLDOC01-appb-C000003
 In formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or 1 to 20 carbon atoms which may include a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.
　酸基を有する樹脂については、特開２０１２－２０８４９４号公報の段落番号０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落番号０６８５～０７００）の記載、特開２０１２－１９８４０８号公報の段落番号００７６～００９９の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸基を有する樹脂は市販品を用いることもできる。 Regarding the resin having an acid group, JP-A-2012-208494, paragraph Nos. 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph Nos. 0685 to 0700), JP-A No. 2012-198408. The description of paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated in the present specification. Further, as the resin having an acid group, a commercially available product can be used.
　酸基を有する樹脂の酸価は、３０～５００ｍｇＫＯＨ／ｇが好ましい。下限は、５０ｍｇＫＯＨ／ｇ以上が好ましく、７０ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、４００ｍｇＫＯＨ／ｇ以下が好ましく、３００ｍｇＫＯＨ／ｇ以下がより好ましく、２００ｍｇＫＯＨ／ｇ以下が更に好ましい。酸基を有する樹脂の重量平均分子量（Ｍｗ）は、５０００～１０００００が好ましい。また、酸基を有する樹脂の数平均分子量（Ｍｎ）は、１０００～２００００が好ましい。 The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and further preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having an acid group is preferably 5,000 to 100,000. The number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.
　酸基を有する樹脂としては、例えば下記構造の樹脂などが挙げられる。
Figure JPOXMLDOC01-appb-C000004
 Examples of the resin having an acid group include resins having the following structures.
Figure JPOXMLDOC01-appb-C000004
　本発明の着色組成物は、分散剤としての樹脂を含むこともできる。分散剤としては、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。酸性分散剤（酸性樹脂）が有する酸基は、カルボキシル基が好ましい。酸性分散剤（酸性樹脂）の酸価は、４０～１０５ｍｇＫＯＨ／ｇが好ましく、５０～１０５ｍｇＫＯＨ／ｇがより好ましく、６０～１０５ｍｇＫＯＨ／ｇがさらに好ましい。また、塩基性分散剤（塩基性樹脂）とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤（塩基性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、塩基性基の量が５０モル％を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基であることが好ましい。 The coloring composition of the present invention may also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%, and the acid dispersant is substantially acid. A resin consisting of only a group is more preferable. The acid group contained in the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and further preferably 60 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group contained in the basic dispersant is preferably an amino group.
　分散剤として用いる樹脂は、酸基を有する繰り返し単位を含むことが好ましい。分散剤として用いる樹脂が酸基を有する繰り返し単位を含むことにより、フォトリソグラフィ法によりパターン形成する際、現像残渣の発生をより抑制できる。 The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, generation of a development residue can be further suppressed when forming a pattern by the photolithography method.
　分散剤として用いる樹脂は、グラフト樹脂であることも好ましい。グラフト樹脂の詳細は、特開２０１２－２５５１２８号公報の段落番号００２５～００９４の記載を参酌でき、この内容は本明細書に組み込まれる。 The resin used as the dispersant is also preferably a graft resin. Details of the graft resin can be referred to the descriptions in paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
　分散剤として用いる樹脂は、主鎖及び側鎖の少なくとも一方に窒素原子を含むポリイミン系分散剤であることも好ましい。ポリイミン系分散剤としては、ｐＫａ１４以下の官能基を有する部分構造を有する主鎖と、原子数４０～１００００の側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子とは、塩基性を呈する窒素原子であれば特に制限はない。ポリイミン系分散剤については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６の記載を参酌でき、この内容は本明細書に組み込まれる。 It is also preferable that the resin used as the dispersant is a polyimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom. The resin having is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom that exhibits basicity. Regarding the polyimine dispersant, the description in paragraph numbers 0102 to 0166 of JP 2012-255128 A can be referred to, and the contents thereof are incorporated in the present specification.
　分散剤として用いる樹脂は、コア部に複数個のポリマー鎖が結合した構造の樹脂であることも好ましい。このような樹脂としては、例えばデンドリマー（星型ポリマーを含む）が挙げられる。また、デンドリマーの具体例としては、特開２０１３－０４３９６２号公報の段落番号０１９６～０２０９に記載された高分子化合物Ｃ－１～Ｃ－３１などが挙げられる。 It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core part. Examples of such resins include dendrimers (including star polymers). In addition, specific examples of the dendrimer include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A-2013-043962.
　また、上述した酸基を有する樹脂（アルカリ可溶性樹脂）を分散剤として用いることもできる。 Also, the above-mentioned resin having an acid group (alkali-soluble resin) can be used as a dispersant.
　また、分散剤として用いる樹脂は、エチレン性不飽和結合基を側鎖に有する繰り返し単位を含む樹脂であることも好ましい。エチレン性不飽和結合基を側鎖に有する繰り返し単位の含有量は、樹脂の全繰り返し単位中１０モル％以上であることが好ましく、１０～８０モル％であることがより好ましく、２０～７０モル％であることが更に好ましい。 The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond group in the side chain. The content of the repeating unit having an ethylenically unsaturated bond group in its side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and more preferably 20 to 70 mol, based on all repeating units of the resin. % Is more preferable.
　分散剤は、市販品としても入手可能であり、そのような具体例としては、ＢＹＫＣｈｅｍｉｅ社製のＤＩＳＰＥＲＢＹＫシリーズ（例えば、ＤＩＳＰＥＲＢＹＫ－１１１、１６１など）、日本ルーブリゾール（株）製のソルスパースシリーズ（例えば、ソルスパース７６５００など）などが挙げられる。また、特開２０１４－１３０３３８号公報の段落番号００４１～０１３０に記載された顔料分散剤を用いることもでき、この内容は本明細書に組み込まれる。なお、上記分散剤として説明した樹脂は、分散剤以外の用途で使用することもできる。例えば、バインダーとして用いることもできる。 The dispersant is also available as a commercially available product, and specific examples thereof include the DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111 and 161, etc.), the Sols Perth series manufactured by Nippon Lubrizol Co., Ltd. For example, Solsperse 76500 etc.) and the like. Further, the pigment dispersant described in paragraph Nos. 0041 to 0130 of JP-A-2014-130338 can be used, and the contents thereof are incorporated in the present specification. The resin described as the above dispersant can be used for purposes other than the dispersant. For example, it can also be used as a binder.
　着色組成物の全固形分中における樹脂の含有量は、５～５０質量％が好ましい。下限は、１０質量％以上が好ましく、１５質量％以上がより好ましい。上限は、４０質量％以下が好ましく、３５質量％以下がより好ましく、３０質量％以下が更に好ましい。また、着色組成物の全固形分中における酸基を有する樹脂（アルカリ可溶性樹脂）の含有量は、５～５０質量％が好ましい。下限は、１０質量％以上が好ましく、１５質量％以上がより好ましい。上限は、４０質量％以下が好ましく、３５質量％以下がより好ましく、３０質量％以下が更に好ましい。また、樹脂全量中における酸基を有する樹脂（アルカリ可溶性樹脂）の含有量は、優れた現像性が得られやすいという理由から３０質量％以上が好ましく、５０質量％以上がより好ましく、７０質量％以上が更に好ましく、８０質量％以上が特に好ましい。上限は、１００質量％とすることができ、９５質量％とすることもでき、９０質量％以下とすることもできる。 The content of the resin in the total solid content of the coloring composition is preferably 5 to 50% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less. The content of the resin having an acid group (alkali-soluble resin) in the total solid content of the coloring composition is preferably 5 to 50% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less. The content of the resin having an acid group (alkali-soluble resin) in the total amount of the resin is preferably 30% by mass or more, more preferably 50% by mass or more, and 70% by mass, because excellent developability is easily obtained. The above is more preferable, and 80 mass% or more is particularly preferable. The upper limit can be 100% by mass, 95% by mass, or 90% by mass or less.
＜＜有機溶剤＞＞
　本発明の着色組成物は、有機溶剤を含有する。有機溶剤としては、各成分の溶解性や着色組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開ＷＯ２０１５／１６６７７９号公報の段落番号０２２３を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤を好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミドなどが挙げられる。ただし有機溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。 << organic solvent >>
The coloring composition of the present invention contains an organic solvent. The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like. For details of these, reference can be made to paragraph No. 0223 of International Publication WO 2015/166779, the contents of which 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. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate and 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. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as the organic solvent due to environmental reasons (for example, 50 mass ppm (parts relative to the total amount of the organic solvent). per million) or less, 10 mass ppm or less, or 1 mass ppm or less).
　本発明においては、金属含有量の少ない有機溶剤を用いることが好ましく、有機溶剤の金属含有量は、例えば１０質量ｐｐｂ（ｐａｒｔｓ　ｐｅｒ　ｂｉｌｌｉｏｎ）以下であることが好ましい。必要に応じて質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）レベルの有機溶剤を用いてもよく、そのような有機溶剤は例えば東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。 In the present invention, it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent having a mass ppt (parts per trilion) level may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
　有機溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下が更に好ましい。フィルタの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 Examples of methods for removing impurities such as metals from organic solvents 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 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
　有機溶剤は、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, as for the isomer, only 1 type may be contained and 2 or more types may be contained.
　本発明において、有機溶剤中の過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 In the present invention, the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
　着色組成物中における有機溶剤の含有量は、１０～９５質量％であることが好ましく、２０～９０質量％であることがより好ましく、３０～９０質量％であることが更に好ましい。 The content of the organic solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 30 to 90% by mass.
　また、本発明の着色組成物は、環境規制の観点から環境規制物質を実質的に含有しないことが好ましい。なお、本発明において、環境規制物質を実質的に含有しないとは、着色組成物中における環境規制物質の含有量が５０質量ｐｐｍ以下であることを意味し、３０質量ｐｐｍ以下であることが好ましく、１０質量ｐｐｍ以下であることが更に好ましく、１質量ｐｐｍ以下であることが特に好ましい。環境規制物質は、例えばベンゼン；トルエン、キシレン等のアルキルベンゼン類；クロロベンゼン等のハロゲン化ベンゼン類等が挙げられる。これらは、ＲＥＡＣＨ（Ｒｅｇｉｓｔｒａｔｉｏｎ　Ｅｖａｌｕａｔｉｏｎ　Ａｕｔｈｏｒｉｚａｔｉｏｎ　ａｎｄ　Ｒｅｓｔｒｉｃｔｉｏｎ　ｏｆ　ＣＨｅｍｉｃａｌｓ）規則、ＰＲＴＲ（Ｐｏｌｌｕｔａｎｔ　Ｒｅｌｅａｓｅ　ａｎｄ　Ｔｒａｎｓｆｅｒ　Ｒｅｇｉｓｔｅｒ）法、ＶＯＣ（Ｖｏｌａｔｉｌｅ　Ｏｒｇａｎｉｃ　Ｃｏｍｐｏｕｎｄｓ）規制等のもとに環境規制物質として登録されており、使用量や取り扱い方法が厳しく規制されている。これらの化合物は、本発明の着色組成物に用いられる各成分などを製造する際に溶媒として用いられることがあり、残留溶媒として着色組成物中に混入することがある。人への安全性、環境への配慮の観点よりこれらの物質は可能な限り低減することが好ましい。環境規制物質を低減する方法としては、系中を加熱や減圧して環境規制物質の沸点以上にして系中から環境規制物質を留去して低減する方法が挙げられる。また、少量の環境規制物質を留去する場合においては、効率を上げる為に該当溶媒と同等の沸点を有する溶媒と共沸させることも有用である。また、ラジカル重合性を有する化合物を含有する場合、減圧留去中にラジカル重合反応が進行して分子間で架橋してしまうことを抑制するために重合禁止剤等を添加して減圧留去してもよい。これらの留去方法は、原料の段階、原料を反応させた生成物（例えば重合した後の樹脂溶液や多官能モノマー溶液）の段階、またはこれらの化合物を混ぜて作製した着色組成物の段階などのいずれの段階でも可能である。 Further, it is preferable that the coloring composition of the present invention does not substantially contain an environmentally controlled substance from the viewpoint of environmental regulation. In the present invention, the phrase "substantially free of environmentally controlled substances" means that the content of the environmentally controlled substances in the colored composition is 50 mass ppm or less, preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of the environmentally controlled substance include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene. These are REACH (Registration Evaluation Authorization and Restriction of CHchemicals) rules, PRTR (Pollutant Release and Transfer Registor) laws and regulations, and VOC (Volunteer Organics) regulated substances, etc. The method is tightly regulated. These compounds may be used as a solvent when producing each component used in the coloring composition of the present invention, and may be mixed in the coloring composition as a residual solvent. From the viewpoints of human safety and environmental consideration, it is preferable to reduce these substances as much as possible. As a method for reducing the environmentally controlled substance, there is a method in which the system is heated or decompressed to a temperature equal to or higher than the boiling point of the environmentally controlled substance and the environmentally controlled substance is distilled off from the system to reduce the amount. Further, in the case of distilling off a small amount of environmentally controlled substances, it is also useful to azeotropically distill with a solvent having a boiling point equivalent to that of the corresponding solvent in order to improve efficiency. Further, in the case of containing a compound having radical polymerizability, a polymerization inhibitor or the like is added and the solvent is distilled off under reduced pressure in order to prevent the radical polymerization reaction from progressing and cross-linking between molecules during the distillation under reduced pressure. May be. These distillation methods include the steps of the raw material, the step of the product obtained by reacting the raw material (for example, the resin solution or polyfunctional monomer solution after polymerization), or the step of the colored composition prepared by mixing these compounds. It is possible at any stage of.
＜＜重合性化合物＞＞
　本発明の着色組成物は、重合性化合物を含有することが好ましい。重合性化合物としては、ラジカル、酸または熱により架橋可能な公知の化合物を用いることができる。本発明において、重合性化合物は、例えば、エチレン性不飽和結合基を有する化合物であることが好ましい。エチレン性不飽和結合基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。本発明で用いられる重合性化合物は、ラジカル重合性化合物であることが好ましい。 << polymerizable compound >>
The colored composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by a radical, an acid or heat can be used. In the present invention, the polymerizable compound is preferably a compound having an ethylenically unsaturated bond group, for example. Examples of the ethylenically unsaturated bond group include a vinyl group, a (meth) allyl group and a (meth) acryloyl group. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.
　重合性化合物としては、モノマー、プレポリマー、オリゴマーなどの化学的形態のいずれであってもよいが、モノマーが好ましい。重合性化合物の分子量は、１００～３０００が好ましい。上限は、２０００以下がより好ましく、１５００以下が更に好ましい。下限は、１５０以上がより好ましく、２５０以上が更に好ましい。 The polymerizable compound may be in any chemical form such as a monomer, a prepolymer or an oligomer, but a monomer is preferable. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, still more preferably 1500 or less. The lower limit is more preferably 150 or more, further preferably 250 or more.
　重合性化合物は、エチレン性不飽和結合基を３個以上含む化合物であることが好ましく、エチレン性不飽和結合基を３～１５個含む化合物であることがより好ましく、エチレン性不飽和結合基を３～６個含む化合物であることが更に好ましい。また、重合性化合物は、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。重合性化合物の具体例としては、特開２００９－２８８７０５号公報の段落番号００９５～０１０８、特開２０１３－０２９７６０号公報の段落０２２７、特開２００８－２９２９７０号公報の段落番号０２５４～０２５７、特開２０１３－２５３２２４号公報の段落番号００３４～００３８、特開２０１２－２０８４９４号公報の段落番号０４７７、特開２０１７－０４８３６７号公報、特許第６０５７８９１号公報、特許第６０３１８０７号公報に記載されている化合物が挙げられ、これらの内容は本明細書に組み込まれる。 The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond groups, and more preferably an ethylenically unsaturated bond group. A compound containing 3 to 6 is more preferable. Further, the polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound. Specific examples of the polymerizable compound include paragraph numbers 0095 to 0108 of JP 2009-288705 A, paragraph 0227 of JP 2013-029760 A, paragraphs 0254 to 0257 of JP 2008-292970 A, and JP Compounds described in paragraphs 0034 to 0038 of 2013-253224, paragraphs 0477 of JP2012-208494A, JP2017-048367A, JP60557891A, and JP6031807A are disclosed. And their contents are incorporated herein.
