WO2015122284A1 - Colored resin composition, cured film using same, color filter and production method therefor, solid-state imaging element, and image display device - Google Patents

Colored resin composition, cured film using same, color filter and production method therefor, solid-state imaging element, and image display device Download PDF

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Publication number
WO2015122284A1
WO2015122284A1 PCT/JP2015/052489 JP2015052489W WO2015122284A1 WO 2015122284 A1 WO2015122284 A1 WO 2015122284A1 JP 2015052489 W JP2015052489 W JP 2015052489W WO 2015122284 A1 WO2015122284 A1 WO 2015122284A1
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resin composition
colored
colored resin
general formula
color filter
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PCT/JP2015/052489
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French (fr)
Japanese (ja)
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陽樹 稲部
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富士フイルム株式会社
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Priority to KR1020167020405A priority Critical patent/KR101752269B1/en
Publication of WO2015122284A1 publication Critical patent/WO2015122284A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14621—Colour filter arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
    • H01L27/14685—Process for coatings or optical elements

Definitions

  • the present invention relates to a colored resin composition.
  • the present invention relates to a colored resin composition preferably used for forming a colored layer of a color filter.
  • the present invention relates to a cured film, a color filter, a solid-state imaging device, and an image display device using the colored resin composition.
  • the present invention also relates to a method for producing a color filter using a colored resin composition.
  • the colorant used in the color filter is commonly required to have the following characteristics. In other words, it has optical characteristics that are favorable for color reproducibility, optical scattering such as light scattering that causes a decrease in contrast of a liquid crystal display, and unevenness in optical density that causes color unevenness and roughness of a solid-state imaging device. There is a need for it to be free, toughness under the environmental conditions used, for example, heat resistance, light resistance, moisture resistance, etc., to have a large molar extinction coefficient and to be thin. For this reason, it is common to use a pigment as a colorant.
  • Patent Document 1 discloses a colored resin composition for a color filter containing a pigment and a polyamic acid.
  • Patent Document 2 discloses a polyhalogenated zinc phthalocyanine pigment composition.
  • R 2 represents a hydrocarbon group, or a hydrocarbon group and —Si (R 2A ) 2 , —CO—, —NR—, —O—, —SO 2 —, and —
  • ⁇ 13> A cured film obtained by curing the colored resin composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 14> A color filter having a colored layer using the colored resin composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 15> a step of forming a colored film by applying the colored resin composition according to any one of ⁇ 1> to ⁇ 12> on a substrate; Heating and curing the colored film at 150 to 350 ° C., Applying a photoresist on the cured colored film; Patterning the photoresist by pattern development of the photoresist, followed by alkali development, Using the patterned photoresist as an etching mask, patterning a colored film under the photoresist by dry etching, Removing the photoresist after patterning;
  • a method for producing a color filter comprising: ⁇ 16> A solid-state imaging device having a color filter according to ⁇ 14> or a color filter obtained by the method for producing a
  • the present invention it is possible to provide a colored resin composition capable of suppressing the formation of needle-like foreign matters in the boundary region between the green pixel and the adjacent colored pixel during high-temperature heating.
  • a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device using the colored resin composition it has become possible to provide a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device using the colored resin composition.
  • the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
  • the solid content at 25 ° C.
  • the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent together with a group (atomic group) having no 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).
  • “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • light means actinic rays or radiation.
  • exposure in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
  • (meth) acrylate represents both and / or acrylate and methacrylate
  • (meth) acryl represents both and / or acryl and “(meth) acrylic”
  • "Acryloyl” represents both and / or acryloyl and methacryloyl.
  • “monomer” and “monomer” are synonymous.
  • a monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer.
  • the polymerizable functional group refers to a group that participates in a polymerization reaction.
  • Me in the chemical formula represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
  • 0.0 mm ID ⁇ 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
  • the colored resin composition of the present invention includes a polyamic acid having a repeating unit represented by the following general formula (1) and PG58.
  • R 1 represents an n + divalent linking group
  • R 2 represents a divalent linking group
  • n represents 1 or 2.
  • a color filter using PG58 is heated at a high temperature in a state where pixels containing a blue pigment (for example, CI Pigment Blue 15: 6 (hereinafter also referred to as “PB15: 6”)) are adjacent to each other.
  • PB15: 6 CI Pigment Blue 15: 6
  • the said subject can be solved by using the coloring resin composition containing PG58 and the polyamic acid which has a repeating unit represented by General formula (1). Moreover, solvent resistance can also be improved. Although this mechanism is presumed, the polyamic acid contained in the colored resin composition of the present invention causes imide cyclization accompanied by a dehydration reaction in the post-baking step after the pixel pattern is formed.
  • the polyamic acid contained in the colored resin composition of the present invention forms a dense film having a very high film density by the imide cyclization, PG58 can be firmly held in the polyimide film. As a result, it is possible to suppress the occurrence of acicular foreign matters during high temperature heating.
  • R 1 is a group derived from an acid anhydride and represents an n + divalent linking group.
  • the polyamic acid having a repeating unit represented by the general formula (1) also functions as a dispersant for dispersing PG58 in the colored resin composition. It also functions as a thermosetting agent.
  • R 1 is preferably an n + divalent linking group having 2 to 22 carbon atoms. Specifically, R 1 is n + 2 consisting of a hydrocarbon group or a combination of a hydrocarbon group and at least one of —CO—, —NR—, —O—, —SO 2 —, and —S—.
  • a valent linking group is preferable, and a hydrocarbon group or an n + divalent linking group composed of a combination of a hydrocarbon group and —CO— is more preferable.
  • R 1 may be an n + divalent linking group comprising a combination of one hydrocarbon group and —CO—, —NR—, —O—, —SO 2 —, or —S—, N + divalent linking group comprising a combination of two or more hydrocarbon groups and two or more groups selected from —CO—, —NR—, —O—, —SO 2 —, and —S—. May be.
  • R 1 is an n + divalent linking group comprising a combination of a hydrocarbon group and at least one of —CO—, —NR—, —SO 2 —, —O— and —S—, -, -NR-, -O-, -SO 2- , and -S- are preferably not adjacent to each other.
  • R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom.
  • the hydrocarbon group contained in the n + divalent linking group may be linear, branched or cyclic, but is preferably cyclic.
  • R 1 preferably includes a cyclic structure, and preferably includes a cyclic hydrocarbon group.
  • the cyclic structure may be an alicyclic ring or an aromatic ring, but is preferably an aromatic ring.
  • the cyclic structure may be monocyclic or polycyclic.
  • the cyclic structure preferably contains a 5- to 8-membered ring, and more preferably contains a 5- or 6-membered ring. Further, the cyclic structure may be monocyclic or heterocyclic.
  • the hetero atom constituting the heterocyclic ring include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • R 1 preferably has an alicyclic hydrocarbon group having 3 to 22 carbon atoms or an aromatic hydrocarbon group having 6 to 22 carbon atoms, and preferably has an aromatic hydrocarbon group having 6 to 22 carbon atoms. And more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • R 2 is a group derived from diamine and represents a divalent linking group.
  • R 2 is preferably a divalent linking group having 1 to 22 carbon atoms.
  • R 2 is selected from a hydrocarbon group, or a hydrocarbon group and —Si (R 2A ) 2 —, —CO—, —NR—, —O—, —SO 2 —, —S—.
  • a divalent linking group containing a group composed of a combination with at least one kind is preferred.
  • R 2 is a divalent linkage comprising a combination of one hydrocarbon group and —Si (R 2A ) 2 —, —CO—, —NR—, —O—, —SO 2 —, or —S—.
  • R 2A represents an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.
  • R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the hydrocarbon group may be linear, branched or cyclic.
  • R 2 preferably contains a cyclic structure, and preferably contains a cyclic hydrocarbon group.
  • the cyclic structure is synonymous with the cyclic structure that R 1 in the general formula (1) may have, and the preferred range is also the same.
  • R 2 is more preferably a divalent linking group having an alicyclic hydrocarbon skeleton having 3 to 22 carbon atoms or an aromatic hydrocarbon skeleton having 6 to 22 carbon atoms, and an aromatic hydrocarbon skeleton having 6 to 18 carbon atoms.
  • a divalent linking group having a phenylene group is particularly preferable.
  • n represents 1 or 2, and 2 is preferable. By setting it to 2, the effect of the present invention is more effectively exhibited.
  • the polyamic acid used in the present invention preferably has a repeating unit (repeating unit A) in which R 2 in the general formula (1) includes a cyclic structure.
  • the polyamic acid used in the present invention further has a repeating unit (repeating unit B) in which R 2 in the general formula (1) includes a hydrocarbon group and the partial structure of —Si (R 2A ) 2 — described above. You may do it.
  • the polyamic acid has a repeating unit including a partial structure of —Si (R 2A ) 2 —, the adhesion to the substrate can be further improved when a cured film is formed using the colored resin composition. it can.
