WO2018180918A1 - 感光性着色樹脂組成物及びその硬化物、カラーフィルタ、並びに表示装置 - Google Patents

感光性着色樹脂組成物及びその硬化物、カラーフィルタ、並びに表示装置 Download PDF

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WO2018180918A1
WO2018180918A1 PCT/JP2018/011502 JP2018011502W WO2018180918A1 WO 2018180918 A1 WO2018180918 A1 WO 2018180918A1 JP 2018011502 W JP2018011502 W JP 2018011502W WO 2018180918 A1 WO2018180918 A1 WO 2018180918A1
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group
resin composition
mass
photosensitive
color material
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PCT/JP2018/011502
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English (en)
French (fr)
Japanese (ja)
Inventor
星児 石原
中村　和彦
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株式会社Ｄｎｐファインケミカル
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Priority to JP2018540504A priority Critical patent/JP6450057B1/ja
Priority to CN201880009816.7A priority patent/CN110249263B/zh
Publication of WO2018180918A1 publication Critical patent/WO2018180918A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc

Definitions

  • the present invention relates to a photosensitive colored resin composition, a cured product thereof, a color filter, and a display device.
  • color filters are used.
  • the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image.
  • an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used.
  • a color filter is used for color adjustment.
  • the color filter is generally formed on the substrate to form the substrate, the colored layer including the colored patterns of the three primary colors of red, green, and blue, and the colored patterns.
  • a light shielding portion As one method for forming such a colored layer, there is known a method in which a photosensitive colored resin composition containing a colorant and a photopolymerizable compound is applied onto a substrate and cured by irradiating ultraviolet rays or the like. It has been.
  • pigments and dyes are used as the coloring material of the photosensitive colored resin composition. Although pigments are generally superior in heat resistance and light resistance as compared to dyes, they have a problem that the transmittance is low and the luminance is not sufficiently improved. Therefore, in recent years, photosensitive resin compositions for color filters using dyes with high transmittance have been studied from the viewpoint of further increasing the brightness of color filters, and the heat resistance and light resistance of dyes have been improved. In order to achieve this, the use of a rake color material in which a dye is insolubilized has been studied.
  • Patent Document 1 discloses a color filter using a specific color material containing a divalent or higher cation in which a plurality of dye skeletons are cross-linked by a cross-linking group and a divalent or higher anion.
  • the color material is excellent in heat resistance, and a color filter using the color material is described as having high contrast, excellent solvent resistance and electrical reliability.
  • Patent Document 1 Even if the specific color material of Patent Document 1 is used, since the heat resistance and light resistance are poor compared to the pigment, the chromaticity is likely to change after high-temperature heating (post-baking) in the color filter manufacturing process. Therefore, the brightness of the colored layer obtained is not yet sufficient, and further improvement is required.
  • a colored layer for a color filter is patterned on a substrate.
  • a colored layer using the photosensitive colored resin composition for example, after forming a coating film of the photosensitive colored resin composition on the substrate, it is exposed through a predetermined mask pattern, and then developed. Thus, a patterned colored layer can be obtained.
  • patterning with a smaller exposure amount has been required.
  • the present inventors try to form a blue colored layer using a phthalocyanine pigment, the colored layer as designed is formed. The knowledge that it may not be obtained was acquired.
  • the present invention has been made based on the above knowledge, and is a photosensitive colored resin capable of forming a pattern with a desired line width while improving luminance after a high-temperature heating step (post-baking) in a color filter manufacturing step. It is an object of the present invention to provide a composition, a color filter with improved luminance formed using the photosensitive colored resin composition, and a display device excellent in display characteristics using the color filter.
  • the photosensitive colored resin composition according to the present invention is a photosensitive colored resin composition containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent
  • the color material includes a phthalocyanine pigment and a color material represented by the following general formula (1),
  • the content of the color material represented by the following general formula (1) is 20% by mass to 85% by mass with respect to the total content of the phthalocyanine pigment and the color material represented by the following general formula (1).
  • the present invention provides a cured product of the photosensitive colored resin composition according to the present invention.
  • the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the present invention. Provide a color filter.
  • the present invention provides a display device having the color filter according to the present invention.
  • the photosensitive coloring resin composition which can form a pattern with desired line width, improving the brightness
  • the said photosensitive coloring resin composition A color filter with improved luminance and a display device with excellent display characteristics using the color filter can be provided.
  • FIG. 1 is a schematic view showing an example of the color filter of the present invention.
  • FIG. 2 is a schematic view showing an example of the display device of the present invention.
  • FIG. 3 is a schematic view showing another example of the display device of the present invention.
  • light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 ⁇ m or less and an electron beam.
  • (meth) acryl represents each of acryl and methacryl
  • (meth) acrylate represents each of acrylate and methacrylate.
  • C.I. I. Pigment Blue “PB”, C.I. I. Pigment violet is abbreviated as “PV” where appropriate.
  • the photosensitive colored resin composition according to the present invention is a photosensitive colored resin composition containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent.
  • the color material includes a phthalocyanine pigment and a color material represented by the following general formula (1),
  • the content of the color material represented by the following general formula (1) is 20% by mass to 85% by mass with respect to the total content of the phthalocyanine pigment and the color material represented by the following general formula (1). It is characterized by.
  • A is an a-valent organic group in which the carbon atom directly bonded to N has no ⁇ bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N.
  • B c- represents a c-valent anion
  • R i to R v each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group
  • R ii , R iii , R iv and R v may combine to form a ring structure
  • R vi and R vii each independently represents an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom, or .
  • Ar 1 represents cyano group represents a divalent aromatic group which may have a substituent
  • a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more.
  • e is 0 or 1, and when e is 0, there is no bond.
  • f and g represent an integer of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less.
  • a plurality of e, f and g may be the same or different.
  • the photosensitive colored resin composition of the present invention has an effect that a pattern can be formed with a desired line width while improving luminance after high-temperature heating (post-baking) in a color filter manufacturing process. Since the post-baking process in the color filter manufacturing process is heated at a high temperature of 230 ° C. or 240 ° C., a pigment has been conventionally used as a coloring material because it is difficult to fade against the high temperature heating. Furthermore, in recent years, in order to increase production efficiency, patterning with a smaller amount of exposure is required. However, when the present inventors try to form a blue colored layer using a phthalocyanine pigment, the colored layer as designed is used. It was found that may not be formed.