　重合性化合物としては、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、ＮＫエステルＡ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコールおよび／またはプロピレングリコール残基を介して結合している構造の化合物（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）が好ましい。また、重合性化合物としては、ジグリセリンＥＯ（エチレンオキシド）変性（メタ）アクリレート（市販品としてはＭ－４６０；東亞合成製）、ペンタエリスリトールテトラアクリレート（新中村化学工業（株）製、ＮＫエステルＡ－ＴＭＭＴ）、１，６－ヘキサンジオールジアクリレート（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＨＤＤＡ）、ＲＰ－１０４０（日本化薬（株）製）、アロニックスＴＯ－２３４９（東亞合成（株）製）、ＮＫオリゴＵＡ－７２００（新中村化学工業（株）製）、８ＵＨ－１００６、８ＵＨ－１０１２（大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることもできる。 As the polymerizable compound, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku (stock) )), 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) Co., Ltd., NK ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues. Compounds (eg, commercially available from Sartomer And are, SR454, SR499) is preferable. As the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) acrylate (M-460 as a commercial product; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A) -TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) , NK oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. You can also
　また、重合性化合物として、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキシ変性トリ（メタ）アクリレート、トリメチロールプロパンエチレンオキシ変性トリ（メタ）アクリレート、イソシアヌル酸エチレンオキシ変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどの３官能の（メタ）アクリレート化合物を用いることも好ましい。３官能の（メタ）アクリレート化合物の市販品としては、アロニックスＭ－３０９、Ｍ－３１０、Ｍ－３２１、Ｍ－３５０、Ｍ－３６０、Ｍ－３１３、Ｍ－３１５、Ｍ－３０６、Ｍ－３０５、Ｍ－３０３、Ｍ－４５２、Ｍ－４５０（東亞合成（株）製）、ＮＫエステル　Ａ９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＴＭＰＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＧＰＯ－３０３、ＴＭＰＴＡ、ＴＨＥ－３３０、ＴＰＡ－３３０、ＰＥＴ－３０（日本化薬（株）製）などが挙げられる。 Further, as the polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate. It is also preferable to use a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, 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 so on.
　重合性化合物は、酸基を有する化合物を用いることもできる。酸基を有する重合性化合物を用いることで、現像時に未露光部の重合性化合物が除去されやすく、現像残渣の発生を抑制できる。酸基としては、カルボキシル基、スルホ基、リン酸基等が挙げられ、カルボキシル基が好ましい。酸基を有する重合性化合物の市販品としては、アロニックスＭ－５１０、Ｍ－５２０、アロニックスＴＯ－２３４９（東亞合成（株）製）等が挙げられる。酸基を有する重合性化合物の好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、より好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性化合物の酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像液に対する溶解性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造や取扱い上、有利である。 A compound having an acid group can also be used as the polymerizable compound. By using the polymerizable compound having an acid group, the polymerizable compound in the unexposed area can be easily removed during development, and the development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group and a phosphoric acid group, and a carboxyl group is preferable. Examples of commercially available polymerizable compounds having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like. The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developing solution is good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling.
　重合性化合物は、カプロラクトン構造を有する化合物であることも好ましい態様である。カプロラクトン構造を有する重合性化合物は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０、ＤＰＣＡ－３０、ＤＰＣＡ－６０、ＤＰＣＡ－１２０等が挙げられる。 It is also a preferred embodiment that the polymerizable compound is 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, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
　重合性化合物は、アルキレンオキシ基を有する重合性化合物を用いることもできる。アルキレンオキシ基を有する重合性化合物は、エチレンオキシ基および／またはプロピレンオキシ基を有する重合性化合物が好ましく、エチレンオキシ基を有する重合性化合物がより好ましく、エチレンオキシ基を４～２０個有する３～６官能（メタ）アクリレート化合物がさらに好ましい。アルキレンオキシ基を有する重合性化合物の市販品としては、例えばサートマー社製のエチレンオキシ基を４個有する４官能（メタ）アクリレートであるＳＲ－４９４、イソブチレンオキシ基を３個有する３官能（メタ）アクリレートであるＫＡＹＡＲＡＤ　ＴＰＡ－３３０などが挙げられる。 As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups. Hexafunctional (meth) acrylate compounds are more preferred. Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and trifunctional (meth) having three isobutyleneoxy groups. Examples include KAYARAD TPA-330, which is an acrylate.
　重合性化合物は、フルオレン骨格を有する重合性化合物を用いることもできる。フルオレン骨格を有する重合性化合物の市販品としては、オグソールＥＡ－０２００、ＥＡ－０３００（大阪ガスケミカル（株）製、フルオレン骨格を有する（メタ）アクリレートモノマー）などが挙げられる。 The polymerizable compound may be a polymerizable compound having a fluorene skeleton. Examples of commercially available polymerizable compounds having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (Osaka Gas Chemical Co., Ltd., (meth) acrylate monomer having a fluorene skeleton).
　重合性化合物としては、トルエンなどの環境規制物質を実質的に含まない化合物を用いることも好ましい。このような化合物の市販品としては、ＫＡＹＡＲＡＤ　ＤＰＨＡ　ＬＴ、ＫＡＹＡＲＡＤ　ＤＰＥＡ－１２　ＬＴ（日本化薬（株）製）などが挙げられる。 As the polymerizable compound, it is also preferable to use a compound that does not substantially contain an environmentally regulated substance such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12LT (manufactured by Nippon Kayaku Co., Ltd.).
　重合性化合物としては、特公昭４８－０４１７０８号公報、特開昭５１－０３７１９３号公報、特公平０２－０３２２９３号公報、特公平０２－０１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－０４９８６０号公報、特公昭５６－０１７６５４号公報、特公昭６２－０３９４１７号公報、特公昭６２－０３９４１８号公報に記載されたエチレンオキサイド系骨格を有するウレタン化合物も好適である。また、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平０１－１０５２３８号公報に記載された分子内にアミノ構造やスルフィド構造を有する重合性化合物を用いることも好ましい。また、重合性化合物としては、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００、ＬＩＮＣ－２０２ＵＡ（共栄社化学（株）製）などの市販品を用いることもできる。 Examples of the polymerizable compound include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. Further, it is also preferable to use the polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909 and JP-A-01-105238. As the polymerizable compound, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600. , T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) and the like may be used.
　着色組成物の全固形分中における重合性化合物の含有量は０．１～５０質量％であることが好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、４５質量％以下がより好ましく、４０質量％以下が更に好ましい。重合性化合物は、１種単独であってもよいし、２種以上を併用してもよい。２種以上を併用する場合は、それらの合計が上記範囲となることが好ましい。 The content of the polymerizable compound in the total solid content of the coloring composition is preferably 0.1 to 50% by mass. The lower limit is more preferably 0.5% by mass or more, still more preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, further preferably 40% by mass or less. The polymerizable compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total of them be in the above range.
　また、着色組成物の全固形分中における重合性化合物と樹脂との合計の含有量は、硬化性、現像性および被膜形成性の観点から１０～６５質量％が好ましい。下限は、１５質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上が更に好ましい。上限は、６０質量％以下が好ましく、５０質量％以下がより好ましく、４０質量％以下が更に好ましい。また、重合性化合物の１００質量部に対して、樹脂を３０～３００質量部含有することが好ましい。下限は５０質量部以上が好ましく、８０質量部以上がより好ましい。上限は２５０質量部以下が好ましく、２００質量部以下がより好ましい。 Further, the total content of the polymerizable compound and the resin in the total solid content of the coloring composition is preferably 10 to 65% by mass from the viewpoint of curability, developability and film forming property. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less. Further, it is preferable to contain 30 to 300 parts by mass of the resin with respect to 100 parts by mass of the polymerizable compound. The lower limit is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more. The upper limit is preferably 250 parts by mass or less, more preferably 200 parts by mass or less.
＜＜光重合開始剤＞＞
　本発明の着色組成物は光重合開始剤を含むことが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。 << photopolymerization initiator >>
The coloring composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light rays in the ultraviolet region to the visible region are preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.
　光重合開始剤としては、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など）、アシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、α－ヒドロキシケトン化合物、α－アミノケトン化合物などが挙げられる。光重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物および３－アリール置換クマリン化合物であることが好ましく、オキシム化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、および、アシルホスフィン化合物から選ばれる化合物であることがより好ましく、オキシム化合物であることが更に好ましい。光重合開始剤については、特開２０１４－１３０１７３号公報の段落００６５～０１１１、特許第６３０１４８９号公報の記載を参酌でき、この内容は本明細書に組み込まれる。 Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (eg, compounds having a triazine skeleton, compounds having an oxadiazole skeleton), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds. , Ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds and the like. The photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole, from the viewpoint of exposure sensitivity. A dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl-substituted coumarin compound are preferable, and an oxime compound and an α-hydroxyketone compound are preferable. More preferably, it is a compound selected from an α-aminoketone compound and an acylphosphine compound, and even more preferably an oxime compound. Regarding the photopolymerization initiator, the descriptions in paragraphs 0065 to 0111 and JP 6301489 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated in the present specification.
　α－ヒドロキシケトン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ－１２７（以上、ＢＡＳＦ社製）などが挙げられる。α－アミノケトン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、ＩＲＧＡＣＵＲＥ－３７９、及び、ＩＲＧＡＣＵＲＥ－３７９ＥＧ（以上、ＢＡＳＦ社製）などが挙げられる。アシルホスフィン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－８１９、ＤＡＲＯＣＵＲ－ＴＰＯ（以上、ＢＡＳＦ社製）などが挙げられる。 Examples of commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF). Commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF). Examples of commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (above, manufactured by BASF).
　オキシム化合物としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）に記載の化合物、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）に記載の化合物、特開２０００－０６６３８５号公報に記載の化合物、特表２００４－５３４７９７号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、特開２０１７－０１９７６６号公報に記載の化合物、特許第６０６５５９６号公報に記載の化合物、国際公開ＷＯ２０１５／１５２１５３号公報に記載の化合物、国際公開ＷＯ２０１７／０５１６８０号公報に記載の化合物、特開２０１７－１９８８６５号公報に記載の化合物、国際公開ＷＯ２０１７／１６４１２７号公報の段落番号００２５～００３８に記載の化合物などが挙げられる。オキシム化合物の具体例としては、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。市販品としては、ＩＲＧＡＣＵＲＥ－ＯＸＥ０１、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３、ＩＲＧＡＣＵＲＥ－ＯＸＥ０４（以上、ＢＡＳＦ社製）、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－１４０５２号公報に記載の光重合開始剤２）が挙げられる。また、オキシム化合物としては、着色性が無い化合物や、透明性が高く変色し難い化合物を用いることも好ましい。市販品としては、アデカアークルズＮＣＩ－７３０、ＮＣＩ－８３１、ＮＣＩ－９３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。 Examples of the oxime compound include the compounds described in JP 2001-233842 A, the compounds described in JP 2000-080068 A, the compounds described in JP 2006-342166 A, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compound described in J. C. S. Compounds described in Perkin II (1979, pp.156-162), Compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in Japanese Patent Laid-Open No. 2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-0197766, compounds described in Patent No. 6065596, International Publication WO2015 / 152153, the compound described in WO 2017/051680, the compound described in JP-A-2017-198865, the paragraph number 0025 of WO 2017/164127. 0038 include compounds described in. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-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 Examples thereof include imino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tengden Electronic New Materials Co., Ltd.), and ADEKA OPTOMER N-1919. (Photopolymerization initiator 2 described in JP 2012-14052 A manufactured by ADEKA Corporation) can be used. As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and being resistant to discoloration. Examples of commercially available products include ADEKA ARKUL'S NCI-730, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation).
　本発明において、光重合開始剤として、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物が挙げられる。この内容は本明細書に組み込まれる。 In the present invention, an oxime compound having a fluorene ring can be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466. This content is incorporated herein.
　本発明において、光重合開始剤として、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられる。この内容は本明細書に組み込まれる。 In the present invention, an oxime compound having a fluorine atom can be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom are described in JP 2010-262028 A, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP 2013-164471 A. Compound (C-3) and the like. This content is incorporated herein.
　本発明において、光重合開始剤として、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落番号００３１～００４７、特開２０１４－１３７４６６号公報の段落番号０００８～００１２、００７０～００７９に記載されている化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載されている化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）が挙げられる。 In the present invention, an oxime compound having a nitro group can be used as the photopolymerization initiator. 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 JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, The compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071 are ADEKA ARCRUZ NCI-831 (manufactured by ADEKA Corporation).
　本発明において、光重合開始剤として、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開ＷＯ２０１５／０３６９１０号公報に記載されるＯＥ－０１～ＯＥ－７５が挙げられる。 In the present invention, an oxime compound having a benzofuran skeleton can be used as the photopolymerization initiator. Specific examples thereof include OE-01 to OE-75 described in International Publication WO2015 / 036910.
　本発明において好ましく使用されるオキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　オキシム化合物は、波長３５０～５００ｎｍの範囲に極大吸収波長を有する化合物が好ましく、波長３６０～４８０ｎｍの範囲に極大吸収波長を有する化合物がより好ましい。また、オキシム化合物の波長３６５ｎｍ又は波長４０５ｎｍにおけるモル吸光係数は、感度の観点から、高いことが好ましく、１,０００～３００，０００であることがより好ましく、２,０００～３００，０００であることが更に好ましく、５,０００～２００，０００であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1,000 to 300,000, and more preferably 2,000 to 300,000. Is more preferable, and 5,000 to 200,000 is particularly preferable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
　光重合開始剤として、２官能あるいは３官能以上の光ラジカル重合開始剤を用いてもよい。そのような光ラジカル重合開始剤を用いることにより、光ラジカル重合開始剤の１分子から２つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して有機溶剤などへの溶解性が向上して、経時で析出しにくくなり、着色組成物の経時安定性を向上させることができる。２官能あるいは３官能以上の光ラジカル重合開始剤の具体例としては、特表２０１０－５２７３３９号公報、特表２０１１－５２４４３６号公報、国際公開ＷＯ２０１５／００４５６５号公報、特表２０１６－５３２６７５号公報の段落番号０４０７～０４１２、国際公開ＷＯ２０１７／０３３６８０号公報の段落番号００３９～００５５に記載されているオキシム化合物の２量体、特表２０１３－５２２４４５号公報に記載されている化合物（Ｅ）および化合物（Ｇ）、国際公開ＷＯ２０１６／０３４９６３号公報に記載されているＣｍｐｄ１～７、特表２０１７－５２３４６５号公報の段落番号０００７に記載されているオキシムエステル類光開始剤、特開２０１７－１６７３９９号公報の段落番号００２０～００３３に記載されている光開始剤、特開２０１７－１５１３４２号公報の段落番号００１７～００２６に記載されている光重合開始剤（Ａ）などが挙げられる。 As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photo-radical polymerization initiator, two or more radicals are generated from one molecule of the photo-radical polymerization initiator, so that good sensitivity can be obtained. Further, in the case of using a compound having an asymmetric structure, the crystallinity is lowered and the solubility in an organic solvent or the like is improved, it is difficult to deposit over time, and the stability over time of the coloring composition can be improved. it can. Specific examples of the bifunctional or trifunctional or more functional photoradical polymerization initiators include those disclosed in JP 2010-527339 A, JP 2011-524436 A, International Publication WO 2015/004565 and JP 2016-532675. Paragraph Nos. 0407 to 0412 and dimers of oxime compounds described in International Publication WO2017 / 033680, Paragraph Nos. 0039 to 0055, compounds (E) and compounds (described in JP-A No. 2013-522445) G), Cmpd1 to 7 described in International Publication WO2016 / 034963, and oxime ester photoinitiator described in Paragraph No. 0007 of JP-A-2017-523465, JP-A-2017-167399. Described in paragraph numbers 0020 to 0033 Initiator, a photopolymerization initiator and (A) are exemplified as described in paragraph Nos. 0017 to 0026 of JP-A-2017-151342.
　着色組成物の全固形分中の光重合開始剤の含有量は０．１～３０質量％が好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がより好ましい。上限は、２０質量％以下が好ましく、１５質量％以下がより好ましい。本発明の着色組成物において、光重合開始剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. In the colored composition of the present invention, the photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used, the total amount thereof is preferably within the above range.