  • the amount of the repeating unit B that may be contained is preferably 0.5 to 15 mol%, more preferably 1 to 10 mol%. Preferably, 3 to 7 mol% is more preferable.
  • the polyamic acid having a repeating unit represented by the general formula (1) can be synthesized by a known method, for example, by selectively combining an acid anhydride and a diamine and reacting them in a solvent.
  • anhydride tricarboxylic acid anhydride or tetracarboxylic acid anhydride can be used, and tetracarboxylic acid anhydride is preferably used.
  • Tricarboxylic acid anhydrides include trimellitic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, 1,2,4-naphthalene tricarboxylic acid-1,2-anhydride, 1, 3,8-naphthalenetricarboxylic acid-1,8-anhydride and the like.
  • tetracarboxylic acid anhydrides include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltrifluoropropanetetracarboxylic acid Anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ′′, 4,4 ′′ -para-phenyltetracarboxylic Acid dianhydride, 3,3 ′′, 4,4 ′′ -metha-phenyltetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclo Pentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclo
  • diamines examples include 4,4'-diaminodiphenyl ether, 4,4 '(or 3,3')-diaminodiphenyl sulfone, 4,4'-diaminobenzanilide, 3,3'- (or 4,4 ' ) Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,5-diaminotoluene, o-tolidine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) ) Biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane 1,3- (or 1,4) diaminocyclohe
  • a monomer constituting the above-mentioned repeating unit B for example, (3-aminopropyl) tetramethyldisiloxane (siloxane diamine)
  • siloxane diamine 3-aminopropyl tetramethyldisiloxane (siloxane diamine)
  • the amount of siloxane diamine is preferably 1 to 20 mol% in the total diamine.
  • Siloxane diamine may be used individually by 1 type, and may use 2 or more types.
  • Examples of the solvent that can be used for synthesizing the polyamic acid having the repeating unit represented by the general formula (1) include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and the like. These amide polar solvents and lactone polar solvents can be used in admixture. Examples of solvents other than lactones include methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol and the like in addition to the amide polar solvent. Lactones are aliphatic cyclic esters having 3 to 12 carbon atoms.
  • ⁇ -propiolactone ⁇ -butyrolactone
  • ⁇ -valerolactone ⁇ -valerolactone
  • ⁇ -caprolactone ⁇ -caprolactone
  • ⁇ -caprolactone ⁇ -caprolactone
  • the polyamic acid having the repeating unit represented by the general formula (1) may be prepared by using the acid anhydride or diamine other than the above-described acid anhydride or other amine component to adjust the molecular weight of the polyamic acid.
  • the other acid component and the other diamine component include a monofunctional acid and an amine component.
  • the monofunctional acid or amine component include monocarboxylic acid, carboxylic dianhydride, monoamine and the like. Specific examples include, but are not limited to, benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, aniline, and the like.
  • the amount of the other acid component or other amine component is 0.5 to 5 based on the total number of moles of carboxylic dianhydride and diamine and other acid components and other amine components used in the synthesis of the polyamic acid.
  • the mol% is preferable, 0.7 to 3 mol% is more preferable, and 0.9 to 2 mol% is more preferable.
  • the weight average molecular weight of the polyamic acid having a repeating unit represented by the general formula (1) is preferably 5000 or more, more preferably 6,000 to 100,000, and further preferably 8,000 to 50,000.
  • the dispersity (mass average molecular weight / number average molecular weight) of the polyamic acid having a repeating unit represented by the general formula (1) is preferably 1.1 to 4.0, more preferably 1.5 to 3.0, More preferably, it is 1.7 to 2.5.
  • the content of the polyamic acid having the repeating unit represented by the general formula (1) in the colored resin composition is preferably 5 to 50% by mass, and preferably 7 to 40% by mass with respect to the total solid content of the colored resin composition. % Is more preferable, and 9 to 30% by mass is further preferable.
  • the amount of the polyamic acid having the repeating unit represented by the general formula (1) with respect to the total mass of the resin components contained in the colored resin composition can be 90% by mass, or 95 to 100% by mass. You can also.
  • the colored resin composition may contain only one type of polyamic acid having a repeating unit represented by the general formula (1), or may contain two or more types. When 2 or more types are included, the total amount thereof preferably corresponds to the above content.
  • the colored resin composition contains PG58.
  • PG58 can be synthesized, for example, by the method described in paragraphs 0084 to 0085 of JP-A-2007-284592, the contents of which are incorporated herein.
  • the average primary particle size of PG58 used in the present invention is practically 10 nm or more.
  • the upper limit is preferably 1 ⁇ m or less, more preferably 500 nm or less, further preferably 200 nm or less, further preferably 100 nm or less, and particularly preferably 50 nm or less from the viewpoint of obtaining better contrast.
  • the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified.
  • the monodispersity of the pigment fine particles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1. 5 is particularly preferred.
  • the average primary particle diameter of the particles is obtained by obtaining the equivalent circle diameter from an image observed with a transmission electron microscope, and taking the average value of the 500 particles.
  • the PG58 particles may be prepared by ordinary methods, for example, by pulverizing by milling (breakdown method) or by precipitation using a good solvent and a poor solvent (buildup method). May be.
  • breakdown method a pigment particle can be refined
  • the latter build-up method
  • the colored resin composition may or may not contain a colorant other than PG58. Other colorants may be used alone or in combination of two or more.
  • the colored resin composition is used as another colorant. It may contain a yellow colorant.
  • a yellow pigment is preferable. I. Pigment yellow 129, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. More preferably at least one selected from CI Pigment Yellow 185; I. Pigment Yellow 129 is more preferable. By setting it as such a structure, the effect of this invention can be improved more.
  • the colored resin composition of the present invention includes a halogenated phthalocyanine pigment having, as a central metal, one selected from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta, and Nb, and One or more phthalocyanine pigments selected from halogenated phthalocyanine pigments having no central metal may be further included.
  • a halogenated phthalocyanine pigment having, as a central metal one selected from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta, and Nb
  • One or more phthalocyanine pigments selected from halogenated phthalocyanine pigments having no central metal may be further included.
  • the content of the phthalocyanine pigment is preferably 5% by mass or less, more preferably 0.5 to 2% by mass with respect to the content of PG58 in the colored resin composition.
  • organic pigments other than the above-described PG58 and yellow pigments, inorganic pigments, dyes, and the like can be used.
  • examples of other organic pigments that can be appropriately added to the colored resin composition of the present invention include: C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,147,151,154,155,167,180,199; C. I. Pigment orange 36, 38, 43, 71; C. I. Pigment red 81,105,122,149,150,155,171,175,176,209,220,224,242,255,264,270; C. I. Pigment violet 19, 23, 32, 39; C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; C. I. Pigment green 7, 36, 37; C. I. Pigment brown 25, 28; C. I. Pigment black 1; Etc.
  • Examples of the inorganic pigment that can be appropriately added to the colored resin composition of the present invention include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper And metal oxides such as titanium, magnesium, chromium, zinc, and antimony, and black pigments such as composite oxides of the above metals, carbon black, and titanium black.
  • Known dyes that can be appropriately added to the colored resin composition of the present invention include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614. No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat.No. 505950, U.S. Pat.
  • the dyes disclosed in JP-A-6-51115 and JP-A-6-194828 can be used.
  • pyrazole azo compounds When classified as a chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used.
  • a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.
  • the content of PG58 in the colored resin composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass with respect to the total solid content of the colored resin composition.
  • the content of the yellow colorant in the colored resin composition is preferably 10 to 100 parts by mass, preferably 20 to 85 parts with respect to PG58 (100 parts by mass). Part by mass is more preferable.
  • the amount of CI Pigment Yellow 185 is preferably 85% by mass or more, more preferably 90% by mass or more, and further preferably 95 to 100% by mass.
  • the composition of the present invention may further contain a pigment derivative.
  • a pigment derivative it is preferable to use a compound having a pigment mother nucleus structure and an amino group in the molecule (hereinafter also referred to as a specific pigment derivative).
  • a specific pigment derivative By using the specific pigment derivative, an interaction is formed between the pigment core structure in the specific pigment derivative and PG58, and the adsorptivity of both can be more effectively ensured.
  • the specific pigment derivative is preferably a compound represented by the following general formula (A).
  • R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group, preferably a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, or a saturated group having 3 to 20 carbon atoms. Or an unsaturated cycloalkyl group or an aryl group.
  • These organic groups may further have a substituent.
  • the substituents that may have are halogen atoms, hydroxyl groups, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups.
  • R 1 and R 2 may be bonded to each other to form a ring.
  • the compound represented by the general formula (A) is preferably a compound having at least one of an amide structure and a urea structure in the molecule. Moreover, it is preferable that the compound represented by general formula (A) is a compound which has a heterocyclic structure.
  • X is an m-valent group containing a pigment mother nucleus structure.
  • the pigment mother nucleus structure is a chromogenic group in an organic pigment, a similar structure, or a partial structure.