  • the blue phthalocyanine pigment absorbs around 300 nm, which is the absorption wavelength (radical generation wavelength) of the photoinitiator, so that the photopolymerization reaction does not proceed sufficiently and insufficient curing inside the colored layer occurs during exposure.
  • the phthalocyanine pigment is represented by the specific general formula (1) by using the color material represented by the specific general formula (1) in combination at a specific ratio. Since the coloring material hardly absorbs wavelengths of around 300 nm, the photosensitive coloring resin composition for the blue colored layer combined with the negative photosensitive binder component is unlikely to be insufficiently cured inside the colored layer during exposure. It becomes easy to form a pattern with a line width of.
  • the color material represented by the specific general formula (1) is used in combination with the phthalocyanine pigment at a specific ratio, thereby suppressing the fading caused by the color material represented by the specific general formula (1).
  • the transmittance can be improved and the luminance of the colored layer finally obtained after high-temperature heating (post-baking) in the color filter manufacturing process can be improved.
  • the photosensitive colored resin composition of the present invention contains at least a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and in a range not impairing the effects of the present invention. Further, other components may be contained. Hereinafter, each component of the photosensitive colored resin composition of the present invention will be described in detail in order.
  • the color material includes a phthalocyanine pigment and the color material represented by the general formula (1), and the content of the color material represented by the following general formula (1) is the phthalocyanine pigment and the following general formula. It is 20 mass% or more and 85 mass% or less with respect to the total content of the color material represented by (1).
  • the phthalocyanine pigment is preferably a blue phthalocyanine pigment because it is used in combination with the colorant represented by the general formula (1), and a copper phthalocyanine pigment is preferable from the viewpoint of relatively excellent luminance.
  • a copper phthalocyanine pigment is preferable from the viewpoint of relatively excellent luminance.
  • the phthalocyanine pigment is C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 15: 3, and C.I. I. It is preferably one or more selected from the group consisting of CI Pigment Blue 15: 4.
  • the color material represented by the general formula (1) contains a divalent or higher valent anion and a divalent or higher cation, in the aggregate of the color material, the anion and the cation are simply one molecule pair.
  • the apparent molecular weight is significantly increased compared to the molecular weight of conventional lake pigments because it can form molecular aggregates in which multiple molecules are associated via ionic bonds, rather than being ionically bonded by one molecule. To do.
  • the formation of such molecular aggregates increases cohesion in the solid state, reduces thermal motion, suppresses ion pair dissociation and cation decomposition, and is estimated to be less susceptible to fading than conventional lake pigments. Is done.
  • a in the general formula (1) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) has no ⁇ bond, and the organic group is saturated at least at the terminal directly bonded to N.
  • An aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group is represented, and O (oxygen atom), S (sulfur atom), and N (nitrogen atom) are present in the carbon chain. It may be included. Since the carbon atom directly bonded to N does not have a ⁇ bond, the color characteristics such as the color tone and transmittance of the cationic coloring portion are not affected by the linking group A and other coloring portions, Similar colors can be retained.
  • an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a ⁇ bond.
  • the carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good.
  • a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
  • the aromatic group having an aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N. Especially, it is preferable that A contains a cyclic
  • the cyclic aliphatic hydrocarbon groups a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness.
  • the bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane.
  • norbornane is preferable.
  • the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable.
  • A is a divalent organic group, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group substituted with two alkylene groups having 1 to 20 carbon atoms such as a xylylene group Etc.
  • the valence a in A is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more.
  • the cation valence a is preferably 3 or more.
  • the upper limit of a is not particularly limited, but a is preferably 4 or less, and more preferably 3 or less, from the viewpoint of ease of production.
  • the alkyl group for R i to R v is not particularly limited. Examples thereof include straight-chain or branched alkyl groups having 1 to 20 carbon atoms.
  • straight-chain or branched alkyl groups having 1 to 8 carbon atoms are preferable, and straight chain having 1 to 5 carbon atoms.
  • a chain or branched alkyl group is more preferable from the viewpoint of luminance and heat resistance.
  • the alkyl group in R i to R v is particularly preferably an ethyl group or a methyl group.
  • the substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, and the substituted alkyl group includes an aralkyl group such as a benzyl group. Etc.
  • the aryl group in R i to R v is not particularly limited.
  • R i to R v are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ii and R iii , or R iv and R v.
  • R i to R v are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ii and R iii , or R iv and R v.
  • R i to R v can each independently have the above-described structure, and among these, R i is preferably a hydrogen atom from the viewpoint of color purity, and R ii to R ii from the viewpoint of ease of production and raw material procurement. More preferably, R v are all the same.
  • R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group.
  • the alkyl group in R vi and R vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and an alkyl having 1 to 4 carbon atoms. More preferably, it is a group.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched.
  • the substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
  • the alkoxy group in R vi and R vii is not particularly limited, but is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and has 1 to 4 carbon atoms. More preferably, it is an alkoxy group.
  • Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, which may be linear or branched.
  • the substituent that the alkoxy group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
  • Examples of the halogen atom in R vi and R vii include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the number of substitutions of R vi and R vii that is, f and g each independently represents an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, and more preferably 0 or more and 1 or less.
  • a plurality of f and g may be the same or different.
  • R vi and R vii may be substituted at any part of the aromatic ring having a resonance structure in the triarylmethane skeleton or the xanthene skeleton, and among them, —NR ii R iii or —NR iv it is preferably substituted in the meta position relative to the substitution position of the amino group represented by R v.
  • the divalent aromatic group in Ar 1 is not particularly limited.
  • the aromatic group for Ar 1 the same aromatic groups as those described for the aromatic group for A can be used.
  • Ar 1 is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group containing a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.
  • a plurality of R i to R vii and Ar 1 in one molecule may be the same or different.
  • the combination of R i to R vii and Ar 1 can be adjusted to a desired color.
  • the anion part (B c ⁇ ) is a c-valent anion and is an anion having a valence of 2 or more, and is not particularly limited. It may be an anion.
  • the organic anion represents an anion containing at least one carbon atom.
  • an inorganic anion represents the anion which does not contain a carbon atom. Specific examples of the organic anion and the inorganic anion include those described in International Publication No. 2012/144520 pamphlet.
  • B c ⁇ is an inorganic anion from the viewpoint of high luminance and excellent heat resistance.
  • the inorganic anion include an oxo acid anion (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO 4 2 ⁇ ), molybdate ion (MoO 4 2 ⁇ ), etc.) and a plurality of oxo acids.