＜＜顔料誘導体＞＞
　本発明の着色組成物は、顔料誘導体を含有することができる。この態様によれば、着色組成物の保存安定性をより向上させることができる。顔料誘導体としては、顔料の一部を、酸基、塩基性基、塩構造を有する基又はフタルイミドメチル基で置換した構造を有する化合物が挙げられる。顔料誘導体としては、式（Ｂ１）で表される化合物が好ましい。 << Pigment derivative >>
The coloring composition of the present invention may contain a pigment derivative. According to this aspect, the storage stability of the colored composition can be further improved. Examples of the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acid group, a basic group, a group having a salt structure or a phthalimidomethyl group. As the pigment derivative, a compound represented by the formula (B1) is preferable.
Figure JPOXMLDOC01-appb-C000007
 　式（Ｂ１）中、Ｐは色素構造を表し、Ｌは単結合または連結基を表し、Ｘは酸基、塩基性基、塩構造を有する基またはフタルイミドメチル基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｍが２以上の場合は複数のＬおよびＸは互いに異なっていてもよく、ｎが２以上の場合は複数のＸは互いに異なっていてもよい。
Figure JPOXMLDOC01-appb-C000007
 In formula (B1), P represents a dye structure, L represents a single bond or a linking group, X represents an acid group, a basic group, a group having a salt structure or a phthalimidomethyl group, and m is an integer of 1 or more. And n represents an integer of 1 or more, and when m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of X may be different from each other.
　Ｐが表す色素構造としては、ピロロピロール色素構造、ジケトピロロピロール色素構造、キナクリドン色素構造、アントラキノン色素構造、ジアントラキノン色素構造、ベンゾイソインドール色素構造、チアジンインジゴ色素構造、アゾ色素構造、キノフタロン色素構造、フタロシアニン色素構造、ナフタロシアニン色素構造、ジオキサジン色素構造、ペリレン色素構造、ペリノン色素構造、ベンゾイミダゾロン色素構造、ベンゾチアゾール色素構造、ベンゾイミダゾール色素構造およびベンゾオキサゾール色素構造などが挙げられる。 The dye structure represented by P is a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a quinacridone dye structure, an anthraquinone dye structure, a dianthraquinone dye structure, a benzoisoindole dye structure, a thiazineindigo dye structure, an azo dye structure, a quinophthalone. Examples thereof include a dye structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, a dioxazine dye structure, a perylene dye structure, a perinone dye structure, a benzimidazolone dye structure, a benzothiazole dye structure, a benzimidazole dye structure and a benzoxazole dye structure.
　Ｌが表す連結基としては、炭化水素基、複素環基、－ＮＲ－、－ＳＯ2－、－Ｓ－、－Ｏ－、－ＣＯ－もしくはこれらの組み合わせからなる基が挙げられる。Ｒは水素原子、アルキル基またはアリール基を表す。 Examples of the linking group represented by L include a hydrocarbon group, a heterocyclic group, —NR—, —SO 2 —, —S—, —O—, —CO—, or a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group.
　Ｘが表す酸基としては、カルボキシル基、スルホ基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基等が挙げられる。カルボン酸アミド基としては、－ＮＨＣＯＲＸ１で表される基が好ましい。スルホン酸アミド基としては、－ＮＨＳＯ２ＲＸ２で表される基が好ましい。イミド酸基としては、－ＳＯ２ＮＨＳＯ２ＲＸ３、－ＣＯＮＨＳＯ２ＲＸ４、－ＣＯＮＨＣＯＲＸ５または－ＳＯ２ＮＨＣＯＲＸ６で表される基が好ましい。ＲＸ１～ＲＸ６は、それぞれ独立に、炭化水素基または複素環基を表す。ＲＸ１～ＲＸ６が表す炭化水素基および複素環基は、さらに置換基を有してもよい。さらなる置換基としては、ハロゲン原子であることが好ましく、フッ素原子であることがより好ましい。Ｘが表す塩基性基としてはアミノ基が挙げられる。Ｘが表す塩構造としては、上述した酸基または塩基性基の塩が挙げられる。 Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imide acid group. The carboxamide group is preferably a group represented by —NHCOR X1 . The sulfonic acid amide group is preferably a group represented by —NHSO 2 R X2 . The imido acid group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 . R X1 to R X6 each independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon group and heterocyclic group represented by R X1 to R X6 may further have a substituent. The further substituent is preferably a halogen atom, and more preferably a fluorine atom. Examples of the basic group represented by X include an amino group. Examples of the salt structure represented by X include salts of the above-mentioned acid group or basic group.
　顔料誘導体としては、下記構造の化合物が挙げられる。また、特開昭５６－１１８４６２号公報、特開昭６３－２６４６７４号公報、特開平０１－２１７０７７号公報、特開平０３－００９９６１号公報、特開平０３－０２６７６７号公報、特開平０３－１５３７８０号公報、特開平０３－０４５６６２号公報、特開平０４－２８５６６９号公報、特開平０６－１４５５４６号公報、特開平０６－２１２０８８号公報、特開平０６－２４０１５８号公報、特開平１０－３００６３号公報、特開平１０－１９５３２６号公報、国際公開ＷＯ２０１１／０２４８９６号公報の段落番号００８６～００９８、国際公開ＷＯ２０１２／１０２３９９号公報の段落番号００６３～００９４、国際公開ＷＯ２０１７／０３８２５２号公報の段落番号００８２等に記載の化合物を用いることもでき、これらの内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000008
 Examples of the pigment derivative include compounds having the following structures. Further, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767 and JP-A-03-153780. Japanese Patent Laid-Open No. 03-045662, Japanese Patent Laid-Open No. 04-285669, Japanese Patent Laid-Open No. 06-145546, Japanese Patent Laid-Open No. 06-212088, Japanese Patent Laid-Open No. 06-240158, Japanese Patent Laid-Open No. 10-30063, JP 10-195326 A, paragraphs 0086 to 0098 in WO 2011/024896, paragraphs 0063 to 0094 in WO 2012/102399, paragraph 0082 in WO 2017/038252, etc. It is also possible to use compounds of Which is incorporated herein.
Figure JPOXMLDOC01-appb-C000008
　顔料誘導体の含有量は顔料１００質量部に対して１～３０質量部であることが好ましい。下限は２質量部以上であることが好ましく、３質量部以上であることがより好ましい。上限は、２５質量部以下であることが好ましく、２０質量部以下であることがより好ましく、１５質量％以下であることが更に好ましい。顔料誘導体は、１種のみを用いてもよいし、２種以上を併用してもよい。２種以上併用する場合はそれらの合計量が上記範囲であることが好ましい。 The content of the pigment derivative is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15% by mass or less. As the pigment derivative, only one kind may be used, or two or more kinds may be used in combination. When two or more kinds are used in combination, the total amount thereof is preferably within the above range.
＜＜環状エーテル基を有する化合物＞＞
　本発明の着色組成物は、環状エーテル基を有する化合物を含有することができる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられる。環状エーテル基を有する化合物は、エポキシ基を有する化合物であることが好ましい。エポキシ基を有する化合物としては、１分子内にエポキシ基を１個以上有する化合物が挙げられ、エポキシ基を２個以上有する化合物が好ましい。エポキシ基の数の上限は、例えば、１００個以下とすることもでき、１０個以下とすることもでき、５個以下とすることもできる。エポキシ基を有する化合物としては、特開２０１３－０１１８６９号公報の段落番号００３４～００３６、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物、特開２０１７－１７９１７２号公報に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。 << Compound Having Cyclic Ether Group >>
The colored composition of the present invention may contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The compound having a cyclic ether group is preferably a compound having an epoxy group. Examples of the compound having an epoxy group include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferable. The upper limit of the number of epoxy groups may be, for example, 100 or less, 10 or less, or 5 or less. Compounds having an epoxy group are described in JP-A-2013-011869, paragraphs 0034 to 0036, JP-A-04043556, paragraphs 0147 to 0156, and JP-A-2014-0889408, paragraphs 0085 to 0092. The compounds described and the compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein.
　エポキシ基を有する化合物は、低分子化合物（例えば、分子量２０００未満、さらには、分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）のいずれでもよい。エポキシ基を有する化合物の重量平均分子量は、２００～１０００００が好ましく、５００～５００００がより好ましい。重量平均分子量の上限は、１００００以下が好ましく、５０００以下がより好ましく、３０００以下が更に好ましい。 The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, further less than 1000), or a macromolecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, still more preferably 3000 or less.
　エポキシ基を有する化合物としては、エポキシ樹脂を好ましく用いることができる。エポキシ樹脂としては、例えばフェノール化合物のグリシジルエーテル化物であるエポキシ樹脂、各種ノボラック樹脂のグリシジルエーテル化物であるエポキシ樹脂、脂環式エポキシ樹脂、脂肪族系エポキシ樹脂、複素環式エポキシ樹脂、グリシジルエステル系エポキシ樹脂、グリシジルアミン系エポキシ樹脂、ハロゲン化フェノール類をグリシジル化したエポキシ樹脂、エポキシ基をもつケイ素化合物とそれ以外のケイ素化合物との縮合物、エポキシ基を持つ重合性不飽和化合物とそれ以外の他の重合性不飽和化合物との共重合体等が挙げられる。エポキシ樹脂のエポキシ当量は、３１０～３３００ｇ／ｅｑであることが好ましく、３１０～１７００ｇ／ｅｑであることがより好ましく、３１０～１０００ｇ／ｅｑであることが更に好ましい。 An epoxy resin can be preferably used as the compound having an epoxy group. Examples of the epoxy resin include an epoxy resin which is a glycidyl ether compound of a phenol compound, an epoxy resin which is a glycidyl ether compound of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester system. Epoxy resin, glycidyl amine epoxy resin, epoxy resin obtained by glycidylating halogenated phenols, condensate of silicon compound having epoxy group and other silicon compound, polymerizable unsaturated compound having epoxy group and other Examples thereof include copolymers with other polymerizable unsaturated compounds. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and further preferably 310 to 1000 g / eq.
　環状エーテル基を有する化合物の市販品としては、例えば、ＥＨＰＥ３１５０（（株）ダイセル製）、ＥＰＩＣＬＯＮ　Ｎ－６９５（ＤＩＣ（株）製）、マープルーフＧ－０１５０Ｍ、Ｇ－０１０５ＳＡ、Ｇ－０１３０ＳＰ、Ｇ－０２５０ＳＰ、Ｇ－１００５Ｓ、Ｇ－１００５ＳＡ、Ｇ－１０１０Ｓ、Ｇ－２０５０Ｍ、Ｇ－０１１００、Ｇ－０１７５８（以上、日油（株）製、エポキシ基含有ポリマー）等が挙げられる。 Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (these are NOF Corporation's epoxy group-containing polymer).
　本発明の着色組成物が環状エーテル基を有する化合物を含有する場合、着色組成物の全固形分中における環状エーテル基を有する化合物の含有量は、０．１～２０質量％が好ましい。下限は、例えば０．５質量％以上が好ましく、１質量％以上がより好ましい。上限は、例えば、１５質量％以下が好ましく、１０質量％以下が更に好ましい。環状エーテル基を有する化合物は１種のみでもよく、２種以上でもよい。２種以上の場合は、それらの合計量が上記範囲となることが好ましい。 When the coloring composition of the present invention contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group in the total solid content of the coloring composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less. The compound having a cyclic ether group may be only one kind or two or more kinds. When two or more kinds are used, the total amount thereof is preferably within the above range.
＜＜シランカップリング剤＞＞
　本発明の着色組成物はシランカップリング剤を含有することができる。この態様によれば、得られる膜の支持体との密着性を向上させることができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、（メタ）アリル基、（メタ）アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、アミノ基、（メタ）アクリロイル基およびエポキシ基が好ましい。シランカップリング剤の具体例としては、特開２００９－２８８７０３号公報の段落番号００１８～００３６に記載の化合物、特開２００９－２４２６０４号公報の段落番号００５６～００６６に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。 << silane coupling agent >>
The coloring composition of the present invention may contain a silane coupling agent. According to this aspect, the adhesion of the obtained film to the support can be improved. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that. Further, the hydrolyzable group means a substituent which is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth) allyl group, (meth) acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, and isocyanate group. , A phenyl group and the like, and an amino group, a (meth) acryloyl group and an epoxy group are preferable. Specific examples of the silane coupling agent include the compounds described in JP-A 2009-288703, paragraphs 0018 to 0036, and the compounds described in JP-A 2009-242604, paragraphs 0056 to 0066. Are incorporated herein by reference.
　着色組成物の全固形分中におけるシランカップリング剤の含有量は、０．１～５質量％が好ましい。上限は、３質量％以下が好ましく、２質量％以下がより好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がより好ましい。シランカップリング剤は、１種のみでもよく、２種以上でもよい。２種以上の場合は、合計量が上記範囲となることが好ましい。 The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be only one kind or two or more kinds. When two or more kinds are used, the total amount is preferably within the above range.
＜＜重合禁止剤＞＞
　本発明の着色組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔｅｒｔ－ブチルカテコール、ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン塩（アンモニウム塩、第一セリウム塩等）が挙げられる。中でも、ｐ－メトキシフェノールが好ましい。着色組成物の全固形分中における重合禁止剤の含有量は、０．０００１～５質量％が好ましい。 << polymerization inhibitor >>
The coloring composition of the present invention may contain a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, cerous salt, etc.) can be mentioned. Of these, p-methoxyphenol is preferable. The content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass.
＜＜界面活性剤＞＞
　本発明の着色組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤については、国際公開ＷＯ２０１５／１６６７７９号公報の段落番号０２３８～０２４５を参酌でき、この内容は本明細書に組み込まれる。 << Surfactant >>
The coloring composition of the present invention may contain a surfactant. As the 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. Regarding the surfactant, paragraph numbers 0238 to 0245 of International Publication WO 2015/166779 can be referred to, and the contents thereof are incorporated in the present specification.
　本発明において、界面活性剤はフッ素系界面活性剤であることが好ましい。着色組成物にフッ素系界面活性剤を含有させることで液特性（特に、流動性）がより向上し、省液性をより改善することができる。また、厚みムラの小さい膜を形成することもできる。 In the present invention, the surfactant is preferably a fluorinated surfactant. By including a fluorine-based surfactant in the coloring composition, liquid characteristics (particularly fluidity) can be further improved, and liquid saving can be further improved. It is also possible to form a film having a small thickness unevenness.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、着色組成物中における溶解性も良好である。 The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 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 the coating film and liquid saving, and also has good solubility in the coloring composition.
　フッ素系界面活性剤としては、特開２０１４－４１３１８号公報の段落番号００６０～００６４（対応する国際公開第２０１４／０１７６６９号の段落番号００６０～００６４）等に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落番号０１１７～０１３２に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックＦ１７１、Ｆ１７２、Ｆ１７３、Ｆ１７６、Ｆ１７７、Ｆ１４１、Ｆ１４２、Ｆ１４３、Ｆ１４４、Ｒ３０、Ｆ４３７、Ｆ４７５、Ｆ４７９、Ｆ４８２、Ｆ５５４、Ｆ７８０、ＥＸＰ、ＭＦＳ－３３０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１、ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３、ＫＨ－４０（以上、旭硝子（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）等が挙げられる。 Examples of the fluorinated surfactant include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-41318 (corresponding paragraphs 0060 to 0064 of WO 2014/017669) and JP-A-2011-2011. Examples thereof include the surfactants described in paragraph Nos. 0117 to 0132 of Japanese Patent No. 132503, the contents of which are incorporated herein. Examples of commercially available fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS. -330 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, Examples include SC-1068, SC-381, SC-383, S-393, KH-40 (above Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above OMNOVA). .
　また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファックＤＳシリーズ（化学工業日報、２０１６年２月２２日）（日経産業新聞、２０１６年２月２３日）、例えばメガファックＤＳ－２１が挙げられる。 Fluorine-based surfactants also have an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved to volatilize the fluorine atom. It can be preferably used. Examples of such a fluorinated surfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafac DS. -21 is included.