  • a skeleton having an azo group, a skeleton having a urea structure, a skeleton having an amide structure examples thereof include a structure containing one or more partial structures selected from a skeleton having a cyclic amide structure, an aromatic ring having a heteroatom-containing 5-membered ring, and an aromatic ring having a heteroatom-containing 6-membered ring.
  • X is a substituent containing these pigment mother nucleus structures.
  • X in the general formula (A) has a pigment mother nucleus structure or a pigment mother nucleus structure and an aromatic ring, a nitrogen-containing aromatic ring, an oxygen-containing aromatic ring, or a sulfur-containing aromatic ring, and an amino group is a pigment mother structure. It is preferably bonded directly or via a linking group to any one of the core structure, aromatic ring, nitrogen-containing aromatic ring, oxygen-containing aromatic ring and sulfur-containing aromatic ring. In particular, it preferably has a pigment mother nucleus structure and an aromatic ring or a nitrogen-containing aromatic ring and is bonded to an amino group by a divalent linking group.
  • m is an integer of 1 to 8, preferably 1 to 6, and more preferably 1 or 2, from the viewpoint of dispersibility and storage stability of the dispersion.
  • pigment derivative used in the present invention is shown, but the invention is not limited thereto.
  • derivatives having a benzimidazole skeleton as the pigment nucleus structure are preferable.
  • pigment derivatives containing a benzimidazole skeleton represented by (1) to (12) are preferable, and those containing a benzimidazole skeleton containing (7) to (12) are preferable.
  • Pigment derivatives are particularly preferred.
  • the following compounds are preferred as the pigment derivative used in the composition of the present invention.
  • a pigment derivative having a carboxylic acid group or a sulfonic acid group or a metal salt / ammonium salt thereof as a substituent is preferable.
  • the pigment derivatives represented by (A) to (I) are preferably used, and the pigment derivatives represented by (A), (B), and (I) are preferably used. Particularly preferred.
  • the content of the pigment derivative is preferably 0.5 to 50 parts by mass, more preferably 1 to 25 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the total pigment including PG58 in the colored resin composition. Further preferred. Only 1 type of pigment derivative may be contained in the colored resin composition, and may be contained 2 or more types. When two or more types are included, the total amount is preferably within the above range.
  • composition of this invention further contains the diamine compound represented by General formula (2).
  • R 3 represents a divalent linking group.
  • R 3 is a group derived from diamine and represents a divalent linking group.
  • R 3 is preferably a divalent linking group having 1 to 22 carbon atoms.
  • R 3 is preferably a hydrocarbon group or a divalent linking group containing a group composed of a combination of a hydrocarbon group and —CO—, —NR—, and —O—.
  • R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the hydrocarbon group may be linear, branched or cyclic.
  • R 3 preferably includes a cyclic structure, and preferably includes a cyclic hydrocarbon group.
  • the cyclic structure is synonymous with the cyclic structure that R 2 in the general formula (1) may have.
  • R 3 in the general formula (2) is preferably a divalent linking group containing the same skeleton as R 2 in the general formula (1).
  • R 3 in the general formula (2) a diamine compound having a divalent linking group containing the same skeleton as R 2 in the general formula (1) is a polyamic acid represented by the general formula (1). Since it is excellent in compatibility, it becomes more effective as a catalyst for the thermosetting reaction of the polyamic acid represented by the general formula (1), and the effects of the present invention can be achieved more effectively.
  • the same skeleton as R 2 means that at least a part of atoms constituting the divalent linking group is common.
  • R 3 may be a phenylene group, a phenylene group may be substituted, or a group consisting of a combination of a phenylene group and —O—.
  • R 3 preferably has the same partial structure as R 2 in general formula (1), and more preferably has the same structure as R 2 in general formula (1).
  • Specific examples of the diamine compound represented by the general formula (2) include diamines that can be used when synthesizing the polyamic acid described above.
  • the content of the diamine compound represented by the general formula (2) in the colored resin composition is preferably 0.01 to 10% by mass, and preferably 0.1 to 2% by mass with respect to the total solid content of the colored resin composition. % Is more preferable, 0.3 to 0.8% by mass is further preferable, and 0.4 to 0.7% by mass is particularly preferable.
  • the diamine compound represented by the general formula (2) may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount corresponds to the said content.
  • the composition of the present invention may further contain 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 colored resin composition are satisfied.
  • organic solvents examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate.
  • Alkyl oxyacetates eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)
  • alkyl 3-oxypropionate Esters eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
  • 2-oxypropionic acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
  • ethers for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether , Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like, and ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbons, Example If, toluene, xylene, and, as alcohols, such as 3-methyl-3-methoxybutanol and the like are preferably exemplified.
  • the content of the organic solvent in the colored resin composition is preferably such that the total solid concentration of the composition is 5% by mass to 80% by mass from the viewpoint of applicability. Is more preferable, and 10% by mass to 50% by mass is particularly preferable.
  • the composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.
  • the colored resin composition of the present invention contains a pigment dispersant, a polymerizable compound, a polymerization initiator, an alkali-soluble resin, a surfactant, an alkaline earth metal ion, and the like as components other than the components described above. Also good.
  • the pigment dispersant may not be substantially contained, but may further contain a pigment dispersant.
  • the pigment dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic.
  • naphthalenesulfonic acid formalin condensates such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
  • the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
  • the pigment dispersant for example, the description in paragraphs 0216 to 0222 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • the total content of the pigment dispersant may be 1 to 80 parts by mass with respect to 100 parts by mass of the pigment containing PG58.
  • the mass may be from 70 parts by mass, and may be from 10 to 60 parts by mass.
  • the content of the pigment dispersant can be 5 parts by mass or less with respect to 100 parts by mass of the pigment containing PG58, and 1 part by mass or less. Or 0 parts by mass. (Polymerizable compound) Since the polyamic acid mentioned above functions also as a thermosetting agent, the composition of this invention does not need to contain a polymeric compound substantially, but may contain a polymeric compound further.
  • the description in paragraphs 0129 to 0136 of JP2011-137125A can be referred to, and the contents thereof are incorporated in the present specification.
  • the content of the polymerizable compound can be 1 to 10% by mass with respect to the total solid content of the composition of the present invention, 0.1 to 3 It can also be made into the mass%.
  • the content of the polymerizable compound can be 1% by mass or less based on the total solid content of the composition of the present invention. It can also be made into the mass% or less, and can also be 0 mass%.
  • composition of this invention may contain a polymerization initiator, it does not need to contain a polymerization initiator substantially.
  • the photopolymerization initiator is not substantially contained.
  • a polymerization initiator it can select suitably from well-known photoinitiators, for example. Only one type of photopolymerization initiator may be used, or two or more types may be used in combination.
  • Examples of the polymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.
  • Examples of the oxime compound include those represented by the following formula (OX-1) or (OX-2) in paragraph 0513 of JP2012-208494A (corresponding US Patent Application Publication No.
  • TRONLY TR-PBG-304 TRONLY TR-PBG-309
  • TRONLY TR-PBG-305 commercial products such as can also be used.
  • the content of the polymerization initiator can be 1 to 5% by mass relative to the total solid content of the composition of the present invention, and 0.1 to It can also be 1 mass%.
  • the content of the polymerization initiator can be 1% by mass or less based on the total solid content of the composition of the present invention. It can also be made into the mass% or less, and can also be 0 mass%.
  • the alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group.
  • a molecule having an acrylic copolymer or a styrene copolymer as a main chain preferably molecule having an acrylic copolymer or a styrene copolymer as a main chain. It can be suitably selected from alkali-soluble resins having a group.
  • paragraphs 0558 to 0571 of JP2012-208494A corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099
  • the contents thereof can be referred to. It is incorporated herein.
  • the content of the alkali-soluble resin can be 0.01 to 10% by mass in the total solid
  • the composition of the present invention may further contain various surfactants from the viewpoint of further improving applicability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the composition of the present invention can further improve liquid properties (particularly fluidity) when it is prepared as a coating solution by containing a fluorosurfactant, and can improve uniformity of coating thickness and saving. Liquidity can be further improved.
  • the fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, 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 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like.
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the content of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably based on the total mass of the composition of the present invention. Is 0.005 mass% to 1.0 mass%.
  • the composition of the present invention may contain only one type of surfactant or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the colored resin composition of the present invention may further contain alkaline earth metal ions (such as calcium ions).
  • alkaline earth metal ions such as calcium ions.
  • the effects of the present invention are excellent, and the generation of needle-like foreign matters due to a mixed crystal of molten zinc phthalocyanine and copper phthalocyanine can be more effectively suppressed.
  • the content of alkaline earth metal ions relative to the mass of PG58 can be 30 to 300 ppm by mass.
  • additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended with the colored resin composition as necessary.
  • these additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
  • the composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the publication.
  • the composition of this invention can be prepared by mixing each component mentioned above.
  • the components constituting the colored resin composition may be combined at once, or may be sequentially mixed after each component is dissolved and dispersed in a solvent.