  • inorganic anions such as polyacid anions and mixtures thereof.
  • a polyacid anion is preferable from the viewpoint of heat resistance.
  • the polyacid may be an isopolyacid anion (M m O n ) c- or a heteropoly acid anion (X l M m O n ) c- .
  • M represents a poly atom
  • X represents a hetero atom
  • m represents a composition ratio of poly atoms
  • n represents a composition ratio of oxygen atoms.
  • the poly atom M include Mo, W, V, Ti, and Nb.
  • the hetero atom X include Si, P, As, S, Fe, and Co.
  • a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyacid anion containing at least tungsten is more preferable.
  • b represents the number of cations
  • d represents the number of anions in the molecular aggregate
  • b and d represent an integer of 1 or more.
  • a plurality of cations in the molecular aggregate may be one kind alone, or two or more kinds may be combined.
  • the anion present in the molecular aggregate may be a single anion or a combination of two or more, and an organic anion and an inorganic anion may be used in combination. .
  • E in the general formula (1) is an integer of 0 or 1.
  • a plurality of e may be the same or different.
  • those containing at least a triarylmethane skeleton are preferably used.
  • a rake color material represented by General formula (1) it can prepare with reference to international publication 2012/144520 pamphlet, for example.
  • the color material in the photosensitive colored resin composition of the present invention includes the phthalocyanine pigment and the color material represented by the general formula (1) as essential components, but the color tone is within the range not impairing the effects of the present invention.
  • other color materials may be used in combination.
  • known pigments, dyes, lake colorants and the like can be used alone or in admixture of two or more.
  • blue color materials include known organic blue pigments different from phthalocyanine pigments, triarylmethane-based lake color materials different from the color material represented by the general formula (1), and the like.
  • a purple color material C.I. I.
  • Known organic purple pigments such as CI Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38.
  • Xanthene dyes and xanthene dye rake color materials as red to reddish purple color materials.
  • the content of the color material represented by the general formula (1) is based on the total content of the phthalocyanine pigment and the color material represented by the general formula (1). Although it is 20 mass% or more and 85 mass% or less, it is preferable that it is 30 mass% or more from the point of the easiness of the patterning with a brightness
  • the total content of the phthalocyanine pigment and the color material represented by the general formula (1) may be 70% by mass or more and 100% by mass or less based on the total amount of the color material. Preferably, it is 80 mass% or more and 100 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less.
  • the average primary particle size of the color material used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a color layer of a color filter, and varies depending on the type of color material used. Is preferably in the range of 10 nm to 100 nm, more preferably 15 nm to 60 nm. When the average primary particle diameter of the color material is in the above range, a display device including a color filter manufactured using the color material dispersion of the present invention can be made with high contrast and high quality. .
  • the average dispersed particle diameter of the color material in the photosensitive colored resin composition varies depending on the type of the color material used, it is preferably within the range of 10 nm to 100 nm, and within the range of 15 nm to 60 nm. It is more preferable.
  • the average dispersed particle diameter of the color material in the photosensitive colored resin composition is a dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. Is.
  • the color material dispersion is appropriately diluted to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). Etc.) and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.).
  • the average distribution particle size here is a volume average particle size.
  • the total content of the coloring material is preferably 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass or less, based on the total solid content of the photosensitive colored resin composition. . If it is at least the lower limit, the colored layer has a sufficient color density when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 ⁇ m to 5.0 ⁇ m). Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board
  • the total content of the color material is 15% by mass or more and 65% by mass or less, more preferably 25%, based on the total solid content of the photosensitive colored resin composition. It is preferable to mix
  • the alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected from those that act as a binder resin and are soluble in an alkali developer used for pattern formation.
  • the alkali-soluble resin can be based on an acid value of 40 mgKOH / g or more.
  • a preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. Specifically, for example, an acrylic copolymer having a carboxy group, a styrene-acrylic copolymer having a carboxy group, etc. Acrylic resin, carboxy group-containing epoxy (meth) acrylate resin, and the like.
  • the alkali-soluble resins or the photopolymerizable compound such as the alkali-soluble resin and a polyfunctional monomer are cross-linked. Can be formed.
  • the film strength of the cured film is further improved and the development resistance is improved, and the thermal contraction of the cured film is suppressed and the adhesiveness with the substrate is excellent.
  • the method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods.
  • a method of introducing an ethylenic double bond into a side chain by adding a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, to the carboxy group of the alkali-soluble resin
  • a structural unit having a hydroxyl group into a copolymer adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond into the side chain.
  • alkali-soluble resin has a hydrocarbon ring from the point which the adhesiveness of a colored layer is excellent.
  • a hydrocarbon ring that is a bulky group in the alkali-soluble resin shrinkage during curing is suppressed, peeling from the substrate is eased, and substrate adhesion is improved.
  • hydrocarbon rings include aliphatic hydrocarbon rings that may have a substituent, aromatic hydrocarbon rings that may have a substituent, and combinations thereof. May have a substituent such as an alkyl group, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, or a halogen atom.
  • the hydrocarbon ring may be contained as a monovalent group or a divalent or higher group.
  • hydrocarbon ring examples include aliphatic groups such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane.
  • substituents examples include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a halogen atom.
  • the hydrocarbon ring When an aliphatic hydrocarbon ring is included as the hydrocarbon ring, it is preferable from the viewpoint of improving the heat resistance and adhesion of the colored layer and improving the luminance of the obtained colored layer.
  • the inclusion of the cardo structure is particularly preferable from the viewpoint of improving the curability of the colored layer, suppressing fading of the coloring material, and improving solvent resistance (NMP swelling suppression).
  • An acrylic resin such as an acrylic copolymer having a constitutional unit having a carboxy group and a styrene-acrylic copolymer having a carboxy group includes, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
  • the carboxy group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
  • an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone Mono (meth) acrylates can also be used.
  • a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone Mono (meth) acrylates
  • anhydride containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group.
  • (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.
  • the alkali-soluble resin in the present invention is a carboxy group-containing copolymer such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring.
  • a carboxy group-containing copolymer such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring.
  • Preferred are those containing a carboxy group such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond. More preferably, it is a copolymer.
  • Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl. (Meth) acrylate, styrene, etc. are mentioned.