　また、フッ素系界面活性剤は、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。このようなフッ素系界面活性剤は、特開２０１６－２１６６０２号公報の記載を参酌でき、この内容は本明細書に組み込まれる。 Further, as the fluorine-based surfactant, it is also preferable to use 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. Regarding such a fluorine-based surfactant, the description in JP-A-2016-216602 can be referred to, and the contents thereof are incorporated in the present specification.
　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。例えば特開２０１１－８９０９０号公報に記載された化合物が挙げられる。フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000009
 　上記の化合物の重量平均分子量は、好ましくは３０００～５００００であり、例えば、１４０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。 A block polymer can also be used as the fluorine-based surfactant. For example, the compounds described in JP 2011-89090 A may be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (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 fluorine-based surfactant used in the present invention.
Figure JPOXMLDOC01-appb-C000009
 The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of repeating units is mol%.
　また、フッ素系界面活性剤は、エチレン性不飽和結合基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落番号００５０～００９０および段落番号０２８９～０２９５に記載された化合物、例えばＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ等が挙げられる。フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落番号００１５～０１５８に記載の化合物を用いることもできる。 Also, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond group in its side chain can be used. As specific examples, the compounds described in JP-A-2010-164965, paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295, such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation. , RS-72-K and the like. As the fluorine-based surfactant, the compounds described in paragraph Nos. 0015 to 0158 of JP-A-2005-117327 can be used.
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（和光純薬工業（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerolpropoxylate, glycerolethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS Company), Sols Perth 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D -6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.
　シリコン系界面活性剤としては、例えば、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ、トーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング（株）製）、ＴＳＦ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＫＰ－３４１、ＫＦ－６００１、ＫＦ－６００２（以上、信越シリコーン株式会社製）、ＢＹＫ３０７、ＢＹＫ３２３、ＢＹＫ３３０（以上、ビックケミー社製）等が挙げられる。また、シリコン系界面活性剤は、下記構造の化合物を用いることもできる。
Figure JPOXMLDOC01-appb-C000010
 Examples of silicone-based surfactants 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 (above, Toray Dow Corning Co., Ltd. )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie) and the like. Further, as the silicon-based surfactant, a compound having the following structure can also be used.
Figure JPOXMLDOC01-appb-C000010
　着色組成物の全固形分中における界面活性剤の含有量は、０．００１質量％～５．０質量％が好ましく、０．００５～３．０質量％がより好ましい。界面活性剤は、１種のみでもよく、２種以上でもよい。２種以上の場合は、合計量が上記範囲となることが好ましい。 The content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. The surfactant may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.
＜＜紫外線吸収剤＞＞
　本発明の着色組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。これらの詳細については、特開２０１２－２０８３７４号公報の段落番号００５２～００７２、特開２０１３－０６８８１４号公報の段落番号０３１７～０３３４、特開２０１６－１６２９４６号公報の段落番号００６１～００８０の記載を参酌でき、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、例えば、ＵＶ－５０３（大東化学（株）製）などが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のＭＹＵＡシリーズ（化学工業日報、２０１６年２月１日）が挙げられる。また、紫外線吸収剤として特許第６２６８９６７号公報の段落番号００４９～００５９に記載の化合物も使用できる。 << UV absorber >>
The coloring composition of the present invention can contain an ultraviolet absorber. As the 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. For details of these, please refer to paragraphs 0052 to 0072 of JP2012-208374A, paragraphs 0317 to 0334 of JP2013-068814A, and paragraphs 0061 to 0080 of JP2016-162946A. Reference may be made to these contents, which are incorporated herein. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.). Examples of the benzotriazole compound include MYUA series manufactured by Miyoshi Oil & Fats (Chemical Industry Daily, February 1, 2016). Further, the compounds described in paragraph Nos. 0049 to 0059 of Japanese Patent No. 6268967 can also be used as the ultraviolet absorber.
　着色組成物の全固形分中における紫外線吸収剤の含有量は、０．０１～１０質量％が好ましく、０．０１～５質量％がより好ましい。本発明において、紫外線吸収剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。 The content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, the ultraviolet absorber may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.
＜＜酸化防止剤＞＞
　本発明の着色組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。前述の置換基としては炭素数１～２２の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、亜リン酸エチルビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ　ＡＯ－２０、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－３３０（以上、（株）ＡＤＥＫＡ）などが挙げられる。また、酸化防止剤は、特許第６２６８９６７号公報の段落番号００２３～００４８に記載の化合物も使用できる。 << Antioxidant >>
The coloring composition of the present invention may contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferable phenol compounds include hindered phenol compounds. A compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. Examples of phosphorus-based antioxidants include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphapin-2-yl ) Oxy] ethyl] amine, ethylbisphosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80G. , ADEKA STAB AO-330 (above, ADEKA Corporation) and the like. Further, as the antioxidant, compounds described in paragraph Nos. 0023 to 0048 of Japanese Patent No. 6268967 can also be used.
　着色組成物の全固形分中における酸化防止剤の含有量は、０．０１～２０質量％であることが好ましく、０．３～１５質量％であることがより好ましい。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。 The content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. As the antioxidant, only one kind may be used, or two or more kinds may be used. When two or more kinds are used, the total amount is preferably within the above range.
＜＜その他成分＞＞
　本発明の着色組成物は、必要に応じて、増感剤、硬化促進剤、フィラー、熱硬化促進剤、可塑剤及びその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など）を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号０１８３以降（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落番号０２３７）の記載、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、本発明の着色組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開ＷＯ２０１４／０２１０２３号公報、国際公開ＷＯ２０１７／０３０００５号公報、特開２０１７－００８２１９号公報に記載された化合物が挙げられる。市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。 << Other ingredients >>
The coloring composition of the present invention, if necessary, a sensitizer, a curing accelerator, a filler, a thermal curing accelerator, a plasticizer and other auxiliaries (for example, conductive particles, a filler, a defoaming agent, Flame retardant, leveling agent, peeling accelerator, perfume, surface tension adjusting agent, chain transfer agent, etc.) may be contained. Properties such as film physical properties can be adjusted by appropriately incorporating these components. These components are described, for example, in paragraph No. 0183 or later (corresponding U.S. Patent Application Publication No. 2013/0034812, paragraph No. 0237) of JP 2012-003225 A, or paragraphs of JP 2008-250074 A. References such as numbers 0101 to 0104 and 0107 to 0109 can be referred to, and the contents thereof are incorporated in this specification. Moreover, the coloring composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protecting group, and the compound is heated at 100 to 250 ° C or heated at 80 to 200 ° C in the presence of an acid / base catalyst. As a result, compounds in which the protecting group is eliminated to function as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publication WO2014 / 021023, International Publication WO2017 / 030005, and Japanese Patent Laid-Open No. 2017-008219. Examples of commercially available products include ADEKA ARCRUZ GPA-5001 (manufactured by ADEKA).
　また、本発明の着色組成物は、得られる膜の屈折率を調整するために金属酸化物を含有させてもよい。金属酸化物としては、ＴｉＯ２、ＺｒＯ２、Ａｌ２Ｏ３、ＳｉＯ２等が挙げられる。金属酸化物の一次粒子径は１～１００ｎｍが好ましく、３～７０ｎｍがより好ましく、５～５０ｎｍが最も好ましい。金属酸化物はコア－シェル構造を有していてもよく、この際、コア部が中空状であってもよい。 Further, the coloring composition of the present invention may contain a metal oxide in order to adjust the refractive index of the obtained film. Examples of the metal oxide include TiO 2 , ZrO 2 , Al 2 O 3 , and SiO 2 . The primary particle diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, most preferably 5 to 50 nm. The metal oxide may have a core-shell structure, in which case the core part may be hollow.
　また、本発明の着色組成物は、耐光性改良剤を含んでもよい。耐光性改良剤としては、特開２０１７－１９８７８７号公報の段落番号００３６～００３７に記載の化合物、特開２０１７－１４６３５０号公報の段落番号００２９～００３４に記載の化合物、特開２０１７－１２９７７４号公報の段落番号００３６～００３７、００４９～００５２に記載の化合物、特開２０１７－１２９６７４号公報の段落番号００３１～００３４、００５８～００５９に記載の化合物、特開２０１７－１２２８０３号公報の段落番号００３６～００３７、００５１～００５４に記載の化合物、国際公開ＷＯ２０１７／１６４１２７号公報の段落番号００２５～００３９に記載の化合物、特開２０１７－１８６５４６号公報の段落番号００３４～００４７に記載の化合物、特開２０１５－０２５１１６号公報の段落番号００１９～００４１に記載の化合物、特開２０１２－１４５６０４号公報の段落番号０１０１～０１２５に記載の化合物、特開２０１２－１０３４７５号公報の段落番号００１８～００２１に記載の化合物、特開２０１１－２５７５９１号公報の段落番号００１５～００１８に記載の化合物、特開２０１１－１９１４８３号公報の段落番号００１７～００２１に記載の化合物、特開２０１１－１４５６６８号公報の段落番号０１０８～０１１６に記載の化合物、特開２０１１－２５３１７４号公報の段落番号０１０３～０１５３に記載の化合物などが挙げられる。 Further, the coloring composition of the present invention may contain a light resistance improver. As the light resistance improver, compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, and JP-A-2017-129774 are disclosed. Paragraph Nos. 0036 to 0037 and 0049 to 0052, JP No. 2017-129674, Paragraph Nos. 0031 to 0034 and 0058 to 0059, JP No. 2017-122803, Paragraph Nos. 0036 to 0037 , 0051 to 0054, the compounds described in paragraphs 0025 to 0039 of International Publication WO2017 / 164127, the compounds described in paragraphs 0034 to 0047 of JP2017-186546, and JP2005-025116A. Paragraph number 0 of the publication 19 to 0041, compounds described in paragraphs 0101 to 0125 of JP2012-145604A, compounds described in paragraphs 0018 to 0021 of JP2012-103475A, JP2011-257591A. The compounds described in paragraphs 0015 to 0018 of the publication, the compounds described in paragraphs 0017 to 0021 of JP2011-191483A, the compounds described in paragraphs 0108 to 0116 of JP2011-145668, Examples thereof include the compounds described in paragraph Nos. 0103 to 0153 of 2011-253174.
　本発明の着色組成物は、顔料などと結合または配位していない遊離の金属の含有量が１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましく、１０ｐｐｍ以下であることが更に好ましく、実質的に含有しないことが特に好ましい。この態様によれば、顔料分散性の安定化（凝集抑止）、分散性改善に伴う分光特性の向上、硬化性成分の安定化や、金属原子・金属イオンの溶出に伴う導電性変動の抑止、表示特性の向上などができる。また、特開２０１２－１５３７９６号公報、特開２０００－３４５０８５号公報、特開２００５－２００５６０号公報、特開平０８－０４３６２０号公報、特開２００４－１４５０７８号公報、特開２０１４－１１９４８７号公報、特開２０１０－０８３９９７号公報、特開２０１７－０９０９３０号公報、特開２０１８－０２５６１２号公報、特開２０１８－０２５７９７号公報、特開２０１７－１５５２２８号公報、特開２０１８－０３６５２１号公報などに記載された効果も得られる。上記の遊離の金属の種類としては、Ｎａ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｍｎ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｒ、Ｃｏ、Ｍｇ、Ａｌ、Ｓｎ、Ｚｒ、Ｇａ、Ｇｅ、Ａｇ、Ａｕ、Ｐｔ、Ｃｓ、Ｎi、Ｃｄ、Ｐｂ，Ｂｉ等が挙げられる。また、本発明の着色組成物は、顔料などと結合または配位していない遊離のハロゲンの含有量が１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましく、１０ｐｐｍ以下であることが更に好ましく、実質的に含有しないことが特に好ましい。ハロゲンとしては、Ｆ、Ｃｌ、Ｂｒ、Ｉ及びそれらの陰イオンが挙げられる。着色組成物中の遊離の金属やハロゲンの低減方法としては、イオン交換水による洗浄、ろ過、限外ろ過、イオン交換樹脂による精製等の方法が挙げられる。 In the coloring composition of the present invention, the content of the free metal that is not bound or coordinated with the pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 10 ppm or less. In particular, it is particularly preferable not to contain substantially. According to this aspect, stabilization of pigment dispersibility (inhibition of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable component, and suppression of conductivity fluctuation due to elution of metal atom / metal ion, The display characteristics can be improved. Further, JP 2012-153796A, JP 2000-345085A, JP 2005-200560A, JP 08-043620A, JP 2004-145078A, JP 2014-119487A, and Described in JP2010-083997A, JP2017-090930A, JP2018-025612A, JP2018-025797A, JP2017-155228A, JP2018-036521A, and the like. The effect is also obtained. The types of the above-mentioned free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Ni, Cd, Pb, Bi etc. are mentioned. In addition, the coloring composition of the present invention preferably has a content of free halogen that is not bound or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, and further preferably 10 ppm or less. It is more preferable, and it is particularly preferable not to contain substantially. Halogen includes F, Cl, Br, I and their anions. Examples of methods for reducing free metals and halogens in the coloring composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
　本発明の着色組成物は、テレフタル酸エステルを含まないことも好ましい。 It is also preferable that the coloring composition of the present invention does not contain a terephthalic acid ester.
　本発明の着色組成物の粘度（２５℃）は、例えば、塗布により膜を形成する場合、１～１００ｍＰａ・ｓであることが好ましい。下限は、２ｍＰａ・ｓ以上がより好ましく、３ｍＰａ・ｓ以上が更に好ましい。上限は、５０ｍＰａ・ｓ以下がより好ましく、３０ｍＰａ・ｓ以下が更に好ましく、１５ｍＰａ・ｓ以下が特に好ましい。 The viscosity (25 ° C.) of the colored composition of the present invention is preferably 1 to 100 mPa · s when forming a film by coating, for example. The lower limit is more preferably 2 mPa · s or more, further preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, further preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.
＜収容容器＞
　本発明の着色組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や着色組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成する多層ボトルや６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 <Container>
The container for the colored composition of the present invention is not particularly limited, and a known container can be used. In addition, as a container, for the purpose of suppressing the mixing of impurities into the raw materials and the coloring composition, a multi-layer bottle in which the inner wall of the container is made of resin of 6 types and 6 layers, or a bottle having a structure of 7 types of 6 types of resin It is also preferred to use As such a container, for example, the container described in JP-A-2015-123351 can be mentioned.
＜着色組成物の製造方法＞
　本発明の着色組成物は、前述の成分を混合して製造できる。着色組成物の製造に際しては、全成分を同時に有機溶剤に溶解および／または分散して着色組成物を製造してもよいし、必要に応じて、各成分を適宜２つ以上の溶液または分散液としておいて、使用時（塗布時）にこれらを混合して着色組成物を製造してもよい。 <Method for producing colored composition>
The coloring composition of the present invention can be produced by mixing the above-mentioned components. In the production of the coloring composition, all components may be dissolved and / or dispersed in an organic solvent at the same time to produce the coloring composition. If necessary, each component may be appropriately used in two or more solutions or dispersions. As described above, these may be mixed at the time of use (at the time of application) to produce a coloring composition.
　また、着色組成物の製造に際して、顔料を分散させるプロセスを含むことが好ましい。顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル（ビーズミル）における顔料の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、顔料を分散させるプロセスおよび分散機は、「分散技術大全、株式会社情報機構発行、２００５年７月１５日」や「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」、特開２０１５－１５７８９３号公報の段落番号００２２に記載のプロセス及び分散機を好適に使用出来る。また顔料を分散させるプロセスにおいては、ソルトミリング工程にて粒子の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開２０１５－１９４５２１号公報、特開２０１２－０４６６２９号公報の記載を参酌できる。 Also, it is preferable to include a process of dispersing the pigment in the production of the coloring composition. In the process of dispersing the pigment, the mechanical force used to disperse the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use the beads having a small diameter, and to increase the filling rate of the beads to perform the treatment under the condition that the pulverization efficiency is increased. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and disperser for dispersing the pigments are described in "Dispersion Technology Taizen, Information Technology Co., Ltd., July 15, 2005" and "Dispersion technology centering on suspension (solid / liquid dispersion system) and industrial application. In fact, the process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive reference materials, published by the Management Development Center Publishing Department, October 10, 1978" can be suitably used. Further, in the process of dispersing the pigment, the particles may be refined in the salt milling step. The materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629.