  • a colored resin composition may be prepared by simultaneously dissolving and dispersing all components in a solvent, and if necessary, each component may be suitably used as two or more solutions / dispersions at the time of use ( These may be mixed at the time of application) to prepare as a composition.
  • PG58 dispersed with a dispersant is blended with other components.
  • the composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
  • a filter used for filter filtration if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
  • filter materials include: fluororesins such as PTFE (polytetrafluoroethylene); polyamide resins such as nylon-6 and nylon-6, 6; polyolefin resins such as polyethylene and polypropylene (PP) (high density, super Including high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.
  • the pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 ⁇ m, preferably about 0.01 to 5 ⁇ m, and more preferably about 0.01 to 2.0 ⁇ m.
  • the pore size of the filter can refer to the nominal value of the filter manufacturer.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
  • two or more filters may be used in combination. For example, filtration can be performed first using a first filter, and then using a second filter having a pore diameter different from that of the first filter. At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or twice or more, respectively.
  • a filter formed of the same material as the first filter described above can be used.
  • the cured film obtained by curing the composition of the present invention is preferably used for forming a colored pattern of a color filter because other colors are unlikely to be mixed on the surface.
  • the composition of the present invention is preferably used for forming a colored pattern such as a color filter used in a solid-state imaging device (for example, CCD, CMOS, etc.) or an image display device such as a liquid crystal display device (LCD).
  • a color filter for a solid-state imaging device such as a CCD and a CMOS can be suitably used as a production application.
  • the composition of the present invention can be preferably used as a colored resin composition for dry etching.
  • the cured film of the present invention is formed by curing the composition of the present invention. Such a cured film is preferably used for a color filter.
  • the colored resin composition layer is formed by applying the composition of the present invention on a support, and unnecessary portions are removed to form a colored pattern.
  • the pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) included in a color filter.
  • the colored resin composition of the present invention may form a pattern by a dry etching method, or may produce a color filter by pattern formation by a so-called photolithography method.
  • a pattern forming method includes a step of forming a photoresist layer on the substrate, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask. Is done.
  • a step of forming a colored resin composition layer by applying the colored resin composition on a support, and exposing the colored resin composition layer in a pattern shape The pattern formation method including a process and the process of developing and removing an unexposed part and forming a colored pattern is illustrated.
  • Such a pattern forming method is used for manufacturing a colored layer of a color filter. That is, the present invention also discloses a method for manufacturing a color filter including the pattern forming method of the present invention.
  • the method for producing a color filter of the present invention comprises a step of applying a colored resin composition onto a substrate to form a colored film (colored layer), and heating the colored film applied on the substrate at 150 to 350 ° C. to cure.
  • a first colored layer 11 is formed from a first colored resin composition as a colored resin composition (step ( A)).
  • the first colored resin composition the above-described colored resin composition of the present invention can be used.
  • the first colored layer 11 is preferably a green transmission layer. By making the first colored layer 11 a green transmissive layer, color sensitivity can be further improved.
  • the first colored layer 11 is applied, for example, by applying a colored resin composition onto a support by a coating method such as spin coating, slit coating, spray coating, spin coating, spin coating, cast coating, roll coating, and the like. And forming a colored layer. In particular, it is preferable to apply by spin coating.
  • the support is not particularly limited as long as it is used for a color filter in addition to a silicon substrate. For example, soda glass, borosilicate glass, quartz glass, and a transparent conductive film attached to these are used for liquid crystal display elements. And a photoelectric conversion element substrate used for a solid-state imaging device, such as an oxide film or silicon nitride.
  • the thickness of the first colored layer 11 after drying is preferably in the range of 0.3 to 2.0 ⁇ m, more preferably in the range of 0.35 to 1.5 ⁇ m, and more preferably in the range of 0.35 to 1.2 ⁇ m. preferable.
  • the first colored layer 11 is preferably cured by heating with a heating device such as a hot plate or an oven.
  • the heating temperature is preferably 90 ° C to 250 ° C, more preferably 100 ° C to 230 ° C.
  • the heating time varies depending on the heating means, but when heated on a hot plate, it is usually about 2 to 30 minutes, and when heated in an oven, it is usually about 30 to 90 minutes.
  • the first colored layer 11 is preferably further subjected to heat treatment (post-bake).
  • the heating temperature for post baking is preferably 150 ° C. to 350 ° C., more preferably 200 ° C. to 250 ° C.
  • the heating time varies depending on the heating means, but is usually about 20 to 90 minutes.
  • step (B) patterning is performed by dry etching so that a removal portion group is formed in the first colored layer 11 (step (B)).
  • a first colored pattern is formed.
  • the first colored layer is formed with the first colored resin composition, and a desired shape (as compared with the case where the removal portion group is provided by exposing and developing the first colored layer)
  • the removal portion group having a rectangular shape can be provided more reliably.
  • Dry etching can be performed on the first colored layer 11 using an etching gas using the patterned photoresist layer as a mask. For example, as shown in the schematic sectional view of FIG. 2, first, a photoresist layer 51 is formed on the first colored layer 11.
  • a positive or negative photoresist is applied on the first colored layer 11 and dried to form a photoresist layer.
  • a pre-bake treatment it is preferable to further perform a pre-bake treatment.
  • a positive type photoresist is used as the photoresist.
  • This positive photoresist is suitable for positive photoresists sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays.
  • a positive resist composition can be used.
  • the radiation g-line, h-line and i-line are preferable, and i-line is particularly preferable.
  • a composition containing a quinonediazide compound and an alkali-soluble resin is preferable as a positive photoresist.
  • the quinonediazide compound include a naphthoquinonediazide compound.
  • the thickness of the dried photoresist layer 51 is preferably 0.1 to 3 ⁇ m, more preferably 0.2 to 2.5 ⁇ m, and still more preferably 0.3 to 2 ⁇ m. Note that the application of the photoresist layer 51 can be suitably performed using the application method for the first colored layer 11.
  • the photoresist layer 51 is exposed and developed to form a resist pattern (patterned photoresist layer) 52 provided with a resist removal portion group 51A.
  • the formation of the resist pattern 52 is not particularly limited, and a conventionally known photolithography technique can be used.
  • a resist pattern 52 as an etching mask used in the next etching is provided on the first colored layer 11.
  • the exposure of the photoresist layer 51 can be performed by exposing a positive or negative photoresist to g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern.
  • the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.
  • a developer any can be used as long as it does not affect the first colored layer containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist.
  • Combinations of various organic solvents and alkaline aqueous solutions can be used.
  • an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable.
  • Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Examples thereof include ammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like.
  • alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.
  • the resist pattern 52 is used as an etching mask, and patterning is performed by dry etching so that the removal portion group 120 is formed in the first colored layer 11.
  • the 1st coloring pattern 12 is formed.
  • the removal unit group 120 includes a first removal unit group 121 and a second removal unit group 122.
  • the removal unit group 120 is provided on the first colored layer 11 in a checkered pattern. Therefore, the 1st coloring pattern 12 in which the removal part group 120 is provided in the 1st coloring layer 11 has a some square 1st coloring pixel in checkered form.
  • the first colored layer 11 is dry etched using the resist pattern 52 as an etching mask.
  • dry etching include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, and the like. And the contents thereof are incorporated herein by reference.
  • Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
  • a mixed gas of fluorine-based gas and oxygen gas (O 2 ) the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N 2 ) and oxygen gas (O 2 ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed.
  • N 2 nitrogen gas
  • O 2 oxygen gas
  • a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed.
  • the form containing these is preferable.
  • a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.
  • Dry etching is performed by obtaining etching conditions in advance by the following method.
  • (1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
  • (2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
  • (3) The first stage etching is performed according to the etching time calculated in (2) above.
  • the second stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
  • Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.
  • the mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O 2 ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape.
  • the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed.
  • the second etching step and the over-etching step are performed in the first etching step after etching to a region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas. From the viewpoint of avoidance, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.
  • the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable.
  • the etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.
  • the etching preferably includes an over-etching process.
  • the overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first.
  • the over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable.
  • the resist pattern (that is, etching mask) 52 remaining after the etching is removed.
  • the removal of the resist pattern 52 includes a step of applying a stripping solution or a solvent to the resist pattern 52 so that the resist pattern 52 can be removed, and a step of removing the resist pattern 52 using cleaning water.
  • a step of applying a stripping solution or a solvent on at least the resist pattern 52 and stagnating for a predetermined time to perform paddle development can be included.
  • the resist pattern 52 may be removed by spraying cleaning water onto the resist pattern 52 from a spray type or shower type spray nozzle.
  • cleaning water pure water can be preferably used.
  • the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support.
  • Step of Forming Second Colored Pixel the second colored pixel adjacent to the first colored pixel is formed by photolithography using the second colored radiation-sensitive composition.
  • the number of steps can be reduced as compared with the case where all steps are performed by dry etching.