  • cyclohexyl (meth) acrylate dicyclopentanyl (meth) acrylate, adamantyl
  • the carboxy group-containing copolymer may further contain other structural units such as a structural unit having an ester group such as methyl (meth) acrylate and ethyl (meth) acrylate.
  • the structural unit having an ester group not only functions as a component that suppresses alkali solubility of the photosensitive colored resin composition, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.
  • the carboxy group-containing copolymer can be made into an alkali-soluble resin having desired performance by appropriately adjusting the charged amount of each structural unit.
  • the charging amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 5% by mass or more and more preferably 10% by mass or more with respect to the total amount of the monomer from the viewpoint of obtaining a good pattern.
  • the amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 50% by mass or less, and 40% by mass or less, based on the total amount of monomers. More preferably.
  • the carboxy group-containing copolymer such as an acrylic copolymer having a structural unit having an ethylenic double bond and a styrene-acrylic copolymer, which is more preferably used as an alkali-soluble resin, an epoxy group and an ethylene
  • the compound having an ionic double bond is preferably 10% by mass or more and 95% by mass or less, and preferably 15% by mass or more and 90% by mass or less, based on the charged amount of the carboxy group-containing ethylenically unsaturated monomer. More preferred.
  • the preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is 1,000 or more, the binder function after curing is improved, and if it is 50,000 or less, pattern formation becomes good during development with an alkaline developer.
  • the weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured by a Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.
  • Acrylate compounds are suitable.
  • the epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones.
  • the epoxy (meth) acrylate resin having a carboxy group it is preferable to have the hydrocarbon ring in the molecule, and among them, the one containing a cardo structure improves the curability of the colored layer and causes the colorant to fade. It is preferable from the standpoint of suppression and the remaining film ratio of the colored layer increases.
  • the epoxy (meth) acrylate resin having a carboxy group may be used alone or in combination of two or more.
  • the alkali-soluble resin is preferably selected from those having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) with respect to an alkaline aqueous solution used for the developer.
  • the alkali-soluble resin preferably has an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for the developer and adhesion to the substrate. It is preferable that it is 80 mgKOH / g or more and 280 mgKOH / g or less.
  • the acid value can be measured according to JIS K 0070: 1992.
  • the ethylenically unsaturated bond equivalent in the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group improves the film strength of the cured film, improves the development resistance, and obtains the effect of excellent adhesion to the substrate. From the viewpoint, it is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Moreover, since the ratio of other structural units, such as the structural unit which has the said carboxy group, and the structural unit which has a hydrocarbon ring, can be relatively increased if it is 100 or more, it is excellent in developability and heat resistance. Yes.
  • the ethylenically unsaturated bond equivalent is a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).
  • Ethylenically unsaturated bond equivalent (g / mol) W (g) / M (mol) (In Formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)
  • the ethylenically unsaturated bond equivalent is determined, for example, by measuring the number of ethylenic double bonds contained in 1 g of the alkali-soluble resin in accordance with the test method for the iodine value described in JIS K 0070: 1992. It may be calculated.
  • the alkali-soluble resin used in the photosensitive colored resin composition may be used singly or in combination of two or more, and the content is not particularly limited, but the photosensitive colored resin
  • the alkali-soluble resin is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less, based on the total solid content of the composition.
  • the content of the alkali-soluble resin is not less than the above lower limit value, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is not more than the above upper limit value, film roughness or lack of pattern can be caused during development. Can be suppressed.
  • the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited as long as it can be polymerized by a photoinitiator, and is usually a compound having two or more ethylenically unsaturated double bonds.
  • a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
  • Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include those described in JP2013-029832A.
  • polyfunctional (meth) acrylates may be used alone or in combination of two or more.
  • the photopolymerizable compound has three (trifunctional) or more polymerizable double bonds.
  • a phosphorus atom-containing polyfunctional (meth) acrylate such as tri (2- (meth) acryloyloxyethyl) phosphate is preferable because fading of the rake color material is easily suppressed and luminance after post-baking is easily improved.
  • the content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but the photopolymerizable compound is preferably 5% by mass or more and 60% based on the total solid content of the photosensitive colored resin composition. It is in the range of 10% by mass or more and 40% by mass or less, more preferably 10% by mass or less.
  • the content of the photopolymerizable compound is not less than the above lower limit, photocuring sufficiently proceeds, the exposed portion can suppress elution during development, and the content of the photopolymerizable compound is not more than the above upper limit. Alkali developability is sufficient.
  • Photoinitiator There is no restriction
  • photoinitiators include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, ⁇ -amino ketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, and the like. be able to.
  • the photoinitiator include aromatic ketones such as benzophenone, 4,4′-bisdiethylaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and ethylbenzoin.
  • aromatic ketones such as benzophenone, 4,4′-bisdiethylaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone
  • benzoin ethers such as benzoin methyl ether
  • ethylbenzoin Benzoin, biimidazoles such as 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, etc.
  • Halomethyloxadiazole compounds such as 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1 , 2-Diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl]- -Morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-Benzoyl-4′-methyldiphenyl sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylamin
  • 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one eg, Irgacure 907, manufactured by BASF
  • 2-benzyl-2- (dimethylamino) -1- 4-Morpholinophenyl) -1-butanone
  • 4,4′-bis (diethylamino) benzophenone for example, High Cure ABP, manufactured by Kawaguchi Pharmaceutical
  • diethylthioxanthone are preferably used.
  • an ⁇ -aminoacetophenone photoinitiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and a thioxanthone photoinitiator such as diethylthioxanthone are combined. Is preferable from the viewpoint of adjusting sensitivity, suppressing water stain and improving development resistance.
  • the photoinitiator preferably includes an oxime ester photoinitiator from the viewpoint of improving sensitivity.
  • an oxime ester photoinitiator By using an oxime ester photoinitiator, in-plane line width variations are easily suppressed when forming a fine line pattern. Furthermore, by using an oxime ester photoinitiator, the development resistance is improved, and the effect of suppressing the occurrence of water stain tends to be increased.
  • water stain means that, when a component that enhances alkali developability is used, a trace of water stain is generated after rinsing with pure water after alkali development. Such a water stain disappears after post-baking, so there is no problem as a product. Arise.
  • the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.
  • the oxime ester photoinitiator those having an aromatic ring are preferable, and those having a condensed ring including an aromatic ring are preferable from the viewpoint of reducing contamination of the photosensitive colored resin composition by decomposition products and contamination of the apparatus. Is more preferable, and it is more preferable to have a condensed ring including a benzene ring and a hetero ring.