　着色組成物の製造にあたり、異物の除去や欠陥の低減などの目的で、着色組成物をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量のポリオレフィン樹脂を含む）等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。 In manufacturing the colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign matters and reducing defects. The filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration and the like. For example, fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight). A filter using a material such as a polyolefin resin is included. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
　フィルタの孔径は、０．０１～７．０μｍが好ましく、０．０１～３．０μｍがより好ましく、０．０５～０．５μｍが更に好ましい。フィルタの孔径が上記範囲であれば、微細な異物をより確実に除去できる。フィルタの孔径値については、フィルタメーカーの公称値を参照することができる。フィルタは、日本ポール株式会社（ＤＦＡ４２０１ＮＩＥＹなど）、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）および株式会社キッツマイクロフィルタ等が提供する各種フィルタを用いることができる。 The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, still more preferably 0.05 to 0.5 μm. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. Regarding the pore size value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.
　また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）が挙げられる。 Also, it is preferable to use a fibrous filter medium as the filter. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Examples of commercially available products include SBP type series (SBP008 etc.), TPR type series (TPR002, TPR005 etc.) and SHPX type series (SHPX003 etc.) manufactured by Loki Techno.
　フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第１のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第２のフィルタでろ過を行ってもよい。 When using filters, different filters (eg, first filter and second filter) may be combined. At that time, the filtration by each filter may be performed only once or may be performed twice or more. Further, filters having different hole diameters may be combined within the above-described range. Further, 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.
＜膜＞
　本発明の膜は、上述した本発明の着色組成物から得られる膜である。本発明の膜は、カラーフィルタなどに用いることができる。具体的には、カラーフィルタの着色層（画素）として好ましく用いることができ、カラーフィルタの赤色着色層（赤色画素）としてより好ましく用いることができる。本発明の膜の膜厚は、目的に応じて適宜調整できる。例えば、膜厚は、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上がさらに好ましい。 <Membrane>
The film of the present invention is a film obtained from the coloring composition of the present invention described above. The film of the present invention can be used for a color filter or the like. Specifically, it can be preferably used as a colored layer (pixel) of a color filter, and more preferably used as a red colored layer (red pixel) of a color filter. The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.
＜カラーフィルタ＞
　次に、本発明のカラーフィルタについて説明する。本発明のカラーフィルタは、上述した本発明の膜を有する。より好ましくは、カラーフィルタの画素として、本発明の膜を有する。本発明のカラーフィルタは、ＣＣＤ（電荷結合素子）やＣＭＯＳ（相補型金属酸化膜半導体）などの固体撮像素子や画像表示装置などに用いることができる。 <Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention has the above-mentioned film of the present invention. More preferably, the pixel of the color filter has the film of the present invention. The color filter of the present invention can be used for a solid-state imaging device such as CCD (charge coupled device) or CMOS (complementary metal oxide semiconductor), an image display device, or the like.
　本発明のカラーフィルタにおいて本発明の膜の膜厚は、目的に応じて適宜調整できる。膜厚は、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上が更に好ましい。 In the color filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.
　本発明のカラーフィルタは、画素の幅が０．５～２０．０μｍであることが好ましい。下限は、１．０μｍ以上であることが好ましく、２．０μｍ以上であることがより好ましい。上限は、１５．０μｍ以下であることが好ましく、１０．０μｍ以下であることがより好ましい。また、画素のヤング率が０．５～２０ＧＰａであることが好ましく、２．５～１５ＧＰａがより好ましい。 The pixel width of the color filter of the present invention is preferably 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, more preferably 10.0 μm or less. The Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
　本発明のカラーフィルタに含まれる各画素は高い平坦性を有することが好ましい。具体的には、画素の表面粗さＲａは、１００ｎｍ以下であることが好ましく、４０ｎｍ以下であることがより好ましく、１５ｎｍ以下であることが更に好ましい。下限は規定されないが、例えば０．１ｎｍ以上であることが好ましい。画素の表面粗さは、例えばＶｅｅｃｏ社製のＡＦＭ（原子間力顕微鏡）　Ｄｉｍｅｎｓｉｏｎ３１００を用いて測定することができる。また、画素上の水の接触角は適宜好ましい値に設定することができるが、典型的には、５０～１１０°の範囲である。接触角は、例えば接触角計ＣＶ－ＤＴ・Ａ型（協和界面科学（株）製）を用いて測定できる。また、画素の体積抵抗値は高いことが好ましい。具体的には、画素の体積抵抗値は１０９Ω・ｃｍ以上であることが好ましく、１０１１Ω・ｃｍ以上であることがより好ましい。上限は規定されないが、例えば１０１４Ω・ｃｍ以下であることが好ましい。画素の体積抵抗値は、例えば超高抵抗計５４１０（アドバンテスト社製）を用いて測定することができる。 Each pixel included in the color filter of the present invention preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using, for example, AFM (atomic force microscope) Dimension 3100 manufactured by Veeco. The contact angle of water on the pixel can be set to a suitable value as appropriate, but is typically in the range of 50 to 110 °. The contact angle can be measured using, for example, a contact angle meter CV-DT • A type (manufactured by Kyowa Interface Science Co., Ltd.). Further, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 9 Ω · cm or more, and more preferably 10 11 Ω · cm or more. The upper limit is not specified, but it is preferably 10 14 Ω · cm or less, for example. The volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest).
　また、本発明のカラーフィルタは、本発明の膜の表面に保護層を設けてもよい。保護層を設けることで、酸素遮断化、低反射化、親疎水化、特定波長の光（紫外線、近赤外線等）の遮蔽等の種々の機能を付与することができる。保護層の厚さとしては、０．０１～１０μｍが好ましく、０．１～５μｍがさらに好ましい。保護層の形成方法としては、有機溶剤に溶解した樹脂組成物を塗布して形成する方法、化学気相蒸着法、成型した樹脂を接着材で貼りつける方法等が挙げられる。保護層を構成する成分としては、（メタ）アクリル樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、ポリオール樹脂、ポリ塩化ビニリデン樹脂、メラミン樹脂、ウレタン樹脂、アラミド樹脂、ポリアミド樹脂、アルキド樹脂、エポキシ樹脂、変性シリコーン樹脂、フッ素樹脂、ポリカーボネート樹脂、ポリアクリロニトリル樹脂、セルロース樹脂、Ｓｉ、Ｃ、Ｗ、Ａｌ２Ｏ３、Ｍｏ、ＳｉＯ２、Ｓｉ２Ｎ４などが挙げられ、これらの成分を二種以上含有しても良い。例えば、酸素遮断化を目的とした保護層の場合、保護層はポリオール樹脂、ＳｉＯ２、Ｓｉ２Ｎ４を含むことが好ましい。また、低反射化を目的とした保護層の場合、保護層は（メタ）アクリル樹脂、フッ素樹脂を含むことが好ましい。 In addition, the color filter of the present invention may be provided with a protective layer on the surface of the film of the present invention. By providing the protective layer, various functions such as oxygen blocking, low reflection, hydrophilicity / hydrophobicity, and blocking of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of the method of forming the protective layer include a method of applying a resin composition dissolved in an organic solvent to form the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. As a component constituting the protective layer, (meth) acrylic resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide Resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al 2 O 3, Mo, etc. SiO 2, Si 2 N 4, and the like, two kinds of these components It may contain above. For example, in the case of a protective layer for the purpose of blocking oxygen, it is preferable that the protective layer contains a polyol resin, SiO 2 , and Si 2 N 4 . Further, in the case of the protective layer aiming at low reflection, the protective layer preferably contains a (meth) acrylic resin or a fluororesin.
　樹脂組成物を塗布して保護層を形成する場合、樹脂組成物の塗布方法としては、スピンコート法、キャスト法、スクリーン印刷法、インクジェット法等の公知の方法を用いることができる。樹脂組成物に含まれる有機溶剤は、公知の有機溶剤（例えば、プロピレングリコール１－モノメチルエーテル２－アセテート、シクロペンタノン、乳酸エチル等）を用いることが出来る。保護層を化学気相蒸着法にて形成する場合、化学気相蒸着法としては、公知の化学気相蒸着法（熱化学気相蒸着法、プラズマ化学気相蒸着法、光化学気相蒸着法）を用いることができる。 When the resin composition is applied to form the protective layer, known methods such as a spin coating method, a casting method, a screen printing method, and an inkjet method can be used as a method for applying the resin composition. As the organic solvent contained in the resin composition, a known organic solvent (eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by the chemical vapor deposition method, known chemical vapor deposition methods (thermochemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) are known as the chemical vapor deposition method. Can be used.
　保護層は、必要に応じて、有機・無機微粒子、特定波長（例えば、紫外線、近赤外線等）の吸収剤、屈折率調整剤、酸化防止剤、密着剤、界面活性剤等の添加剤を含有しても良い。有機・無機微粒子の例としては、例えば、高分子微粒子（例えば、シリコーン樹脂微粒子、ポリスチレン微粒子、メラミン樹脂微粒子）、酸化チタン、酸化亜鉛、酸化ジルコニウム、酸化インジウム、酸化アルミニウム、窒化チタン、酸窒化チタン、フッ化マグネシウム、中空シリカ、シリカ、炭酸カルシウム、硫酸バリウム等が挙げられる。特定波長の吸収剤は公知の吸収剤を用いることができる。紫外線吸収剤および近赤外線吸収剤としては、上述した素材が挙げられる。これらの添加剤の含有量は適宜調整できるが、保護層の全重量に対して０．１～７０質量％が好ましく、１～６０質量％がさらに好ましい。 The protective layer contains additives such as organic / inorganic fine particles, an absorber of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjusting agent, an antioxidant, an adhesive agent, a surfactant, etc., if necessary. You may. Examples of organic / inorganic particles include polymer particles (eg, silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , Magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate and the like. A known absorber can be used as the absorber having a specific wavelength. Examples of the ultraviolet absorber and the near infrared absorber include the materials described above. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total weight of the protective layer.
　また、保護層としては、特開２０１７－１５１１７６号公報の段落番号００７３～００９２に記載の保護層を用いることもできる。 As the protective layer, the protective layer described in paragraph Nos. 0073 to 0092 of JP-A-2017-151176 may be used.
　カラーフィルタは、隔壁で区画された領域に各色の画素（着色層）が埋め込まれた構造を有していてもよい。この場合の隔壁は各画素に対して低屈折率であることが好ましい。また、ＵＳ２０１８／００４０６５６号公報に記載の構成で隔壁を形成しても良い。 The color filter may have a structure in which each color pixel (coloring layer) is embedded in a region partitioned by a partition wall. In this case, the partition wall preferably has a low refractive index for each pixel. Further, the partition wall may be formed with the configuration described in US2018 / 0040656.
＜カラーフィルタの製造方法＞
　次に、本発明のカラーフィルタの製造方法について説明する。本発明のカラーフィルタは、上述した本発明の着色組成物を用いて支持体上に着色組成物層を形成する工程と、フォトリソグラフィ法により着色組成物層に対してパターンを形成する工程と、を経て製造できる。フォトリソグラフィ法によるパターン形成は、着色組成物層をパターン状に露光する工程と、着色組成物層の未露光部を現像除去してパターン（画素）を形成する工程と、を含むことが好ましい。必要に応じて、着色組成物層をベークする工程（プリベーク工程）、および、現像されたパターン（画素）をベークする工程（ポストベーク工程）を設けてもよい。以下、各工程について説明する。 <Method of manufacturing color filter>
Next, a method for manufacturing the color filter of the present invention will be described. The color filter of the present invention, a step of forming a coloring composition layer on a support using the coloring composition of the present invention described above, a step of forming a pattern for the coloring composition layer by photolithography, Can be manufactured through. The pattern formation by the photolithography method preferably includes a step of exposing the coloring composition layer in a pattern, and a step of developing and removing an unexposed portion of the coloring composition layer to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-bake step) and a step of baking the developed pattern (pixel) may be provided (post-bake step). Hereinafter, each step will be described.
　着色組成物層を形成する工程では、本発明の着色組成物を用いて、支持体上に着色組成物層を形成する。支持体としては、特に限定は無く、用途に応じて適宜選択できる。例えば、ガラス基板、シリコン基板などが挙げられ、シリコン基板であることが好ましい。また、シリコン基板には、電荷結合素子（ＣＣＤ）、相補型金属酸化膜半導体（ＣＭＯＳ）、透明導電膜などが形成されていてもよい。また、シリコン基板には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、シリコン基板には、上部の層との密着性改良、物質の拡散防止或いは基板表面の平坦化のために下塗り層が設けられていてもよい。 In the step of forming a coloring composition layer, the coloring composition layer of the present invention is used to form a coloring composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. For example, a glass substrate, a silicon substrate, etc. are mentioned, and a silicon substrate is preferable. Further, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film and the like may be formed on the silicon substrate. In addition, a black matrix that isolates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with an undercoat layer for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the substrate surface.
　着色組成物の塗布方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。また、着色組成物の塗布方法については、国際公開ＷＯ２０１７／０３０１７４号公報、国際公開ＷＯ２０１７／０１８４１９号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。 As a method for applying the coloring composition, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spraying method; a roll coating method; a spin coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395A). Methods described in the publication); inkjet (for example, on-demand method, piezo method, thermal method), ejection-type printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprint methods and the like. The method for applying the inkjet method is not particularly limited, and for example, the method described in “Expanding and Usable Inkjet-Infinite Possibilities Seen in Patents”, issued by Sumi Betechno Research, February 2005 (especially from page 115) (See page 133), Japanese Patent Application Laid-Open No. 2003-262716, Japanese Patent Application Laid-Open No. 2003-185831, Japanese Patent Application Laid-Open No. 2003-261827, Japanese Patent Application Laid-Open No. 2012-126830, Japanese Patent Application Laid-Open No. 2006-169325, and the like. Can be mentioned. Regarding the method for applying the coloring composition, the descriptions in International Publication WO2017 / 030174 and International Publication WO2017 / 018419 can be referred to, and the contents thereof are incorporated in the present specification.
　支持体上に形成した着色組成物層は、乾燥（プリベーク）してもよい。低温プロセスにより膜を製造する場合は、プリベークを行わなくてもよい。プリベークを行う場合、プリベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１１０℃以下が更に好ましい。下限は、例えば、５０℃以上とすることができ、８０℃以上とすることもできる。プリベーク時間は、１０～３００秒が好ましく、４０～２５０秒がより好ましく、８０～２２０秒がさらに好ましい。プリベークは、ホットプレート、オーブン等で行うことができる。 The colored composition layer formed on the support may be dried (prebaked). If the film is produced by a low temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and further preferably 110 ° C or lower. The lower limit may be, for example, 50 ° C. or higher, and may be 80 ° C. or higher. The prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Prebaking can be performed with a hot plate, an oven, or the like.
　次に、着色組成物層をパターン状に露光する（露光工程）。例えば、着色組成物層に対し、ステッパー露光機やスキャナ露光機などを用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン状に露光することができる。これにより、露光部分を硬化することができる。 Next, the colored composition layer is exposed in a pattern (exposure step). For example, the colored composition layer can be exposed in a pattern by using a stepper exposure device, a scanner exposure device, or the like through a mask having a predetermined mask pattern. Thereby, the exposed portion can be cured.
　露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等が挙げられる。また、波長３００ｎｍ以下の光（好ましくは波長１８０～３００ｎｍの光）を用いることもできる。波長３００ｎｍ以下の光としては、ＫｒＦ線（波長２４８ｎｍ）、ＡｒＦ線（波長１９３ｎｍ）などが挙げられ、ＫｒＦ線（波長２４８ｎｍ）が好ましい。また、３００ｎｍ以上の長波な光源も利用できる。 Radiation (light) that can be used at the time of exposure includes g rays, i rays, and the like. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm) are preferable. Also, a long-wavelength light source of 300 nm or more can be used.