  • the second colored radiation-sensitive property is formed inside each removed portion in the first removed portion group 121 and the second removed portion group 122.
  • the composition is embedded, and the second colored radiation-sensitive composition is used to form the first colored layer (that is, the first colored pattern 12 in which the removal portion group 120 is formed on the first colored layer 11).
  • Two colored radiation-sensitive layers 21 are laminated (step (C)).
  • the 2nd coloring pattern 22 which has a some 2nd coloring pixel in the removal part group 120 of the 1st coloring layer 11 is formed.
  • the second colored pixel is preferably a square pixel.
  • the second colored radiation sensitive layer 21 can be formed in the same manner as the method for forming the first colored layer 11 described above.
  • the thickness of the second colored radiation-sensitive layer 21 after post-baking is preferably 0.1 to 1.5 ⁇ m, and more preferably 0.1 to 1.0 ⁇ m.
  • the second colored radiation-sensitive layer 21 is exposed and developed at a position 21A corresponding to the first removal portion group 121 provided in the first colored layer 11 of the second colored radiation-sensitive layer 21.
  • 21 and the plurality of second colored pixels 22R provided inside each removal portion of the second removal portion group 122 are removed (step (D)) (see the schematic cross-sectional view of FIG. 7).
  • radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line).
  • Irradiation dose is more preferably 30mJ / cm 2 ⁇ 3000mJ / cm 2 is preferably 50mJ / cm 2 ⁇ 2500mJ / cm 2, 100mJ / cm 2 ⁇ 500mJ / cm 2 is particularly preferred.
  • the developer is synonymous with the developer described in the step of forming the first colored pixels described above.
  • a development method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method)
  • the paddle method is particularly preferable.
  • the development time is not particularly limited as long as the colored layer in the unexposed area is sufficiently dissolved, and is usually 10 seconds to 300 seconds. Preferably, it is 20 seconds to 120 seconds.
  • the temperature of the developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C.
  • the method for manufacturing a color filter of the present invention may further include a step of forming a third colored pixel after the step of forming the second colored pixel.
  • the third colored radiation-sensitive composition is embedded in each removed portion in the second removed portion group 122, The first colored layer (that is, the first colored pattern 12 in which the second colored pattern 22 is formed in the first removal portion group 121) so that a plurality of third colored pixels are formed.
  • a third colored radiation-sensitive layer 31 is formed on the third colored radiation-sensitive composition (step (E)).
  • the 3rd coloring pattern 32 which has a some 3rd coloring pixel in the 2nd removal part group 122 of the 1st coloring layer 11 is formed.
  • the third colored pixel is preferably a square pixel.
  • the formation of the third colored radiation-sensitive layer 31 can be performed in the same manner as the step of forming the colored layer using the colored resin composition in the first embodiment described above.
  • the thickness of the third colored resin composition layer 31 after post-baking is preferably in the range of 0.1 to 1 ⁇ m, more preferably in the range of 0.2 to 0.8, and in the range of 0.3 to 0.6 ⁇ m. Is more preferable.
  • the third colored radiation-sensitive layer 31 is exposed and developed at a position 31A corresponding to the second removal portion group 122 provided in the first colored layer 11 of the third colored radiation-sensitive layer 31.
  • the color filter 100 having the first colored pattern 12, the second colored pattern 22, and the third colored pattern 32 is manufactured. (Step (F)).
  • the second colored radiation-sensitive composition and the third colored radiation-sensitive composition described above each contain a colorant.
  • the colorant may include those described above in the coloring composition of the present invention, but one of the second colored pixel and the third colored pixel is a blue transmissive portion, and the other is a red transmissive portion. preferable.
  • the colorant contained in the coloring composition for forming the blue transmission part is C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 or more It is preferable.
  • the colorant contained in the coloring composition for forming the red transmitting part is preferably at least one selected from those described in paragraph numbers 0037 and 0039 of JP2012-172003A. Is incorporated herein by reference.
  • the content of the colorant composition with respect to the total solid content is preferably 30% by mass or more, and 35% by mass. More preferably, it is more preferably 40% by mass or more. Moreover, content with respect to the total solid of the composition of a coloring agent is 90 mass% or less normally, and it is preferable that it is 80 mass% or less.
  • a negative radiation sensitive composition is used for each of the second colored radiation sensitive composition and the third colored radiation sensitive composition.
  • This negative radiation sensitive composition includes negative radiation sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer laser, electron beams, ion beams and X rays. Sex compositions can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
  • the negative radiation-sensitive composition is preferably a composition containing a photopolymerization initiator, a polymerization component (polymerizable compound), a binder resin (alkali-soluble resin, etc.) and the like. Examples described in paragraph Nos. 0017 to 0064 of Kaikai 2005-326453 may be mentioned, the contents of which are incorporated herein.
  • a negative radiation sensitive composition utilizes the fact that the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound upon irradiation with radiation, and as a result, the alkali soluble state becomes alkali insoluble. To do.
  • a pattern can be formed by a wet etching method.
  • An example of a method for forming a pattern by the wet etching method is shown below.
  • the colored resin composition described above is applied to form a colored film.
  • soda glass, alkali-free glass, borosilicate glass, quartz glass, or the like can be usually used.
  • the coating methods such as spinner, spray coating, dipping, roll coating, bar coating, and die coating are used.
  • the applied colored resin composition is preferably dried in the range of 50 to 180 ° C.
  • a photoresist for pattern formation is applied on the colored film to form a photoresist layer.
  • the thickness of the photoresist layer is preferably from 0.1 to 3 ⁇ m, preferably from 0.2 to 2.5 ⁇ m, more preferably from 0.3 to 2 ⁇ m.
  • a mask is formed on the photoresist layer coating. Place, irradiate with actinic radiation and expose. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays and visible rays are preferable.
  • the colored film is heat-treated to finish the patterning of the colored film.
  • the heat treatment is performed for 5 minutes to 5 hours while selecting the temperature and raising the temperature stepwise or selecting a temperature range and continuously raising the temperature.
  • the heat treatment temperature is preferably 180 to 400 ° C, and more preferably 180 to 350 ° C. For example, heat treatment is performed at 130 ° C., 200 ° C., and 300 ° C. for 30 minutes.
  • a color filter can be formed by forming an overcoat film made of acrylic polymer, polysiloxane, polyimide, or the like as necessary, and sputtering a metal oxide film such as ITO.
  • the colored resin composition layer can be patterned by a photolithography method.
  • a photolithography method For details of the photolithography method, reference can be made to paragraph numbers 0173 to 0185 of JP2013-227497A, the contents of which are incorporated herein.
  • the color filter of the present invention is formed of a colored resin composition having a high colorant concentration, the thickness of the colored pattern can be extremely reduced (for example, 0.7 ⁇ m or less). In addition, since other colors hardly remain on the surface and color mixing does not easily occur, a color filter in which crosstalk (light color mixing) is suppressed can be obtained.
  • the color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels.
  • the color filter for a solid-state imaging device of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.
  • the thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably from 0.1 to 1.0 ⁇ m, more preferably from 0.1 to 0.8 ⁇ m.
  • the size (pattern width) of the colored pattern (colored pixel) can be 2.5 ⁇ m or less, can be 2.0 ⁇ m or less, and can be 0.9 to 1.4 ⁇ m. In particular, by using a dry etching method, a colored pattern having the above size can be efficiently produced.
  • the solid-state imaging device of the present invention includes the above-described color filter of the present invention.
  • the configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .
  • a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support.
  • light collecting means for example, a microlens, etc., the same shall apply hereinafter
  • the color filter of the present invention can be used not only for the solid-state imaging device but also for image display devices such as liquid crystal display devices and organic EL display devices, and is particularly suitable for use in liquid crystal display devices.
  • the liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.
  • display devices For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the color filter of the present invention may be used in a color TFT liquid crystal display device.
  • the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
  • the present invention is applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
  • the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system.
  • COA Color-filter On Array
  • the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above.
  • the COA method has high resolution and excellent long-term durability.
  • a liquid crystal display device can be provided.
  • a resin film may be provided on the color filter layer.
  • the liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film.
  • the color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
  • these components for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
  • backlighting SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.
  • the color filter according to the present invention When the color filter according to the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue LED light sources (RGB-LED).
  • RGB-LED red, green and blue LED light sources
  • Synthesis Examples 2 to 3 Polyamic acid PA-2 to PA having a solid content concentration of 20% by mass in the same manner as in Synthesis Example 1 except that the type and amount of raw materials used in the synthesis of polyamic acid are changed as shown in Table 1 below. -3 was obtained.
  • the green colored resin compositions G-2 to G- were prepared in the same manner as the green colored resin composition G-1, except that the composition of the green colored resin composition G-1 was changed to the composition shown in Table 2 below. 34 was prepared.
  • PG58 C.I. I. Pigment Green 58 (polyhalogenated zinc phthalocyanine green pigment, manufactured by DIC Corporation)
  • PY129 C.I. I. Pigment Yellow 129 (copper azomethine yellow pigment)
  • PY150 C.I. I. Pigment Yellow 150 (Nickel azo yellow pigment)
  • PY185 C.I. I.