  • oxime ester photoinitiators examples include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, Special Table 2010-527339, Special Table 2010-527338, It can be appropriately selected from oxime ester photoinitiators described in JP2013-041153A.
  • Irgacure OXE-01 having a carbazole skeleton (manufactured by BASF), Adeka Arcles NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials), ADEKA having a diphenyl sulfide skeleton Arcles NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (manufactured by Changzhou Power Electronics New Materials), TR-PBG-365 (Changzhou Power Electronics New Materials, Inc.) having a fluorene skeleton Or SPI-04 (manufactured by Sanyo) may be used.
  • an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of improving luminance.
  • an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
  • two or more oxime ester photoinitiators are used in combination, two or more oxime ester compounds having different sensitivities are appropriately selected and combined to maintain a good sensitivity while maintaining the line width during pattern formation. Further, it is preferable in that the development resistance and luminance are easily improved and the effect of suppressing the occurrence of water stain is high.
  • the combined use of two types of oxime ester photoinitiators having a diphenyl sulfide skeleton, or the combined use of an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a fluorene skeleton increases heat resistance. From the viewpoint that the luminance is easily improved.
  • the shape of the micropores can be easily improved without greatly reducing the brightness and sensitivity.
  • the photosensitive colored resin composition of the present invention forms, for example, a colored layer on the TFT substrate in order to form a reflective color filter. It is also suitable for applications in which through holes for conduction are formed in the colored layer.
  • “billing” refers to a problem in which dimensional accuracy is deteriorated due to non-uniformity of straight lines or curves at the pattern end.
  • a photoinitiator having a tertiary amine structure such as an ⁇ -aminoacetophenone series has a tertiary amine structure that is an oxygen quencher in the molecule, so that radicals generated from the initiator are hardly deactivated by oxygen, and sensitivity It is because it can improve.
  • a thioxanthone photoinitiator with an oxime ester photoinitiator in terms of sensitivity adjustment, water stain suppression and development resistance improvement, and two or more oxime ester photoinitiators and thioxanthone
  • a combination of a photoinitiator is preferable in that the brightness and development resistance are improved, the sensitivity is easily adjusted, the effect of suppressing the occurrence of water stain is high, and the development resistance is improved.
  • the total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but with respect to the total solid content of the photosensitive colored resin composition, Preferably it is 0.1 mass% or more and 12.0 mass% or less, More preferably, it exists in the range of 1.0 mass% or more and 8.0 mass% or less.
  • this content is not less than the above lower limit, photocuring is sufficiently advanced and the exposed portion is prevented from being eluted during development.
  • solid content is all except a solvent, and a liquid photopolymerizable compound etc. are also contained.
  • the solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the photosensitive colored resin composition and can dissolve or disperse them.
  • a solvent can be used individually or in combination of 2 or more types.
  • Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such
  • glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate, butyl carbitol acetate (BCA), carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol mono Glycol ether solvents such as chill ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl
  • glycol ether acetate solvents examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), carbitol acetate, 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate
  • BCA butyl carbitol acetate
  • carbitol acetate 3-methoxy-3-methyl-1-butyl acetate
  • ethyl ethoxypropionate One or more selected from the group consisting of lactic acid, ethyl lactate, and 3-methoxybutyl acetate is preferable from the viewpoint of solubility of other components and applicability.
  • the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. Usually, it is preferably in the range of 55% by mass to 95% by mass with respect to the total amount of the photosensitive colored resin composition containing the solvent, and more preferably in the range of 65% by mass to 88% by mass. It is more preferable. When the content of the solvent is within the above range, the coating property can be excellent.
  • the colorant is preferably used by being dispersed in a solvent by a dispersant.
  • the dispersant can be appropriately selected from conventionally known dispersants. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer dispersant is preferable because it can be uniformly and finely dispersed.
  • polymer dispersant examples include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; polyethyleneimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxy group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxy) Polyester, polyamide or ester-amide co-condensate having a group The reaction product obtained by reacting one or more compound selected from among the three compounds of the polyester amide)), and the like.
  • a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value is preferable from the viewpoint that the colorant can be suitably dispersed and the dispersion stability is good.
  • a polymer dispersant containing a polymer containing a structural unit having a tertiary amine is preferable from the viewpoint of good dispersibility, no precipitation of foreign matters when forming a coating film, and improvement of luminance and contrast.
  • the structural unit having a tertiary amine is a site having an affinity for the colorant.
  • a polymer containing a structural unit having a tertiary amine usually contains a structural unit that becomes a site having an affinity for a solvent.
  • a polymer containing a structural unit having a tertiary amine among them, a block part containing a structural unit having a tertiary amine (hereinafter sometimes referred to as A block) and a block part having solvent affinity (in the following, it is preferable that a block copolymer having a B block) is excellent in heat resistance and capable of forming a coating film having high luminance.
  • the structural unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may constitute the main chain.
  • a structural unit having a tertiary amine in the side chain is preferable, and among them, the structural unit represented by the following general formula (I) is preferable because the main chain skeleton is hardly thermally decomposed and has high heat resistance. It is more preferable.
  • R 1 is a hydrogen atom or a methyl group
  • Q is a divalent linking group
  • R 2 is an alkylene group having 1 to 8 carbon atoms, — [CH (R 5 ) —CH
  • R 3 And R 4 each independently represents an optionally substituted chain or cyclic hydrocarbon group, or R 3 and R 4 are bonded to each other to form a cyclic structure
  • R 5 and R 6 are Each independently represents a hydrogen atom or a methyl group.
  • x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18.
  • Examples of the divalent linking group Q in the general formula (I) include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, an ether group having 1 to 10 carbon atoms (— R′—OR ′′ —: R ′ and R ′′ are each independently an alkylene group) and combinations thereof.
  • Q is a —COO— group or —CONH— from the viewpoint of heat resistance of the polymer obtained, solubility in propylene glycol monomethyl ether acetate (PGMEA) suitably used as a solvent, and a relatively inexpensive material. It is preferably a group.
  • the divalent organic group R 2 in the general formula (I) is an alkylene group having 1 to 8 carbon atoms, — [CH (R 5 ) —CH (R 6 ) —O] x —CH (R 5 ) —CH (R 6 ) — or — [(CH 2 ) y —O] z — (CH 2 ) y —.
  • the alkylene group having 1 to 8 carbon atoms may be linear or branched.