　また、露光に際して、光を連続的に照射して露光してもよく、パルス的に照射して露光（パルス露光）してもよい。なお、パルス露光とは、短時間（例えば、ミリ秒レベル以下）のサイクルで光の照射と休止を繰り返して露光する方式の露光方法のことである。パルス露光の場合、パルス幅は、１００ナノ秒（ｎｓ）以下であることが好ましく、５０ナノ秒以下であることがより好ましく、３０ナノ秒以下であることが更に好ましい。パルス幅の下限は、特に限定はないが、１フェムト秒（ｆｓ）以上とすることができ、１０フェムト秒以上とすることもできる。周波数は、１ｋＨｚ以上であることが好ましく、２ｋＨｚ以上であることがより好ましく、４ｋＨｚ以上であることが更に好ましい。周波数の上限は５０ｋＨｚ以下であることが好ましく、２０ｋＨｚ以下であることがより好ましく、１０ｋＨｚ以下であることが更に好ましい。最大瞬間照度は、５０００００００Ｗ／ｍ２以上であることが好ましく、１００００００００Ｗ／ｍ２以上であることがより好ましく、２００００００００Ｗ／ｍ２以上であることが更に好ましい。また、最大瞬間照度の上限は、１０００００００００Ｗ／ｍ２以下であることが好ましく、８００００００００Ｗ／ｍ２以下であることがより好ましく、５００００００００Ｗ／ｍ２以下であることが更に好ましい。なお、パルス幅とは、パルス周期における光が照射されている時間のことである。また、周波数とは、１秒あたりのパルス周期の回数のことである。また、最大瞬間照度とは、パルス周期における光が照射されている時間内での平均照度のことである。また、パルス周期とは、パルス露光における光の照射と休止を１サイクルとする周期のことである。 Further, upon exposure, light may be continuously irradiated to perform exposure, or pulsed irradiation may be performed (pulse exposure). Note that the pulse exposure is an exposure method of a type in which light irradiation and rest are repeated in a short-time (for example, millisecond level or less) cycle. In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and further preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, and may be 10 femtoseconds or more. The frequency is preferably 1 kHz or higher, more preferably 2 kHz or higher, even more preferably 4 kHz or higher. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and further preferably 10 kHz or less. Maximum instantaneous intensity is preferably at 50000000W / m 2 or more, more preferably 100000000W / m 2 or more, more preferably 200000000W / m 2 or more. The upper limit of the maximum instantaneous intensity is preferably at 1000000000W / m 2 or less, more preferably 800000000W / m 2 or less, further preferably 500000000W / m 2 or less. The pulse width is the time during which light is emitted in the pulse cycle. The frequency is the number of pulse cycles per second. The maximum instantaneous illuminance is the average illuminance within the time during which light is emitted in the pulse cycle. In addition, the pulse cycle is a cycle in which light irradiation and rest in pulse exposure are one cycle.
　照射量（露光量）は、例えば、０．０３～２．５Ｊ／ｃｍ２が好ましく、０．０５～１．０Ｊ／ｃｍ２がより好ましい。露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、または、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、または、５０体積％）で露光してもよい。また、露光照度は適宜設定することが可能であり、通常１０００Ｗ／ｍ２～１０００００Ｗ／ｍ２（例えば、５０００Ｗ／ｍ２、１５０００Ｗ／ｍ２、または、３５０００Ｗ／ｍ２）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ２、酸素濃度３５体積％で照度２００００Ｗ／ｍ２などとすることができる。 Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm 2, more preferably 0.05 ~ 1.0J / cm 2. The oxygen concentration at the time of exposure can be appropriately selected. In addition to performing in the air, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially The exposure may be carried out under oxygen-free conditions or under a high oxygen atmosphere in which the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume or 50% by volume). In addition, the exposure illuminance can be set appropriately and is usually selected from the range of 1000 W / m 2 to 100000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , or 35000 W / m 2 ). You can 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.
　次に、着色組成物層の未露光部を現像除去してパターン（画素）を形成する。着色組成物層の未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の着色組成物層が現像液に溶出し、光硬化した部分だけが残る。現像液の温度は、例えば、２０～３０℃が好ましい。現像時間は、２０～１８０秒が好ましい。また、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。 Next, the unexposed portion of the colored composition layer is developed and removed to form a pattern (pixel). The development removal of the unexposed part of the coloring composition layer can be performed using a developing solution. As a result, the unexposed portion of the colored composition layer in the exposure step is eluted into the developing solution, and only the photocured portion remains. The temperature of the developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the process of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.
　現像液は、有機溶剤、アルカリ現像液などが挙げられる。アルカリ現像液としては、アルカリ剤を純水で希釈したアルカリ性水溶液であることが好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましい。また、現像液は、さらに界面活性剤を含有していてもよい。界面活性剤としては、上述した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば１．５～１００倍の範囲に設定することができる。また、現像後純水で洗浄（リンス）することも好ましい。また、リンスは、現像後の着色組成物層が形成された支持体を回転させつつ、現像後の着色組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルを支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。 Developers include organic solvents and alkaline developers. The alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide. Organic compounds such as, 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 hydrogen carbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate. As the alkaline 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 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Further, the developing solution may further contain a surfactant. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable. The developer may be produced once as a concentrated solution and diluted to a required concentration at the time of use, from the viewpoint of convenience of transportation and storage. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. Further, it is also preferable to wash (rinse) with pure water after the development. In addition, the rinsing is preferably performed by supplying a rinse liquid to the colored composition layer after development while rotating the support on which the colored composition layer after development is formed. It is also preferable that the nozzle for discharging the rinse liquid is moved from the central portion of the support to the peripheral portion of the support. At this time, when moving from the central portion of the support body of the nozzle to the peripheral edge portion, the movement speed of the nozzle may be gradually reduced. By performing the rinse in this manner, it is possible to suppress the in-plane variation of the rinse. Further, the same effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the peripheral portion.
　現像後、乾燥を施した後に追加露光処理や加熱処理（ポストベーク）を行うことも好ましい。追加露光処理やポストベークは、硬化を完全なものとするための現像後の硬化処理である。ポストベークにおける加熱温度は、例えば１００～２４０℃が好ましく、２００～２４０℃がより好ましい。ポストベークは、現像後の膜を、上記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。追加露光処理を行う場合、露光に用いられる光は、波長４００ｎｍ以下の光であることが好ましい。また、追加露光処理は、ＫＲ１０２０１７０１２２１３０Ａに記載の方法で行ってもよい。 After development, it is also preferable to carry out additional exposure processing and heating processing (post-baking) after drying. The additional exposure process and the post-baking are curing processes after development to complete the curing. The heating temperature in the post-baking is preferably 100 to 240 ° C, more preferably 200 to 240 ° C. Post-baking can be performed in a continuous or batch manner by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the film after development can meet the above conditions. . When the additional exposure process is performed, the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in KR1020170122130A.
＜固体撮像素子＞
　本発明の固体撮像素子は、上述した本発明の膜を有する。本発明の固体撮像素子の構成としては、本発明の膜を備え、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。 <Solid-state image sensor>
The solid-state image sensor of the present invention has the above-mentioned film of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations.
　基板上に、固体撮像素子（ＣＣＤ（電荷結合素子）イメージセンサ、ＣＭＯＳ（相補型金属酸化膜半導体）イメージセンサ等）の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる転送電極を有し、フォトダイオードおよび転送電極上にフォトダイオードの受光部のみ開口した遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等からなるデバイス保護膜を有し、デバイス保護膜上に、カラーフィルタを有する構成である。更に、デバイス保護膜上であってカラーフィルタの下（基板に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、カラーフィルタ上に集光手段を有する構成等であってもよい。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各着色画素が埋め込まれた構造を有していてもよい。この場合の隔壁は各着色画素に対して低屈折率であることが好ましい。このような構造を有する撮像装置の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報、国際公開ＷＯ２０１８／０４３６５４号公報に記載の装置が挙げられる。本発明の固体撮像素子を備えた撮像装置は、デジタルカメラや、撮像機能を有する電子機器（携帯電話等）の他、車載カメラや監視カメラ用としても用いることができる。 On the substrate, there are provided a plurality of photodiodes forming a light receiving area of a solid-state image pickup device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and transfer electrodes made of polysilicon or the like. A device protection film made of silicon nitride or the like, which has a light-shielding film that is opened only on the photodiode and the light-receiving portion of the photodiode on the transfer electrode and covers the entire light-shielding film and the photodiode light-receiving portion on the light-shielding film. And has a color filter on the device protective film. Furthermore, a structure having a light collecting means (for example, a microlens or the like; hereinafter the same) on the device protective film and below the color filter (on the side close to the substrate), or a structure having a light collecting means on the color filter is used. It may be. Further, the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each colored pixel. Examples of the imaging device having such a structure include the devices described in JP2012-227478A, JP2014-179577A, and International Publication WO2018 / 043654. The image pickup apparatus provided with the solid-state image pickup element of the present invention can be used not only for digital cameras and electronic devices (such as mobile phones) having an image pickup function, but also for vehicle-mounted cameras and surveillance cameras.
＜画像表示装置＞
　本発明の画像表示装置は、上述した本発明の膜を有する。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス表示装置などが挙げられる。画像表示装置の定義や各画像表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木昭夫著、（株）工業調査会、１９９０年発行）」、「ディスプレイデバイス（伊吹順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田龍男編集、（株）工業調査会、１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。 <Image display device>
The image display device of the present invention has the above-mentioned film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of the image display device and the details of each image display device, see, for example, "Electronic Display Device (Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (Junsho Ibuki, Industrial Books ( (Published in 1989) ”etc. Further, the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Institute Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, liquid crystal display devices of various systems described in the above-mentioned “next-generation liquid crystal display technology”.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
＜樹脂の重量平均分子量（Ｍｗ）の測定）
　樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により、以下の条件で測定した。
カラムの種類：ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｈと、ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００と、ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００とを連結したカラム
展開溶媒：テトラヒドロフラン
カラム温度：４０℃
流量（サンプル注入量）：１．０μＬ（サンプル濃度：０．１質量％）
装置名：東ソー製　ＨＬＣ－８２２０ＧＰＣ
検出器：ＲＩ（屈折率）検出器
検量線ベース樹脂：ポリスチレン樹脂 <Measurement of weight average molecular weight (Mw) of resin)
The weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) under the following conditions.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 are connected to each other. Column developing solvent: Tetrahydrofuran Column temperature: 40 ° C
Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1% by mass)
Device name: Tosoh HLC-8220GPC
Detector: RI (refractive index) detector Calibration curve Base resin: Polystyrene resin
＜顔料の短軸長および長軸長の測定＞
　走査型電子顕微鏡を用い、加速電圧５ｋＶ、撮像倍率１０万倍で撮影した画像をデジタル化して、顔料の長軸方向、短軸方向の画像輝度データ（長軸方向の座標、短軸方向の座標、および輝度の３成分からなる。）を作成した。デジタル化では、画像を幅方向に１２８０分割して、輝度８ビットで処理して２５６階調のデータを得て、分割した各座標ポイントの画像輝度を所定の階調値に変換した。次に、得られた画像輝度データにおいて、粒子の長軸にあたる方向の座標を横軸にとり、長軸方向の各座標ポイントにおける輝度の平均値（即ち、１２８０分割した各座標ポイントにおける輝度の平均値）を縦軸にとって輝度曲線を作成した。作成した輝度曲線を微分して微分曲線を作成し、作成した微分曲線のピーク位置から顔料の境界の座標を特定した。顔料の長軸にあたる方向の座標を横軸にとる操作を３回繰り返し、最も長い軸長を長軸長とした。短軸方向でも座標を横軸にとる操作を３回繰り返し、最も短い軸長を短軸長とした。詳しくは、長軸長とは、粒子の長さを最も長く取ることができる軸（直線）を長軸として決定し、この長軸の長さとする。一方、短軸とは、長軸と直交する直線で粒子長さを取ったときに最も長さが長くなる軸として決定し、この軸の長さを短軸長とした。
　また、１００個の顔料の短軸長および長軸長の算術平均値を算出して、顔料の短軸長の平均値および顔料の長軸長の平均値を算出した。 <Measurement of short axis length and long axis length of pigment>
Image brightness data (long-axis direction coordinates, short-axis direction coordinates) of the pigment in the long-axis direction and the short-axis direction are digitized using a scanning electron microscope at an accelerating voltage of 5 kV and an imaging magnification of 100,000 times. , And the luminance). In the digitization, the image was divided into 1280 in the width direction, processed with 8-bit luminance to obtain data of 256 gradations, and the image luminance of each divided coordinate point was converted into a predetermined gradation value. Next, in the obtained image brightness data, the horizontal axis represents the coordinate in the direction of the long axis of the particle, and the average value of the brightness at each coordinate point in the long axis direction (that is, the average value of the brightness at each of the 1280 divided coordinate points). ) Was plotted on the vertical axis to create a luminance curve. The created brightness curve was differentiated to create a differential curve, and the coordinates of the boundary of the pigment were specified from the peak position of the created differential curve. The operation of setting the coordinate in the direction corresponding to the long axis of the pigment as the horizontal axis was repeated 3 times, and the longest axis length was defined as the long axis length. Even in the short axis direction, the operation of setting the coordinate on the horizontal axis was repeated three times, and the shortest axis length was defined as the short axis length. Specifically, the major axis length is determined by defining the axis (straight line) that can maximize the length of the particle as the major axis, and using the major axis length. On the other hand, the minor axis is determined as the axis that has the longest length when the particle length is taken on a straight line orthogonal to the major axis, and the length of this axis is defined as the minor axis length.
Further, the arithmetic mean values of the minor axis length and the major axis length of 100 pigments were calculated, and the average value of the minor axis length of the pigment and the average value of the major axis length of the pigment were calculated.
　＜顔料分散液の調製＞
　（顔料分散液Ａ１－１～Ａ１－７）
　Ｃ．Ｉ．ピグメントグリーン５８の９質量部、Ｃ．Ｉ．ピグメントイエロー１８５の６質量部、顔料誘導体Ｙ１の２．５質量部、分散剤Ｄ１の５質量部、および、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）の７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液１－１～Ａ１－７を調製した。顔料分散液中に含まれる顔料１および顔料２の長軸長および短軸長はそれぞれ下記表の値であった。なお、分散時間を変えることで、顔料１および顔料２の長軸長および短軸長がそれぞれ下記表に記載の値となるように調整した。これらの顔料分散液は、固形分濃度が２２．５質量％であり、顔料含有量が１５質量％であった。
　顔料誘導体Ｙ１：下記構造の化合物。
Figure JPOXMLDOC01-appb-C000011
 　分散剤Ｄ１：下記構造の樹脂（Ｍｗ＝２４０００、主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。）
Figure JPOXMLDOC01-appb-C000012
 <Preparation of pigment dispersion>
(Pigment dispersion A1-1 to A1-7)
C. I. Pigment Green 58 9 parts by mass, C.I. I. Pigment Yellow 185 (6 parts by mass), pigment derivative Y1 (2.5 parts by mass), dispersant D1 (5 parts by mass), and propylene glycol monomethyl ether acetate (PGMEA) (77.5 parts by mass). 230 parts by mass of 0.3 mm zirconia beads were added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersion liquids 1-1 to A1-7. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. The major axis length and minor axis length of Pigment 1 and Pigment 2 were adjusted to the values shown in the following table by changing the dispersion time. These pigment dispersions had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
Pigment derivative Y1: a compound having the following structure.
Figure JPOXMLDOC01-appb-C000011
 Dispersant D1: Resin having the following structure (Mw = 24000, the numerical value added to the main chain is a molar ratio, and the numerical value added to the side chain is the number of repeating units).