  • Pigment Yellow 185 (isoindoline-based yellow pigment)
  • D-1 Pigment derivative having the following structural formula (manufactured by FUJIFILM Corporation)
  • D-2 Pigment derivative having the following structural formula (manufactured by FUJIFILM Corporation)
  • D-3 Pigment derivative having the following structural formula (manufactured by FUJIFILM Corporation)
  • C-1 p-phenylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.)
  • C-2 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • C-3 4,4′-diaminobenzanilide (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • C-4 Hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • F-1 Made by DIC, MegaFuck F-781F (fluorine-based surfactant)
  • BL
  • the cured coating film obtained by the curing treatment was immersed in N-methylpyrrolidone for 60 seconds, and the change in spectral transmittance of the cured coating film before and after immersion was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).
  • the solvent resistance was evaluated by the obtained color difference ⁇ Eab. The smaller ⁇ Eab, the smaller the change in spectral transmittance before and after immersion in the solvent, and the better the solvent resistance.
  • Table 2 summarizes the evaluation results of solvent resistance.
  • Green pixel pattern formation process by dry etching> (Formation of green layer) After applying the above-mentioned green colored resin composition on a silicon wafer with a spin coater, drying on a hot plate at 100 ° C. for 180 seconds, and then performing a heat treatment (post bake) at 240 ° C. for 30 minutes in a nitrogen atmosphere. A green colored film was formed. The thickness of this green colored film was 0.6 ⁇ m.
  • the obtained photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.) and subjected to heat treatment for 1 minute at a temperature at which the temperature of the photoresist layer or the atmospheric temperature was 90 ° C. Thereafter, development processing was performed with a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials) for 1 minute, and further post-baking processing was performed at 110 ° C. for 1 minute to form a resist pattern.
  • This resist pattern is a pattern in which square-shaped resist films formed with a side of 1.25 ⁇ m are arranged in a checkered pattern in consideration of etching conversion difference (pattern width reduction by etching).
  • the amount of green layer scraping was 534 nm (89% etching amount), and there was a remaining film of about 58 nm.
  • RF power 600 W
  • antenna bias 100 W
  • wafer bias 250 W
  • chamber internal pressure 2.0 Pa
  • substrate temperature 50 ° C.
  • gas mixture type and flow rate of N 2 500 mL / min.
  • O 2 50 mL / min.
  • the second etching process and the over-etching process were performed with the over-etching rate in the total etching being 20%.
  • the etching rate of the green layer under the second stage etching conditions was 600 nm / min or more, and it took about 10 seconds to etch the remaining film of the green layer.
  • the sum of 80 seconds of the first stage etching time and 10 seconds of the second stage etching time was calculated as the etching time.
  • the resist pattern is removed for 120 seconds using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials), and the resist pattern is removed, followed by washing with pure water. Spin drying was performed. Thereafter, a dehydration baking process was performed at 100 ° C. for 2 minutes. As described above, a green pattern in which square green pixels having a side of 1.2 ⁇ m are arranged in a checkered pattern was obtained. Thus, it was confirmed that a fine pixel pattern suitable for a color filter for a solid-state imaging device can be formed by processing the green colored film formed from the green resin composition of the present invention by dry etching.
  • region is an area
  • Comparative Example 2 (Verification of effects when PG36 is used as a green pigment) A mixture having the following composition was stirred and mixed uniformly, and then mixed and dispersed by a bead mill for 3 hours, whereby C.I. I. Using Pigment Green 36, a green colored resin composition G36-PA using the above-described polyamic acid PA-1 as a cured resin was prepared.
  • Polyhalogenated copper phthalocyanine pigment CI Pigment Green 36
  • CI Pigment Green 150 7.30 parts by mass
  • a green colored resin composition G36-EP using Pigment Green 36 and an epoxy resin as a cured resin was prepared.
  • Polyhalogenated copper phthalocyanine pigment CI Pigment Green 36
  • Nickel azo yellow pigment CI Pigment Yellow 150
  • Dispersant A 4.20 parts by mass
  • Epoxy resin A manufactured by Daicel Chemical Industries, EHPE 3150
  • ⁇ -butyrolactone 40.00 parts by mass 3-methyl-3-methoxybutanol 40.00 parts by mass
  • the photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.), and heat treatment was performed for 1 minute at a temperature at which the temperature of the photoresist layer or the atmospheric temperature was 90 ° C. Thereafter, a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was immersed in the photoresist, and the photoresist and the lower green colored film were developed at the same time (this is the upper photoresist film).

Abstract

Provided are: a colored resin composition capable of suppressing the formation of needle-shaped contaminants in a boundary area between green pixels and adjacent colored pixels during high-temperature heating; a cured film using same; a color filter and a production method therefor; a solid-state imaging element; and an image display device. The colored resin composition includes polyamic acid having a repeated unit indicated by general formula (1) and a C.I. pigment green 58. In the general formula (1), R1 indicates an n + 2-valent linking group, R2 indicates a divalent linking group, and n indicates 1 or 2.

Description

着色樹脂組成物およびこれを用いた硬化膜、カラーフィルタおよびその製造方法、固体撮像素子ならびに画像表示装置COLORED RESIN COMPOSITION AND CURED FILM USING THE SAME, COLOR FILTER AND METHOD FOR MANUFACTURING THE SAME
　本発明は着色樹脂組成物に関する。特に、カラーフィルタの着色層形成に好ましく用いられる着色樹脂組成物に関する。さらに、上記着色樹脂組成物を用いた硬化膜、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。また、着色樹脂組成物を用いたカラーフィルタの製造方法にも関する。 The present invention relates to a colored resin composition. In particular, the present invention relates to a colored resin composition preferably used for forming a colored layer of a color filter. Furthermore, the present invention relates to a cured film, a color filter, a solid-state imaging device, and an image display device using the colored resin composition. The present invention also relates to a method for producing a color filter using a colored resin composition.
　近年、パーソナルコンピュータ、特に大画面液晶テレビの発達に伴い、液晶ディスプレイ（ＬＣＤ）、とりわけカラー液晶ディスプレイの需要が増加する傾向にある。更なる高画質化の要求から有機ＥＬディスプレイの普及も待ち望まれている。一方、デジタルカメラ、カメラ付き携帯電話の普及から、ＣＣＤイメージセンサーなどの固体撮像素子も需要が大きく伸びている。
　これらの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おり、更なる高画質化の要求とともにコストダウンへの要求が高まっている。このようなカラーフィルタは、通常、赤（Ｒ）、緑（Ｇ）、および青（Ｂ）の３原色の着色パターンを備えており、表示デバイスや撮像素子において、通過する光を３原色へ分画する役割を果たしている。 In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, the demand for liquid crystal displays (LCD), especially color liquid crystal displays, has been increasing. The spread of organic EL displays is also awaited due to the demand for higher image quality. On the other hand, with the widespread use of digital cameras and camera-equipped mobile phones, the demand for solid-state imaging devices such as CCD image sensors has greatly increased.
Color filters are used as key devices for these displays and optical elements, and the demand for cost reduction is increasing along with the demand for higher image quality. Such a color filter is usually provided with a coloring pattern of three primary colors of red (R), green (G), and blue (B), and in a display device or an image sensor, light passing therethrough is divided into three primary colors. It plays a role to draw.
　カラーフィルタに使用されている着色剤には、共通して次のような特性が求められる。
　即ち、色再現性上好ましい分光特性を有すること、液晶ディスプレイのコントラスト低下の原因である光散乱や固体撮像素子の色ムラ・ザラツキ感の原因となる光学濃度の不均一性といった光学的な乱れがないこと、使用される環境条件下における堅牢性、例えば、耐熱性、耐光性、耐湿性等が良好であること、モル吸光係数が大きく薄膜化が可能なこと等が必要とされている。このため、着色剤としては顔料を用いることが一般的である。
　特許文献１には、顔料とポリアミド酸を含むカラーフィルタ用着色樹脂組成物が開示されている。特許文献２には、ポリハロゲン化亜鉛フタロシアニン顔料組成物が開示されている。 The colorant used in the color filter is commonly required to have the following characteristics.
In other words, it has optical characteristics that are favorable for color reproducibility, optical scattering such as light scattering that causes a decrease in contrast of a liquid crystal display, and unevenness in optical density that causes color unevenness and roughness of a solid-state imaging device. There is a need for it to be free, toughness under the environmental conditions used, for example, heat resistance, light resistance, moisture resistance, etc., to have a large molar extinction coefficient and to be thin. For this reason, it is common to use a pigment as a colorant.
Patent Document 1 discloses a colored resin composition for a color filter containing a pigment and a polyamic acid. Patent Document 2 discloses a polyhalogenated zinc phthalocyanine pigment composition.