  • R 5 and R 6 are each independently a hydrogen atom or a methyl group.
  • R 2 is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility. Among them, R 2 is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Groups are more preferred.
  • Examples of the cyclic structure formed by combining R 3 and R 4 in the general formula (I) include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. It is done.
  • the nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring.
  • Examples of the structural unit represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and other alkyl group-substituted amino groups.
  • Examples include group-containing (meth) acrylates, alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and the like.
  • dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
  • At least a part of the amino group of the structural unit having the tertiary amine may be salted with a salt-forming agent.
  • the structural unit contained in the solvent affinity block part a structural unit copolymerizable with the conventionally known general formula (I) can be appropriately selected and used.
  • the B block may be the same as the B block of International Publication No. 2016/104493.
  • the dispersant is a polymer having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less that includes the structure represented by the general formula (I), and has good dispersibility. It is preferable from the viewpoint of improving luminance and contrast without depositing foreign matters.
  • the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and is also excellent in alkali developability and solvent resolubility.
  • the amine value is the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of a sample, and can be measured by the method defined in JIS-K7237: 1995. .
  • the organic acid compound When measured by this method, even if it is an amino group that forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant is itself The amine value of can be measured.
  • the acid value of the dispersant used in the present invention is preferably 0 mgKOH / g from the viewpoint of further improving the solvent re-solubility and development adhesion, and from the viewpoint of substrate adhesion and dispersion stability.
  • it is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more.
  • the acid value of the dispersing agent used for this invention is 18 mgKOH / g or less from the point which can prevent the deterioration of image development adhesiveness and the solvent resolubility.
  • the acid value of the dispersant is more preferably 12 mgKOH / g or less, and even more preferably 8 mgKOH / g or less, from the viewpoint that the development adhesion and the solvent re-solubility are improved.
  • the acid value of the block copolymer before salt formation is 0 mgKOH from the viewpoint of further improving the solvent resolubility and development adhesion, and from the standpoint of substrate adhesion and dispersion stability.
  • the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 12 mgKOH / g or less, from the viewpoint of improving development adhesion and solvent resolubility.
  • it is still more preferable that it is 8 mgKOH / g or less.
  • the glass transition temperature of a dispersing agent is 30 degreeC or more from the point which image development adhesiveness improves. That is, whether the dispersant is a block copolymer before salt formation or a salt block copolymer, the glass transition temperature is preferably 30 ° C. or higher.
  • the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C.), and the development adhesion may be lowered. This is presumably because when the glass transition temperature is close to the developer temperature, the movement of the dispersant increases during development, resulting in poor development adhesion.
  • the glass transition temperature is 30 ° C.
  • the glass transition temperature of the dispersant is preferably 32 ° C. or higher, more preferably 35 ° C. or higher, from the viewpoint of development adhesion. On the other hand, the temperature is preferably 200 ° C. or lower from the viewpoint of operability during use, such as easy precision weighing.
  • the glass transition temperature of the dispersant in the present invention can be determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.
  • the glass transition temperature (Tg) of a block part and a block copolymer can be calculated by the following formula.
  • the monomer whose glass transition temperature (Tgi) of the homopolymer of the monomer is 10 ° C. or higher from the viewpoint that the glass transition temperature of the dispersant used in the present invention is a specific value or higher and development adhesion is improved.
  • Tgi glass transition temperature of the homopolymer of the monomer
  • the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5.
  • the range of 0.1 to 1.0 is more preferable from the viewpoint of the dispersibility and dispersion stability of the color material.
  • the weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, and preferably 2000 to 15000 from the viewpoint of good colorant dispersibility and dispersion stability. More preferably, it is more preferably 3000 to 12000.
  • the weight average molecular weight is determined as a standard polystyrene conversion value by (Mw) and gel permeation chromatography (GPC).
  • Mw polystyrene conversion value by
  • GPC gel permeation chromatography
  • the dispersibility of the coloring material is that the polymer containing a structural unit having a tertiary amine is a block copolymer, and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid.
  • organic acid compound used for such a dispersant include, for example, organic acid compounds described in JP 2012-236882 A and the like.
  • the halogenated hydrocarbon is preferably at least one of allyl halides such as allyl bromide and benzyl chloride and aralkyl halides from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
  • the content in the case of using the dispersant is not particularly limited as long as it can uniformly disperse the coloring material.
  • the content is 1 with respect to the total solid content of the photosensitive colored resin composition. It can be used in the range of from mass% to 40 mass%. Furthermore, it is preferable to mix
  • the photosensitive colored resin composition according to the present invention preferably further contains an antioxidant from the viewpoint of improving heat resistance, suppressing fading of the coloring material, and improving luminance.
  • the photosensitive colored resin composition according to the present invention contains an antioxidant in combination with an oxime ester photoinitiator, so that when the micropores are formed in a cured film, the excess in the micropores is not impaired. Since the radical chain reaction can be controlled, it is possible to more easily form micropores having a desired shape.
  • the antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones.
  • antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. It is preferable to use a hindered phenol type antioxidant from the point which makes the shape of a point and a micropore favorable. It may be a latent antioxidant as described in WO2014 / 021023.
  • hindered phenol-based antioxidant for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3 , 5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2′-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP-S, Manufactured by Sumitomo Chemical Co., Ltd., 6,6'-thiobis (2-tert-butyl-4-methylphenol) (Trade name: Irganox 1081, manufactured
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .
  • antioxidant is 0.1 mass part or more and 10.0 mass part or less with respect to 100 mass parts of total solids in a colored resin composition, 0.5 It is more preferable that the amount is not less than 5.0 parts by mass. If it is more than the said lower limit, it is excellent in heat resistance and light resistance. On the other hand, if it is below the said upper limit, the colored resin composition of this invention can be made into a highly sensitive photosensitive resin composition.
  • the content of the antioxidant is 1 part by mass of the antioxidant with respect to 100 parts by mass of the total amount of the oxime ester photoinitiator.
  • the amount is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and still more preferably 5 parts by mass or more and 65 parts by mass or less. If it is in the said range, it is excellent in the effect of the said combination.
  • the photosensitive colored resin composition of the present invention may contain various additives as necessary.
  • the additives include mercapto compounds, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.
  • Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.
  • the P / V ratio ((color material component mass in the composition) / (solid content mass other than color material components in the composition) ratio) is a blue colored resin composition.