Figure JPOXMLDOC01-appb-C000012
　（顔料分散液Ａ２－１～Ａ２－７）
　Ｃ．Ｉ．ピグメントグリーン３６の９質量部、Ｃ．Ｉ．ピグメントイエロー１５０の６質量部、顔料誘導体Ｙ１の２．５質量部、分散剤Ｄ１の５質量部、および、ＰＧＭＥＡの７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液Ａ２－１～Ａ２－７を調製した。顔料分散液中に含まれる顔料１および顔料２の長軸長および短軸長はそれぞれ下記表の値であった。なお、分散時間を変えることで、顔料１および顔料２の長軸長および短軸長がそれぞれ下記表に記載の値となるように調整した。これらの顔料分散液は、固形分濃度が２２．５質量％であり、顔料含有量が１５質量％であった。 (Pigment dispersion A2-1 to A2-7)
C. I. Pigment Green 36 9 parts by mass, C.I. I. Pigment Yellow 150 (6 parts by mass), pigment derivative Y1 (2.5 parts by mass), dispersant D1 (5 parts by mass), and PGMEA (77.5 parts by mass) are mixed in a mixed solution and zirconia beads 230 having a diameter of 0.3 mm are mixed. After adding parts by mass and performing a dispersion treatment using a paint shaker, the beads were separated by filtration to prepare pigment dispersions A2-1 to A2-7. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. The major axis length and minor axis length of Pigment 1 and Pigment 2 were adjusted to the values shown in the following table by changing the dispersion time. These pigment dispersions had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
　（顔料分散液Ａ３）
　Ｃ．Ｉ．ピグメントグリーン５８の９質量部、Ｃ．Ｉ．ピグメントイエロー１３９の６質量部、顔料誘導体Ｙ１の２．５質量部、分散剤Ｄ１の５質量部、および、ＰＧＭＥＡの７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液Ａ３を調製した。顔料分散液中に含まれる顔料１および顔料２の長軸長および短軸長はそれぞれ下記表の値であった。この顔料分散液は、固形分濃度が２２．５質量％であり、顔料含有量が１５質量％であった。 (Pigment dispersion A3)
C. I. Pigment Green 58 9 parts by mass, C.I. I. Pigment Yellow 139 (6 parts by mass), Pigment Derivative Y1 (2.5 parts by mass), Dispersant D1 (5 parts by mass), and PGMEA (77.5 parts by mass) in a mixed solution. After adding a mass part and performing a dispersion process using a paint shaker, the beads were separated by filtration to prepare a pigment dispersion A3. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
　（顔料分散液Ａ４）
　Ｃ．Ｉ．ピグメントレッド２５４の１０．５質量部、Ｃ．Ｉ．ピグメントイエロー１３９の４．５質量部、顔料誘導体Ｙ１の２．０質量部、分散剤Ｄ１の５．５質量部、および、ＰＧＭＥＡの７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液Ａ４を調製した。顔料分散液中に含まれる顔料１および顔料２の長軸長および短軸長はそれぞれ下記表の値であった。この顔料分散液は、固形分濃度が２２．５質量％であり、顔料含有量が１５質量％であった。 (Pigment dispersion A4)
C. I. Pigment Red 254, 10.5 parts by mass, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y1 (2.0 parts by mass), Dispersant D1 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed to prepare a mixed solution having a diameter of 0.3 mm. 230 parts by mass of the zirconia beads of was added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare a pigment dispersion A4. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
　（顔料分散液Ａ５－１、Ａ５－２）
　Ｃ．Ｉ．ピグメントレッド１７７の１０．５質量部、Ｃ．Ｉ．ピグメントイエロー１３９の４．５質量部、顔料誘導体Ｙ２の２．０質量部、分散剤Ｄ２の５．５質量部、および、ＰＧＭＥＡの７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液Ａ５－１、Ａ５－２を調製した。顔料分散液中に含まれる顔料１および顔料２の長軸長および短軸長はそれぞれ下記表の値であった。なお、分散時間を変えることで、顔料１および顔料２の長軸長および短軸長がそれぞれ下記表に記載の値となるように調整した。これらの顔料分散液は、固形分濃度が２２．５質量％であり、顔料含有量が１５質量％であった。
　顔料誘導体Ｙ２：下記構造の化合物
Figure JPOXMLDOC01-appb-C000013
 　分散剤Ｄ２：下記構造の化合物
Figure JPOXMLDOC01-appb-C000014
 (Pigment dispersion A5-1, A5-2)
C. I. Pigment Red 177, 10.5 parts by mass, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y2 (2.0 parts by mass), Dispersant D2 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed in a mixed solution having a diameter of 0.3 mm. 230 parts by mass of the zirconia beads of was added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersions A5-1 and A5-2. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. The major axis length and minor axis length of Pigment 1 and Pigment 2 were adjusted to the values shown in the following table by changing the dispersion time. These pigment dispersions had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
Pigment derivative Y2: compound having the following structure
Figure JPOXMLDOC01-appb-C000013
 Dispersant D2: compound having the following structure
Figure JPOXMLDOC01-appb-C000014
　（顔料分散液Ａ６）
　Ｃ．Ｉ．ピグメントレッド２６４の１０．５質量部、Ｃ．Ｉ．ピグメントイエロー１３９の４．５質量部、顔料誘導体Ｙ１の２．０質量部、分散剤Ｄ１の５．５質量部、および、ＰＧＭＥＡの７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液Ａ６を調製した。顔料分散液中に含まれる顔料１および顔料２の長軸長および短軸長はそれぞれ下記表の値であった。この顔料分散液は、固形分濃度が２２．５質量％であり、顔料含有量が１５質量％であった。 (Pigment dispersion A6)
C. I. Pigment Red 264, 10.5 parts by mass, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y1 (2.0 parts by mass), Dispersant D1 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed to prepare a mixed solution having a diameter of 0.3 mm. After adding 230 parts by mass of zirconia beads of Example 1 and performing a dispersion treatment using a paint shaker, the beads were separated by filtration to prepare a pigment dispersion A6. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
　（顔料分散液Ａ７）
　Ｃ．Ｉ．ピグメントレッド２７２の１０．５質量部、Ｃ．Ｉ．ピグメントイエロー１３９の４．５質量部、顔料誘導体Ｙ１の２．０質量部、分散剤Ｄ１の５．５質量部、および、ＰＧＭＥＡの７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液Ａ７を調製した。顔料分散液中に含まれる顔料１および顔料２の長軸長および短軸長はそれぞれ下記表の値であった。この顔料分散液は、固形分濃度が２２．５質量％であり、顔料含有量が１５質量％であった。 (Pigment dispersion A7)
C. I. Pigment Red 272, 10.5 parts by mass, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y1 (2.0 parts by mass), Dispersant D1 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed to prepare a mixed solution having a diameter of 0.3 mm. After adding 230 parts by mass of zirconia beads of Example 1 and performing a dispersion treatment using a paint shaker, the beads were separated by filtration to prepare a pigment dispersion A7. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
　（顔料分散液Ａ８）
　赤色顔料１の１０．５質量部、Ｃ．Ｉ．ピグメントイエロー１３９の４．５質量部、顔料誘導体Ｙ１の２．０質量部、分散剤Ｄ１の５．５質量部、および、ＰＧＭＥＡの７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液Ａ８を調製した。顔料分散液中に含まれる顔料１および顔料２の長軸長および短軸長はそれぞれ下記表の値であった。この顔料分散液は、固形分濃度が２２．５質量％であり、顔料含有量が１５質量％であった。
　赤色顔料１：下記構造の化合物
Figure JPOXMLDOC01-appb-C000015
 (Pigment dispersion A8)
10.5 parts by mass of red pigment 1, C.I. I. Pigment Yellow 139 (4.5 parts by mass), Pigment Derivative Y1 (2.0 parts by mass), Dispersant D1 (5.5 parts by mass), and PGMEA (77.5 parts by mass) are mixed to prepare a mixed solution having a diameter of 0.3 mm. 230 parts by mass of zirconia beads were added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare a pigment dispersion A8. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
Red pigment 1: compound with the following structure
Figure JPOXMLDOC01-appb-C000015
　（顔料分散液Ａ９－１、Ａ９－２）
　Ｃ．Ｉ．ピグメントブルー１５：６の１２質量部、Ｃ．Ｉ．ピグメントバイオレット２３の３質量部、顔料誘導体Ｙ１の２．７質量部、分散剤Ｄ１の４．８質量部、および、ＰＧＭＥＡの７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液Ａ９－１、Ａ９－２を調製した。顔料分散液中に含まれる顔料１および顔料２の長軸長および短軸長はそれぞれ下記表の値であった。なお、分散時間を変えることで、顔料１および顔料２の長軸長および短軸長がそれぞれ下記表に記載の値となるように調整した。これらの顔料分散液は、固形分濃度が２２．５質量％であり、顔料含有量が１５質量％であった。 (Pigment dispersion A9-1, A9-2)
C. I. Pigment Blue 15: 6 12 parts by mass, C.I. I. Pigment Violet 23, 2.7 parts by mass of the pigment derivative Y1, 4.8 parts by mass of the dispersant D1, and 77.5 parts by mass of PGMEA. 230 parts by mass of beads were added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersions A9-1 and A9-2. The major axis length and the minor axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion are the values in the following table. The major axis length and minor axis length of Pigment 1 and Pigment 2 were adjusted to the values shown in the following table by changing the dispersion time. These pigment dispersions had a solid content concentration of 22.5% by mass and a pigment content of 15% by mass.
　（顔料分散液Ａ１０）
　Ｃ．Ｉ．ピグメントブルー１５：６の１２質量部、特開２０１５－０４１０５８号公報の段落番号０２９２に記載のＶ染料１の３質量部、顔料誘導体Ｙ１の２．７質量部、分散剤Ｄ１の４．８質量部、および、ＰＧＭＥＡの７７．５質量部を混合した混合液に、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて分散処理を行った後、ビーズをろ過で分離して顔料分散液Ａ１０を調製した。顔料分散液中に含まれる顔料１の長軸長および短軸長はそれぞれ下記表の値であった。この顔料分散液は、固形分濃度が２２．５質量％であり、色材含有量（顔料と染料の合計量）が１５質量％であった。 (Pigment dispersion A10)
C. I. Pigment Blue 15: 6, 12 parts by mass, 3 parts by mass of V dye 1 described in paragraph No. 0292 of JP-A-2005-041058, 2.7 parts by mass of pigment derivative Y1, 4.8 parts by mass of dispersant D1. Parts, and 77.5 parts by mass of PGMEA, 230 parts by mass of zirconia beads having a diameter of 0.3 mm was added to the mixed solution, and dispersion treatment was performed using a paint shaker, and then the beads were separated by filtration. To prepare Pigment Dispersion Liquid A10. The major axis length and the minor axis length of Pigment 1 contained in the pigment dispersion are the values in the following table. This pigment dispersion had a solid content concentration of 22.5% by mass and a coloring material content (total amount of pigment and dye) of 15% by mass.
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
　上記表中、の略語は以下の通りである。
　ＰＧ３６　：Ｃ．Ｉ．ピグメントグリーン３６
　ＰＧ５８　：Ｃ．Ｉ．ピグメントグリーン５８
　ＰＲ２５４　：Ｃ．Ｉ．ピグメントレッド２５４
　ＰＲ２６４　：Ｃ．Ｉ．ピグメントレッド２６４
　ＰＲ２７２　：Ｃ．Ｉ．ピグメントレッド２７２
　赤色顔料１　：上述した構造の化合物
　ＰＲ１７７　：Ｃ．Ｉ．ピグメントレッド１７７
　ＰＢ１５：６　：Ｃ．Ｉ．ピグメントブルー１５：６
　ＰＹ１８５　：Ｃ．Ｉ．ピグメントイエロー１８５
　ＰＹ１５０　：Ｃ．Ｉ．ピグメントイエロー１５０
　ＰＹ１３９　：Ｃ．Ｉ．ピグメントイエロー１３９
　ＰＶ２３　：Ｃ．Ｉ．ピグメントバイオレット２３ The abbreviations in the above table are as follows.
PG36: C.I. I. Pigment Green 36
PG58: C.I. I. Pigment Green 58
PR254: C.I. I. Pigment Red 254
PR264: C.I. I. Pigment Red 264
PR272: C.I. I. Pigment Red 272
Red Pigment 1: Compound of the above structure PR177: C.I. I. Pigment Red 177
PB15: 6: C. I. Pigment Blue 15: 6
PY185: C.I. I. Pigment Yellow 185
PY150: C.I. I. Pigment Yellow 150
PY139: C.I. I. Pigment Yellow 139
PV23: C.I. I. Pigment Violet 23
＜着色組成物の調製＞
　下記表に記載の原料を混合した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して着色組成物を調製した。組成物１０１～１１８、Ｃ１０１～Ｃ１０３は緑色着色組成物であり、組成物２０１～２０５、Ｃ２０１は赤色着色組成物であり、組成物３０１、３０２、Ｃ３０１は青色着色組成物であった。 <Preparation of coloring composition>
After mixing the raw materials described in the following table, a coloring composition was prepared by filtering with a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm. The compositions 101 to 118 and C101 to C103 were green coloring compositions, the compositions 201 to 205 and C201 were red coloring compositions, and the compositions 301, 302 and C301 were blue coloring compositions.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
　上記表に記載の原料は以下の通りである。 The raw materials listed in the above table are as follows.
（顔料分散液）
　顔料分散液Ａ１－１～Ａ１－７、Ａ２－１～Ａ２－７、Ａ３、Ａ４、Ａ５－１、Ａ５－２、Ａ６、Ａ７、Ａ８、Ａ９－１、Ａ９－２、Ａ１０：上述した顔料分散液Ａ１－１～Ａ１－７、Ａ２－１～Ａ２－７、Ａ３、Ａ４、Ａ５－１、Ａ５－２、Ａ６、Ａ７、Ａ８、Ａ９－１、Ａ９－２、Ａ１０ (Pigment dispersion)
Pigment dispersions A1-1 to A1-7, A2-1 to A2-7, A3, A4, A5-1, A5-2, A6, A7, A8, A9-1, A9-2, A10: the above-mentioned pigments Dispersions A1-1 to A1-7, A2-1 to A2-7, A3, A4, A5-1, A5-2, A6, A7, A8, A9-1, A9-2, A10
（樹脂）
　Ｂ１：下記構造の樹脂（主鎖に付記した数値はモル比である。Ｍｗ：１０，０００、酸価：７０ｍｇＫＯＨ／ｇ、Ｃ＝Ｃ価：１．４ｍｍｏｌ／ｇ）
Figure JPOXMLDOC01-appb-C000020
 (resin)
B1: Resin having the following structure (numerals attached to the main chain are molar ratios: Mw: 10,000, acid value: 70 mgKOH / g, C = C value: 1.4 mmol / g)
Figure JPOXMLDOC01-appb-C000020
（重合性モノマー）
　Ｍ１：オグソールＥＡ－０３００（大阪ガスケミカル（株）製、フルオレン骨格を有する（メタ）アクリレートモノマー、Ｃ＝Ｃ価：２．１ｍｍｏｌ／ｇ）
　Ｍ２：下記構造の化合物（Ｃ＝Ｃ価：１０．４ｍｍｏｌ／ｇ）
Figure JPOXMLDOC01-appb-C000021
 (Polymerizable monomer)
M1: Ogsol EA-0300 (Osaka Gas Chemical Co., Ltd., (meth) acrylate monomer having a fluorene skeleton, C = C value: 2.1 mmol / g)
M2: compound having the following structure (C = C value: 10.4 mmol / g)
Figure JPOXMLDOC01-appb-C000021
（開始剤）
　Ｉ１、Ｉ３、Ｉ５：下記構造の化合物
Figure JPOXMLDOC01-appb-C000022
 (Initiator)
I1, I3, I5: compounds having the following structures
Figure JPOXMLDOC01-appb-C000022
　（界面活性剤）
　Ｗ１：下記構造の化合物
Figure JPOXMLDOC01-appb-C000023
 (Surfactant)
W1: compound having the following structure
Figure JPOXMLDOC01-appb-C000023
　（添加剤）
　Ｔ１：ＥＨＰＥ３１５０（（株）ダイセル製、エポキシ樹脂）
　Ｔ２：下記構造の化合物（シランカップリング剤）
Figure JPOXMLDOC01-appb-C000024
 (Additive)
T1: EHPE3150 (manufactured by Daicel Corporation, epoxy resin)
T2: Compound having the following structure (silane coupling agent)
Figure JPOXMLDOC01-appb-C000024
＜膜収縮性の評価＞
　ガラス基板上にＣＴ－４０００（富士フイルムエレクトロニクスマテリアルズ（株）製）を膜厚が０．１μｍとなるようにスピンコート法で塗布し、ホットプレートを用いて２２０℃で１時間加熱して下地層を形成した。この下地層付きのガラス基板上に、ポストベーク後の膜厚が下記表に記載の膜厚となるように各着色組成物をスピンコート法で塗布し、その後、ホットプレートを用いて１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（キヤノン（株）製）を用い、オープンフレームのマスクを介してｉ線を露光量１０００ｍＪ／ｃｍ２でガラス基板全面に照射して露光を行った。次いで、ホットプレートを用い、２００℃で５分間加熱することで、膜を形成した。得られた膜の膜厚について、触診式プロファイリングシステムＤｅｋｔａｋＸＴ（ＢＲＵＫＥＲ社製）を用いて測定した。
　次に、上記で作製した膜を温度１１０℃湿度８５％の恒温恒湿下で１００時間静置した。耐湿性試験を行った後の膜の膜厚を測定して下記の式から膜の収縮率を測定し、以下の基準にて膜収縮性を評価した。膜の膜厚は耐湿試験前・後の膜のそれぞれについて、ガラス基板の直径方向に５等分した位置で測定し、その平均値を採用した。
　膜の収縮率（％）＝{（耐湿試験前の膜の膜厚－耐湿試験後の膜の膜厚）／耐湿試験前の膜の膜厚}×１００
（評価基準） 
　Ａ：膜の収縮率が５％未満である
　Ｂ：膜の収縮率が５％以上１０％未満である
　Ｃ：膜の収縮率が１０％以上２０％未満である
　Ｄ：膜の収縮率が２０％以上である <Evaluation of membrane shrinkage>
CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied on a glass substrate by spin coating to a film thickness of 0.1 μm, and heated at 220 ° C. for 1 hour using a hot plate. The formation was formed. Each coloring composition was applied onto this glass substrate with an underlayer by spin coating so that the film thickness after post-baking would be the film thickness shown in the table below, and then at 100 ° C. using a hot plate. Heated for 2 minutes. Then, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), the entire surface of the glass substrate was exposed to i-line through a mask of an open frame at an exposure dose of 1000 mJ / cm 2 . Next, using a hot plate, the film was formed by heating at 200 ° C. for 5 minutes. The film thickness of the obtained film was measured using a palpation-type profiling system DektakXT (manufactured by BRUKER).