特開２００３－２２７９２１号公報Japanese Patent Laid-Open No. 2003-227921 特開２００７－２８４５９２号公報JP 2007-284592 A
　本願発明者が検討したところ、緑色顔料としてＣ．Ｉ．ピグメントグリーン５８（以下、「ＰＧ５８」ともいう。）を用いたカラーフィルタは、高温加熱時に緑色画素と隣接した着色画素との境界領域に針状の異物を形成してしまうことがわかった。
　特許文献１には、顔料としてＰＧ５８を用いることについて記載されていない。特許文献２に記載の技術では、針状の異物を抑制することが困難である。
　本発明はかかる課題を解決するものであって、高温加熱時に緑色画素と隣接した着色画素との境界領域に針状の異物が形成されることを抑制できる着色樹脂組成物を提供することを目的とする。 When this inventor examined, as a green pigment, C.I. I. It has been found that a color filter using Pigment Green 58 (hereinafter also referred to as “PG58”) forms needle-like foreign matters in the boundary region between the green pixel and the adjacent colored pixel when heated at a high temperature.
Patent Document 1 does not describe the use of PG58 as a pigment. With the technique described in Patent Document 2, it is difficult to suppress needle-like foreign matters.
This invention solves this subject, and it aims at providing the colored resin composition which can suppress that a needle-like foreign material is formed in the boundary area | region of the color pixel adjacent to the green pixel at the time of high temperature heating. And
　上記課題のもと、本願発明者が検討を行った結果、ＰＧ５８と、特定構造を有するポリアミック酸とを含む着色樹脂組成物を用いることにより、上記課題を解決可能であることを見出し、本発明を完成させるに至った。
　具体的には、下記手段＜１＞により、好ましくは、手段＜２＞～＜１７＞により、上記課題は解決された。
＜１＞下記一般式（１）で表される繰り返し単位を有するポリアミック酸およびＣ．Ｉ．ピグメントグリーン５８を含む、着色樹脂組成物；
Figure JPOXMLDOC01-appb-C000003
 一般式（１）中、Ｒ1はｎ＋２価の連結基を表し、Ｒ2は２価の連結基を表し、ｎは１または２を表す。
＜２＞下記一般式（２）で表されるジアミン化合物をさらに含む、＜１＞に記載の着色樹脂組成物；
Figure JPOXMLDOC01-appb-C000004
 一般式（２）中、Ｒ3は２価の連結基を表す。
＜３＞黄色の着色剤をさらに含む、＜１＞または＜２＞に記載の着色樹脂組成物。
＜４＞黄色の着色剤として、Ｃ．Ｉ．ピグメントイエロー１２９を含む、＜３＞に記載の着色樹脂組成物。
＜５＞一般式（１）中、Ｒ1は炭素数２～２２のｎ＋２価の連結基を表す、＜１＞～＜４＞のいずれかに記載の着色樹脂組成物。
＜６＞一般式（１）中、Ｒ1は環状構造を含むｎ＋２価の連結基を表す、＜１＞～＜４＞のいずれかに記載の着色樹脂組成物。
＜７＞一般式（１Ａ）中、Ｒ2は炭素数１～２２の２価の連結基を表す、＜１＞～＜６＞のいずれかに記載の着色樹脂組成物。
＜８＞一般式（１）中、Ｒ2は炭化水素基、または、炭化水素基と－Ｓｉ（Ｒ2A）2、－ＣＯ－、－ＮＲ－、－Ｏ－、－ＳＯ2－、および－Ｓ－から選択される少なくとも１種との組み合わせからなる基を含む２価の連結基を表す、＜１＞～＜６＞のいずれかに記載の着色樹脂組成物；但し、Ｒ2Aはそれぞれ独立して炭素数１～６のアルキル基を表し、－ＮＲ－におけるＲは水素原子または炭素数１～６のアルキル基を表す。
＜９＞一般式（２）中、Ｒ3は炭素数１～２２の２価の連結基を表す、＜１＞～＜８＞のいずれかに記載の着色樹脂組成物。
＜１０＞一般式（２）中、Ｒ3は環状構造を含む２価の連結基を表す、＜１＞～＜８＞のいずれかに記載の着色樹脂組成物。
＜１１＞一般式（２）中のＲ3は、一般式（１）中のＲ2と同一の骨格を含む２価の連結基を表す、＜１＞～＜８＞のいずれかに記載の着色樹脂組成物。
＜１２＞固体撮像素子用に用いられる、＜１＞～＜１１＞のいずれかに記載の着色樹脂組成物。
＜１３＞＜１＞～＜１２＞のいずれかに記載の着色樹脂組成物を硬化してなる硬化膜。
＜１４＞＜１＞～＜１２＞のいずれかに記載の着色樹脂組成物を用いた着色層を有するカラーフィルタ。
＜１５＞＜１＞～＜１２＞のいずれかに記載の着色樹脂組成物を基板上に塗布して着色膜を形成する工程、
着色膜を１５０～３５０℃で加熱し、硬化させる工程、
硬化された着色膜の上にフォトレジストを塗布する工程、
フォトレジストをパターン露光した後、アルカリ現像することによって、フォトレジストをパターニングする工程、
パターニングされたフォトレジストをエッチングマスクとして、フォトレジストの下層の着色膜をドライエッチングによりパターニングする工程、
パターニング後のフォトレジストを除去する工程、
を含む、カラーフィルタの製造方法。
＜１６＞＜１４＞に記載のカラーフィルタまたは＜１５＞に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する固体撮像素子。
＜１７＞＜１４＞に記載のカラーフィルタまたは＜１５＞に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する画像表示装置。 As a result of investigations by the inventors of the present invention based on the above problems, it has been found that the above problems can be solved by using a colored resin composition containing PG58 and a polyamic acid having a specific structure. It came to complete.
Specifically, the above problem has been solved by the following means <1>, preferably by means <2> to <17>.
<1> A polyamic acid having a repeating unit represented by the following general formula (1) and C.I. I. A colored resin composition comprising CI Pigment Green 58;
Figure JPOXMLDOC01-appb-C000003
 In general formula (1), R 1 represents an n + divalent linking group, R 2 represents a divalent linking group, and n represents 1 or 2.
<2> The colored resin composition according to <1>, further including a diamine compound represented by the following general formula (2);
Figure JPOXMLDOC01-appb-C000004
 In general formula (2), R 3 represents a divalent linking group.
<3> The colored resin composition according to <1> or <2>, further including a yellow colorant.
<4> C.I. I. The colored resin composition according to <3>, comprising Pigment Yellow 129.
<5> The colored resin composition according to any one of <1> to <4>, wherein R 1 in formula (1) represents an n + divalent linking group having 2 to 22 carbon atoms.
<6> The colored resin composition according to any one of <1> to <4>, wherein R 1 in formula (1) represents an n + divalent linking group including a cyclic structure.
<7> The colored resin composition according to any one of <1> to <6>, wherein R 2 represents a divalent linking group having 1 to 22 carbon atoms in the general formula (1A).
<8> In the general formula (1), R 2 represents a hydrocarbon group, or a hydrocarbon group and —Si (R 2A ) 2 , —CO—, —NR—, —O—, —SO 2 —, and — The colored resin composition according to any one of <1> to <6>, which represents a divalent linking group containing a group consisting of a combination with at least one selected from S-; wherein R 2A is independently Represents an alkyl group having 1 to 6 carbon atoms, and R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
<9> The colored resin composition according to any one of <1> to <8>, wherein R 3 represents a divalent linking group having 1 to 22 carbon atoms in the general formula (2).
<10> The colored resin composition according to any one of <1> to <8>, wherein R 3 represents a divalent linking group including a cyclic structure in the general formula (2).
R 3 in <11> general formula (2) represents a divalent linking group containing the same skeleton and R 2 in general formula (1), according to any one of <1> to <8> Colored resin composition.
<12> The colored resin composition according to any one of <1> to <11>, which is used for a solid-state imaging device.
<13> A cured film obtained by curing the colored resin composition according to any one of <1> to <12>.
<14> A color filter having a colored layer using the colored resin composition according to any one of <1> to <12>.
<15> a step of forming a colored film by applying the colored resin composition according to any one of <1> to <12> on a substrate;
Heating and curing the colored film at 150 to 350 ° C.,
Applying a photoresist on the cured colored film;
Patterning the photoresist by pattern development of the photoresist, followed by alkali development,
Using the patterned photoresist as an etching mask, patterning a colored film under the photoresist by dry etching,
Removing the photoresist after patterning;
A method for producing a color filter, comprising:
<16> A solid-state imaging device having a color filter according to <14> or a color filter obtained by the method for producing a color filter according to <15>.
<17> An image display device having the color filter according to <14> or the color filter obtained by the method for producing a color filter according to <15>.