  • the P / V ratio is preferably 0.20 or more, more preferably 0.28 or more, and further preferably 0.35 or more from the viewpoint of desired color development. preferable.
  • it is preferably 0.65 or less, It is more preferably 0.50 or less, and still more preferably 0.45 or less.
  • the method for producing the photosensitive colored resin composition of the present invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, preferably a dispersant, an antioxidant, and, if desired. It is preferable from the point of improving the contrast that the colorant can be uniformly dispersed in the solvent by a dispersant, and contains various additive components used, and is prepared by mixing using a known mixing means. can do.
  • a color material and a dispersant are added to a solvent to prepare a color material dispersion, and the alkali-soluble resin, light, A method of mixing a polymerizable compound, a photoinitiator, and various additive components used as desired; (2) In a solvent, a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator (3) In a solvent, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a photoinitiator are optionally used.
  • the above methods (1) and (4) are preferable from the viewpoint that the aggregation of the coloring material can be effectively prevented and dispersed uniformly.
  • the method for preparing the colorant dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) A dispersant is mixed and stirred in advance to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt between the amino group of the dispersant and the organic acid compound.
  • the dispersing machine for performing the dispersion treatment examples include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill.
  • the bead diameter to be used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.
  • the photosensitive colored resin composition of the present invention can be suitably used for color filter applications because it can form a pattern with a desired line width while improving the luminance after repeating the high-temperature heating process.
  • the cured product according to the present invention is a cured product of the photosensitive colored resin composition according to the present invention.
  • the cured product according to the present invention is obtained, for example, by forming a coating film of the photosensitive colored resin composition according to the present invention, drying the coating film, and then developing the film, if necessary. Can do.
  • a method for forming, exposing, and developing a coating film for example, a method similar to the method used in forming a colored layer provided in the color filter according to the present invention described later can be used.
  • the cured product according to the present invention has improved brightness even after the high-temperature heating step, and a pattern is formed with a desired line width, and is suitably used as a colored layer of a color filter. .
  • the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive colored resin composition according to the present invention. It is a cured product.
  • FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention.
  • the color filter 10 of the present invention has a substrate 1, a light shielding part 2, and a colored layer 3.
  • At least one of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored resin composition according to the present invention, that is, a colored layer formed by curing the colored resin composition.
  • the colored layer is usually formed in an opening of a light-shielding part on the substrate to be described later, and is usually composed of a colored pattern of three or more colors.
  • the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used.
  • variety, area, etc. of a colored layer can be set arbitrarily.
  • the thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the photosensitive colored resin composition.
  • the colored layer can be formed by the following method, for example.
  • the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, so that a photopolymerizable compound such as an alkali-soluble resin and a polyfunctional monomer is irradiated with light.
  • a polymerization reaction is performed to obtain a cured coating film.
  • the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam.
  • the exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
  • the heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.
  • a coating film is formed with a desired pattern by melt
  • a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used.
  • An appropriate amount of a surfactant or the like may be added to the alkaline solution.
  • a general method can be adopted as the developing method.
  • the developer is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer.
  • the heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.
  • the light shielding part in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be the same as that used as a light shielding part in a general color filter.
  • the pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape.
  • the light shielding part may be a metal thin film such as chromium by sputtering, vacuum deposition or the like.
  • the light shielding part may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder.
  • the thickness of the light-shielding part is set to about 0.2 ⁇ m to 0.4 ⁇ m in the case of a metal thin film, and about 0.5 ⁇ m to 2 ⁇ m in the case where a black pigment is dispersed or dissolved in a binder resin. Set by.
  • substrate As the substrate, a transparent substrate or a silicon substrate, which will be described later, or an aluminum, silver, or silver / copper / palladium alloy thin film formed on the substrate is used. On these substrates, another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed.
  • the transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used.
  • transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
  • the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing about 100 micrometers or more and 1 mm or less can be used, for example.
  • the color filter of the present invention includes, for example, an overcoat layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, etc., in addition to the substrate, the light shielding portion, and the colored layer. Also good.
  • a display device includes the color filter according to the present invention.
  • the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device and an organic light emitting display device.
  • the liquid crystal display device of the present invention includes the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
  • a liquid crystal display device of the present invention will be described with reference to the drawings.
  • FIG. 2 is a schematic diagram illustrating an example of a display device of the present invention, and is a schematic diagram illustrating an example of a liquid crystal display device.
  • the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
  • the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.
  • the driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used. Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
  • a method for forming a liquid crystal layer a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
  • An organic light emitting display device includes the above-described color filter according to the present invention and an organic light emitter. Such an organic light emitting display device of the present invention will be described with reference to the drawings.
  • FIG. 3 is a schematic diagram illustrating another example of the display device of the present invention, and is a schematic diagram illustrating an example of an organic light emitting display device.
  • the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80.
  • An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.
  • the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60.
  • the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80 known structures can be appropriately used.
  • the organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
  • the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.
  • the acid value of the block copolymer before salt formation was calculated
  • the amine value of the block copolymer before salt formation was determined by a method according to the method described in JIS K 7237: 1995.
  • the weight average molecular weight (Mw) of the block copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above.
  • the glass transition temperature (Tg) of the block copolymer before salt formation and after salt formation is determined by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology Co., Ltd.) according to the method described in JIS K7121. It measured using.
  • DSC differential scanning calorimetry
  • EEMA 1-ethoxyethyl methacrylate
  • TMSMA 2- (trimethylsilyloxy) ethyl methacrylate
  • EHMA 2-ethylhexyl methacrylate
  • BMA n-butyl methacrylate
  • BzMA benzyl methacrylate
  • MMA methyl methacrylate
  • DMMA dimethylaminoethyl methacrylate
  • MAA methacrylic acid
  • the structural unit was derived from 2-hydroxyethyl methacrylate (HEMA).
  • HEMA 2-hydroxyethyl methacrylate
  • the obtained block copolymer PGMEA solution was reprecipitated in hexane, purified by filtration and vacuum drying, and the block copolymer 1 containing the structural unit represented by the general formula (I) (amine value 95 mgKOH / g, acid value 8 mgKOH / g, Tg38 ° C.).
  • the weight average molecular weight Mw was 7730.