Next, the film produced above was allowed to stand for 100 hours under a constant temperature and humidity of 110 ° C. and 85% humidity. The film thickness of the film after the moisture resistance test was measured, the shrinkage rate of the film was measured from the following equation, and the film shrinkage was evaluated according to the following criteria. The film thickness of each film before and after the moisture resistance test was measured at five equally divided positions in the diameter direction of the glass substrate, and the average value thereof was adopted.
Shrinkage rate (%) of film = {(film thickness before humidity resistance test−film thickness after humidity resistance test) / film thickness before humidity resistance test} × 100
(Evaluation criteria)
A: Shrinkage of the film is less than 5% B: Shrinkage of the film is 5% or more and less than 10% C: Shrinkage of the film is 10% or more and less than 20% D: Shrinkage of the film is 20 % Or more
＜色価の評価＞
　ガラス基板上に、下記表に記載の着色組成物をスピンコート法で塗布した。次いで、ホットプレートを用い、１００℃で２分間加熱して下記表に示す膜厚の膜を形成した。得られた膜に対し、下記に表に記載の波長の光を入射し、その透過率を分光器（ＵＶ４１００、（株）日立ハイテクノロジーズ製）により測定して、光学濃度（ＯＤ値）を測定した。
得られた光学濃度を膜厚で規格化することで、色価の相対値を得た。なお、緑色着色組成物を用いて形成した膜については、波長６６０ｎｍの光を入射した。また、赤色着色組成物を用いて径背した膜については、波長５３０ｎｍの光を入射した。また、青色着色組成物を用いて形成した膜については、波長６１０ｎｍの光を入射した。 <Evaluation of color value>
The coloring composition described in the following table was applied onto a glass substrate by spin coating. Then, using a hot plate, heating was performed at 100 ° C. for 2 minutes to form a film having a film thickness shown in the following table. Light having wavelengths shown in the table below is incident on the obtained film, and its transmittance is measured by a spectroscope (UV4100, manufactured by Hitachi High-Technologies Corporation) to measure an optical density (OD value). did.
The obtained optical density was normalized by the film thickness to obtain the relative value of color value. Note that the film formed using the green coloring composition was irradiated with light having a wavelength of 660 nm. In addition, light having a wavelength of 530 nm was incident on the film formed by using the red coloring composition. In addition, light having a wavelength of 610 nm was incident on the film formed using the blue coloring composition.
＜パターン形成性および残渣の評価＞
　８インチ（２０．３２ｃｍ）シリコンウエハに、ＣＴ－４０００Ｌ（富士フイルムエレクトロニクスマテリアルズ（株）製）をポストベーク後に厚さが０．１μｍになるようにスピンコーターを用いて塗布し、ホットプレートを用いて２２０℃で３００秒間加熱して下塗り層を形成し、下塗り層付シリコンウエハを得た。
　次いで、各着色組成物をポストベーク後の膜厚が下記表に記載の膜厚となるようにスピンコート法で塗布した。次いで、ホットプレートを用い、１００℃で２分間ポストベークした。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（キヤノン（株）製）を用い、画素（パターン）サイズが１μｍ四方で形成されるベイヤーパターンを有するマスクを介して２００ｍＪ／ｃｍ２の露光量にてｉ線で露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した。次いで、ホットプレートを用い、２００℃で５分間加熱することで、画素（パターン）を形成した。 <Evaluation of pattern formability and residue>
CT-4000L (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer by a spin coater to a thickness of 0.1 μm after post-baking, and a hot plate was applied. It was heated at 220 ° C. for 300 seconds to form an undercoat layer, and a silicon wafer with an undercoat layer was obtained.
Next, each coloring composition was applied by spin coating so that the film thickness after post-baking would be the film thickness described in the following table. Then, it was post-baked at 100 ° C. for 2 minutes using a hot plate. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), an exposure amount of 200 mJ / cm 2 was applied through a mask having a Bayer pattern formed with a pixel (pattern) size of 1 μm square. Exposed with lines. Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with a spin shower and further washed with pure water. Next, by using a hot plate and heating at 200 ° C. for 5 minutes, pixels (pattern) were formed.
（パターン形成性の評価方法）
　得られた画素を、高分解能ＦＥＢ（Ｆｉｅｌｄ　Ｅｍｉｓｓｉｏｎ　Ｂｅａｍ）測長装置（ＨＩＴＡＣＨＩ　ＣＤ－ＳＥＭ）Ｓ９３８０ＩＩ（（株）日立ハイテクノロジーズ製）を用いて、画像部（パターン）を観察した。
　Ａ：狙いの線幅のパターンが歪み無く形成されており、パターン中心の線幅と端の線幅の差が５％未満であった。
　Ｂ：ほぼ狙いの線幅のパターンが形成されているが、パターン中心の線幅と端の線幅の差が５％以上１０％未満であった。
　Ｃ：ほぼ狙いの線幅のパターンが形成されているが、パターン中心の線幅と端の線幅の差が１０％以上３０％未満であった。
　Ｄ：Ａ～Ｃ以外である、もしくは、パターンを形成できなかった。 (Pattern formability evaluation method)
An image portion (pattern) of the obtained pixels was observed using a high resolution FEB (Field Emission Beam) length measuring device (HITACHI CD-SEM) S9380II (manufactured by Hitachi High-Technologies Corporation).
A: A pattern having a target line width was formed without distortion, and the difference between the line width at the center of the pattern and the line width at the end was less than 5%.
B: A pattern having a target line width was formed, but the difference between the line width at the center of the pattern and the line width at the end was 5% or more and less than 10%.
C: A pattern having an almost intended line width was formed, but the difference between the line width at the center of the pattern and the line width at the end was 10% or more and less than 30%.
D: Other than A to C, or the pattern could not be formed.
（残渣の評価方法）
　得られた画素を、高分解能ＦＥＢ（Ｆｉｅｌｄ　Ｅｍｉｓｓｉｏｎ　Ｂｅａｍ）測長装置（ＨＩＴＡＣＨＩ　ＣＤ－ＳＥＭ）Ｓ９３８０ＩＩ（（株）日立ハイテクノロジーズ製）を用いて、非画像部（画素間）の残渣を観察した。
　Ａ：残渣が全く見られない。
　Ｂ：非画像部の０％を超え５％未満の領域に残渣が見られた。
　Ｃ：非画像部の５％以上１０％未満の領域に残渣が見られた。
　Ｄ：非画像部の１０％以上の領域に残渣が見られた。 (Residue evaluation method)
The obtained pixels were observed for residues in non-image areas (between pixels) using a high resolution FEB (Field Emission Beam) length measuring device (HITACHI CD-SEM) S9380II (manufactured by Hitachi High-Technologies Corporation).
A: No residue is seen at all.
B: Residue was found in the area of more than 0% and less than 5% of the non-image area.
C: Residue was found in the area of 5% or more and less than 10% of the non-image area.
D: Residue was seen in 10% or more of the non-image area.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　上記表に示す通り、組成物１０１～１１８、２０１～２０５、３０１、３０２を用いた実施例はいずれも、膜収縮が抑制された膜を形成することができた。更には、パターン形成性および残渣の評価も良好であった。また、実施例１０１、１０７～１１１の結果、および、試験例１１２～１１７の結果から明らかなように、長軸長／短軸長の値が１．４以上３．０以下の顔料を用いることで、より色価の高い膜を形成することができた。 As shown in the above table, in each of the examples using the compositions 101 to 118, 201 to 205, 301 and 302, a film in which the film contraction was suppressed could be formed. Furthermore, the pattern formability and the evaluation of the residue were also good. Further, as is clear from the results of Examples 101, 107 to 111 and the results of Test Examples 112 to 117, use of a pigment having a major axis length / minor axis length value of 1.4 or more and 3.0 or less. Thus, a film having a higher color value could be formed.
（試験例１００１）
　シリコンウエハ上に、Ｇｒｅｅｎ組成物をポストベーク後の膜厚が１．０μｍになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（キヤノン（株）製）を用い、３６５ｎｍの波長の光を１０００ｍＪ／ｃｍ２の露光量で２μｍ四方のドットパターンのマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱（ポストベーク）することで、Ｇｒｅｅｎ組成物をパターニングした。同様にＲｅｄ組成物、Ｂｌｕｅ組成物を順次パターニングし、赤、緑及び青の着色パターン（ベイヤーパターン）を形成した。
　Ｇｒｅｅｎ組成物としては、組成物１０１を使用した。Ｒｅｄ組成物としては、組成物２０１を使用した。Ｂｌｕｅ組成物としては組成物３０１を使用した。
　なお、ベイヤーパターンとは、米国特許第３，９７１，０６５号明細書に開示されているような、一個の赤色（Ｒｅｄ）素子と、二個の緑色（Ｇｒｅｅｎ）素子と、一個の青色（Ｂｌｕｅ）素子とを有する色フィルタ素子の２×２アレイを繰り返したパターンである。
　得られたカラーフィルタを公知の方法に従い固体撮像素子に組み込んだ。この固体撮像素子は好適な画像認識能を有していた。 (Test Example 1001)
The Green composition was applied onto a silicon wafer by spin coating so that the film thickness after post-baking would be 1.0 μm. Then, using a hot plate, it heated at 100 degreeC for 2 minutes. Then, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm was exposed through a mask having a dot pattern of 2 μm square at an exposure dose of 1000 mJ / cm 2 . Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with a spin shower and further washed with pure water. Next, the Green composition was patterned by heating (post-baking) at 200 ° C. for 5 minutes using a hot plate. Similarly, the Red composition and the Blue composition were sequentially patterned to form red, green, and blue colored patterns (Bayer patterns).
Composition 101 was used as the Green composition. Composition 201 was used as the Red composition. Composition 301 was used as the Blue composition.
The Bayer pattern is, as disclosed in U.S. Pat. No. 3,971,065, one red element, two green elements, and one blue element. ) Element and a 2 × 2 array of color filter elements are repeated.
The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had a suitable image recognition ability.

Claims (18)

  1. 　着色剤と樹脂と有機溶剤とを含む着色組成物であって、
    　前記着色組成物の全固形分中に前記着色剤を５０質量％以上含有し、
    　前記着色剤は、短軸長と長軸長との比率である長軸長／短軸長の値が１．４以上の顔料Ａを４０質量％以上含有する、着色組成物。     A coloring composition containing a colorant, a resin and an organic solvent,
    Containing 50% by mass or more of the colorant in the total solid content of the coloring composition,
    The coloring composition contains 40% by mass or more of pigment A having a major axis length / minor axis length value of 1.4 or more, which is a ratio of the minor axis length to the major axis length.
  2. 　着色組成物の全固形分中に前記着色剤を６０質量％以上含有する、請求項１に記載の着色組成物。 The coloring composition according to claim 1, which contains 60% by mass or more of the coloring agent in the total solid content of the coloring composition.
  3. 　前記顔料Ａは、前記長軸長／短軸長の値が１．４以上３．０以下である、請求項１または２に記載の着色組成物。 The coloring composition according to claim 1 or 2, wherein the pigment A has a major axis length / minor axis length value of 1.4 or more and 3.0 or less.
  4. 　前記顔料Ａの長軸長の平均値が１５～１５０ｎｍである、請求項１～３のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 3, wherein the pigment A has an average major axis length of 15 to 150 nm.
  5. 　前記顔料Ａの短軸長の平均値が１０～１００ｎｍである、請求項１～４のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 4, wherein the pigment A has an average minor axis length of 10 to 100 nm.
  6. 　前記顔料Ａは赤色顔料である、請求項１～５のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 5, wherein the pigment A is a red pigment.
  7. 　前記赤色顔料は、カラーインデックスピグメントレッド２５４、カラーインデックスピグメントレッド２６４、および、カラーインデックスピグメントレッド２７２から選ばれる少なくとも１種である、請求項６に記載の着色組成物。 The coloring composition according to claim 6, wherein the red pigment is at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272.
  8. 　光重合開始剤と重合性化合物とを含む、請求項１～７のいずれか１項に記載の着色組成物。 The colored composition according to any one of claims 1 to 7, comprising a photopolymerization initiator and a polymerizable compound.
  9. 　前記樹脂はアルカリ可溶性樹脂を含む、請求項１～８のいずれか１項に記載の着色組成物。 The colored composition according to any one of claims 1 to 8, wherein the resin contains an alkali-soluble resin.
  10. 　フォトリソグラフィ法でのパターン形成用である、請求項１～９のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 9, which is for forming a pattern by a photolithography method.
  11. 　固体撮像素子用である、請求項１～１０のいずれか１項に記載の着色組成物。 The colored composition according to any one of claims 1 to 10, which is used for a solid-state imaging device.
  12. 　カラーフィルタ用である、請求項１～１０のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 10, which is for a color filter.
  13. 　赤色の画素形成用である、請求項１２に記載の着色組成物。 The colored composition according to claim 12, which is for forming a red pixel.
  14. 　請求項１～１３のいずれか１項に記載の着色組成物から得られる膜。 A film obtained from the coloring composition according to any one of claims 1 to 13.
  15. 　請求項１～１３のいずれか１項に記載の着色組成物を用いて支持体上に着色組成物層を形成する工程と、フォトリソグラフィ法により着色組成物層に対してパターンを形成する工程と、を有するカラーフィルタの製造方法。 A step of forming a coloring composition layer on a support using the coloring composition according to any one of claims 1 to 13, and a step of forming a pattern on the coloring composition layer by a photolithography method. A method of manufacturing a color filter having:
  16. 　請求項１４に記載の膜を有するカラーフィルタ。 A color filter having the film according to claim 14.
  17. 　請求項１４に記載の膜を有する固体撮像素子。 A solid-state image sensor having the film according to claim 14.
  18. 　請求項１４に記載の膜を有する画像表示装置。 An image display device having the film according to claim 14.
PCT/JP2019/038684 2018-10-10 2019-10-01 Coloring composition, film, method for producing color filter, color filter, solid state imaging device and image display device WO2020075568A1 (en)

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