  • Pigment Blue 15: 6 (PB15: 6, trade name FASTOGEN BLUE A510 manufactured by DIC Corporation) 13.0 parts by mass, particle size 2.0 mm Zirconia beads 100 parts by mass, paint shaker (Asada Tekkosha) as a preliminary crushing The mixture was then shaken for 1 hour, then changed to 200 parts of zirconia beads having a particle size of 0.1 mm, and dispersed for 4 hours with a paint shaker as the main crushing to obtain a colorant dispersion A.
  • paint shaker Asada Tekkosha
  • Preparation Example 3 Preparation of photosensitive binder component CR-3
  • SPI-04 manufactured by Sanyo, oxime ester photoinitiator having a fluorene skeleton
  • OXE-02 manufactured by BASF, oxime ester photoinitiator having a carbazole skeleton
  • Preparation Example 4 Preparation of photosensitive binder component CR-4
  • SPI-04 manufactured by Sanyo, oxime ester photoinitiator having a fluorene skeleton
  • SPI-04 manufactured by Sanyo, oxime ester photoinitiator having a fluorene skeleton
  • TR-PBG-3057 manufactured by Changzhou Power Electronics New Materials Co., Ltd., an oxime ester photoinitiator having a diphenyl sulfide skeleton
  • a photosensitive binder component CR-4 was obtained.
  • Example 1 Preparation of photosensitive colored resin composition
  • 4.0 parts by weight of colorant dispersion A, 22.6 parts by weight of colorant dispersion C, 24.6 parts by weight of photosensitive binder component CR-1 of Preparation Example 1, surfactant Megafac R08MH (manufactured by DIC) 0 0.02 part by mass and 48.8 parts by mass of PGMEA were mixed to obtain a photosensitive colored resin composition of Example 1.
  • Example 2 to 5 Comparative Examples 1 to 10: Preparation of photosensitive colored resin composition
  • Example 2 to 5 were the same as Example 1 except that the color material dispersion used was changed so that the color material ratios (mass ratios) shown in Table 1-1 to Table 1-3 were obtained.
  • the photosensitive colored resin compositions of Comparative Examples 1 to 10 were obtained.
  • Example 6 Preparation of photosensitive colored resin composition
  • a photosensitive colored resin composition of Example 6 was obtained in the same manner as in Example 1 except that the photosensitive binder component CR-1 in Example 1 was changed to the photosensitive binder component CR-2 in Preparation Example 2. .
  • Example 7 to 10 Comparative Examples 11 to 20: Preparation of photosensitive colored resin composition
  • Examples 7 to 10 were the same as Example 6 except that the color material dispersion used was changed so that the color material ratios (mass ratios) shown in Table 2-1 to Table 2-3 were obtained.
  • the photosensitive colored resin compositions of Comparative Examples 11 to 20 were obtained.
  • Example 11 Preparation of photosensitive colored resin composition
  • a photosensitive colored resin composition of Example 11 was obtained in the same manner as in Example 1 except that the photosensitive binder component CR-1 of Example 1 was changed to the photosensitive binder component CR-3 of Preparation Example 3. .
  • Example 12 Preparation of photosensitive colored resin composition
  • a photosensitive colored resin composition of Example 12 was obtained in the same manner as in Example 1 except that the photosensitive binder component CR-1 in Example 1 was changed to the photosensitive binder component CR-4 in Preparation Example 4. .
  • the table shows the luminance after post-baking at 230 ° C. for 25 minutes and the luminance after the heat resistance test (after 230 ° C.
  • ⁇ Eab ⁇ (L 1 ⁇ L 0 ) 2 + (a 1 ⁇ a 0 ) 2 + (b 1 ⁇ b 0 ) 2 ⁇ 1/2 ⁇ Eab is 3 or less, A is ⁇ Eab is more than 3 and less than 5 is B, ⁇ Eab is more than 5 and less than 10 is C, and ⁇ Eab is more than 10 is D. It is evaluated that the smaller the value of ⁇ Eab, the better the heat resistance.
  • UV light of 60 mJ / cm 2 was irradiated using a super high pressure mercury lamp through a photomask pattern having a pattern (pattern for evaluating micropores) in which a chrome mask was arranged. Then, the glass plate on which the colored layer was formed was shower-developed using 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and post-baked for 30 minutes in a 230 ° C. clean oven.
  • the width (line width) of the actually measured independent thin line when the opening width of the photomask was 90 ⁇ m and the design line width was 95 ⁇ m was measured.
  • Line width shift The line width shift value ( ⁇ m), which is a deviation from the design line width, was calculated by the following formula.
  • Line width shift value ( ⁇ m) Measured line width ( ⁇ m) ⁇ 95 ( ⁇ m) A: Line width shift value of ⁇ 2 ⁇ m or more and 2 ⁇ m or less B: Line width shift value of ⁇ 4 ⁇ m or more and less than ⁇ 2 ⁇ m C: Line width shift value of less than ⁇ 4 ⁇ m or more than 2 ⁇ m It is evaluated that a pattern can be formed with a width.
  • Deviations in the size of the micropores formed in the colored layer with respect to the dimension of 2 to 6% in absolute value C: formed in the colored layer with respect to the dimension of the chrome mask arranged in the independent fine line pattern Deviation of the dimension of the formed micropore is larger than 6% and not more than 8% in absolute value.
  • D The dimension deviation of the microhole formed in the colored layer is different from the dimension of the chromium mask arranged in the independent thin line pattern. The absolute value is larger than 8%. Note that the dimensional deviation was calculated as an average value of the dimensional deviation of each side.
  • the photosensitive coloring resin compositions of Examples 1 to 12 in which the coloring material is a combination of the phthalocyanine pigment and the coloring material represented by the general formula (1) at a specific ratio are 230 ° C. Both the brightness after the post-baking for 25 minutes and the brightness after the heat test (after the post-baking at 230 ° C. for 25 minutes + 240 ° C. for 25 minutes + 240 ° C. for 25 minutes) improved the high temperature heating process (post baking) It was clarified that a pattern can be formed with a desired line width while improving the luminance later.
  • any of the comparative examples in which the phthalocyanine pigment is combined with a rake color material different from the color material represented by the general formula (1) has poor heat resistance, and even when used in the same ratio as in the examples, The brightness after the high-temperature heating process (post-baking) was low.
  • the violet pigment is combined with the phthalocyanine pigment
  • the heat resistance itself is not a problem
  • the brightness after the high-temperature heating process (post-baking) is low, and the shift value from the design line width is large and the desired line width is obtained. It was difficult to obtain a pattern.

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