　本発明によれば、高温加熱時に緑色画素と隣接した着色画素との境界領域に針状の異物が形成されることを抑制できる着色樹脂組成物を提供可能になった。また、上記着色樹脂組成物を用いた硬化膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置を提供可能になった。 According to the present invention, it is possible to provide a colored resin composition capable of suppressing the formation of needle-like foreign matters in the boundary region between the green pixel and the adjacent colored pixel during high-temperature heating. In addition, it has become possible to provide a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device using the colored resin composition.
第１着色層の概略断面図である。It is a schematic sectional drawing of a 1st colored layer. 第１着色層の上にフォトレジスト層が形成された状態を示す概略断面図である。It is a schematic sectional drawing which shows the state in which the photoresist layer was formed on the 1st colored layer. 第１着色層の上にレジストパターンが形成された状態を示す概略断面図である。It is a schematic sectional drawing which shows the state in which the resist pattern was formed on the 1st colored layer. エッチングによって第１着色層に貫通孔群が設けられることにより、第１着色パターンが形成された状態を示す概略断面図である。It is a schematic sectional drawing which shows the state in which the 1st colored pattern was formed by providing a through-hole group in the 1st colored layer by etching. 図４におけるレジストパターンが除去された状態を示す概略断面図である。It is a schematic sectional drawing which shows the state from which the resist pattern in FIG. 4 was removed. 第２着色パターンおよび第２着色感放射線性層が形成された状態を示す概略断面図である。It is a schematic sectional drawing which shows the state in which the 2nd coloring pattern and the 2nd coloring radiation sensitive layer were formed. 図６における第２着色感放射線性層と、第２着色パターンを構成する第２着色画素の一部とが、除去された状態を示す概略断面図である。It is a schematic sectional drawing which shows the state from which the 2nd coloring radiation sensitive layer in FIG. 6 and a part of 2nd coloring pixel which comprises a 2nd coloring pattern were removed. 第３着色パターンおよび第３着色感放射線性層が形成された状態を示す概略断面図である。It is a schematic sectional drawing which shows the state in which the 3rd coloring pattern and the 3rd coloring radiation sensitive layer were formed. 図８における第３着色感放射線性層が除去された状態を示す概略断面図である。It is a schematic sectional drawing which shows the state from which the 3rd coloring radiation sensitive layer in FIG. 8 was removed.
　以下において、本発明の内容について詳細に説明する。尚、本願明細書において「～」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。
　本明細書において、全固形分とは、組成物の全組成から溶剤を除いた成分の総質量をいう。また、２５℃における固形分をいう。 Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition. The solid content at 25 ° C.
　本明細書における基（原子団）の表記に於いて、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）をも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　また、本明細書中における「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等を意味する。また、本発明において光とは、活性光線または放射線を意味する。本明細書中における「露光」とは、特に断らない限り、水銀灯、エキシマレーザーに代表される遠紫外線、Ｘ線、ＥＵＶ光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も露光に含める。 In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. To do. 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 addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
　また、本明細書において、“（メタ）アクリレート”はアクリレートおよびメタクリレートの双方、または、いずれかを表し、“（メタ）アクリル”はアクリルおよびメタクリルの双方、または、いずれかを表し、“（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。
　また、本明細書において、“単量体”と“モノマー”とは同義である。単量体は、オリゴマーおよびポリマーと区別され、重量平均分子量が２，０００以下の化合物をいう。本明細書において、重合性化合物とは、重合性官能基を有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性官能基とは、重合反応に関与する基を言う。 In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
　本明細書において、化学式中のＭｅはメチル基を、Ｅｔはエチル基を、Ｐｒはプロピル基を、Ｂｕはブチル基を、Ｐｈはフェニル基をそれぞれ示す。
　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。
　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測定によるポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてＴＳＫｇｅｌ Ｓｕｐｅｒ　ＡＷＭ―Ｈ（東ソー（株）製、６．０ｍｍＩＤ×１５．０ｃｍを、溶離液として１０ｍｍｏｌ／Ｌ　リチウムブロミドＮＭＰ(Ｎ－メチルピロリジノン)溶液を用いることによって求めることができる。 In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
　本発明の着色樹脂組成物（以下、単に、「本発明の組成物」ということがある）は、下記一般式（１）で表される繰り返し単位を有するポリアミック酸およびＰＧ５８を含むことを特徴とする。
Figure JPOXMLDOC01-appb-C000005
 　一般式（１）中、Ｒ1はｎ＋２価の連結基を表し、Ｒ2は２価の連結基を表し、ｎは１または２を表す。
　例えば、ＰＧ５８を用いたカラーフィルタは、青色顔料（例えばＣ．Ｉ．ピグメントブルー１５：６（以下、「ＰＢ１５：６」ともいう。））を含む画素を隣接させた状態で高温加熱を行うと、ＰＧ５８の一部が隣接する青色画素に熱拡散し、熱拡散したＰＧ５８と青色顔料との混晶を形成し、青色画素と緑色画素の境界領域に針状の異物が形成されてしまうことがわかった。これに対して、本発明では、ＰＧ５８と、一般式（１）で表される繰り返し単位を有するポリアミック酸とを含む着色樹脂組成物を用いることにより、上記課題を解決することができる。また、耐溶剤性も向上させることができる。
　このメカニズムは推定であるが、本発明の着色樹脂組成物に含有されるポリアミック酸は、画素パターン形成後のポストベーク工程で脱水反応を伴うイミド環化を起こす。本発明の着色樹脂組成物に含有されるポリアミック酸は、上記イミド環化によって非常に膜密度が高い緻密な膜を形成するため、ＰＧ５８をポリイミド膜中に強固に保持することができる。結果として、高温加熱時における針状異物の発生を抑制することができる。 The colored resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) includes a polyamic acid having a repeating unit represented by the following general formula (1) and PG58. To do.
Figure JPOXMLDOC01-appb-C000005
 In general formula (1), R 1 represents an n + divalent linking group, R 2 represents a divalent linking group, and n represents 1 or 2.
For example, when a color filter using PG58 is heated at a high temperature in a state where pixels containing a blue pigment (for example, CI Pigment Blue 15: 6 (hereinafter also referred to as “PB15: 6”)) are adjacent to each other. , A part of PG 58 is thermally diffused to the adjacent blue pixel, a mixed crystal of the thermally diffused PG 58 and the blue pigment is formed, and needle-like foreign matters are formed in the boundary region between the blue pixel and the green pixel. all right. On the other hand, in this invention, the said subject can be solved by using the coloring resin composition containing PG58 and the polyamic acid which has a repeating unit represented by General formula (1). Moreover, solvent resistance can also be improved.
Although this mechanism is presumed, the polyamic acid contained in the colored resin composition of the present invention causes imide cyclization accompanied by a dehydration reaction in the post-baking step after the pixel pattern is formed. Since the polyamic acid contained in the colored resin composition of the present invention forms a dense film having a very high film density by the imide cyclization, PG58 can be firmly held in the polyimide film. As a result, it is possible to suppress the occurrence of acicular foreign matters during high temperature heating.
＜一般式（１）で表される繰り返し単位を有するポリアミック酸＞
　一般式（１）中、Ｒ1は　酸無水物に由来する基であり、ｎ＋２価の連結基を表す。一般式（１）で表される繰り返し単位を有するポリアミック酸は、着色樹脂組成物中にてＰＧ５８を分散させる分散剤としても機能する。また、熱硬化剤としても機能する。
　Ｒ1は、炭素数２～２２のｎ＋２価の連結基であることが好ましい。具体的に、Ｒ1は、炭化水素基、または、炭化水素基と、－ＣＯ－、－ＮＲ－、－Ｏ－、－ＳＯ2－、および－Ｓ－の少なくとも１種との組み合わせからなるｎ＋２価の連結基が好ましく、炭化水素基、または、炭化水素基と－ＣＯ－との組み合わせからなるｎ＋２価の連結基がより好ましい。Ｒ1は、１つの炭化水素基と、－ＣＯ－、－ＮＲ－、－Ｏ－、－ＳＯ2－、または－Ｓ－との組み合わせからなるｎ＋２価の連結基であってもよいし、２つ以上の炭化水素基と、－ＣＯ－、－ＮＲ－、－Ｏ－、－ＳＯ2－、および－Ｓ－から選択される２つ以上の基との組み合わせからなるｎ＋２価の連結基であってもよい。また、Ｒ1が炭化水素基と、－ＣＯ－、－ＮＲ－、－ＳＯ2－、－Ｏ－および－Ｓ－の少なくとも１種との組み合わせからなるｎ＋２価の連結基である場合、－ＣＯ－、－ＮＲ－、－Ｏ－、－ＳＯ2－、および－Ｓ－は、隣接していないことが好ましい。
　上記－ＮＲ－におけるＲは、水素原子または炭素数１～６のアルキル基を表し、水素原子が好ましい。ｎ＋２価の連結基が有する炭化水素基は、直鎖状、分岐鎖状または環状のいずれであってもよいが、環状が好ましい。
　Ｒ1は、環状構造を含むことが好ましく、環状の炭化水素基を含むことが好ましい。環状構造は、脂環であっても芳香族環であってもよいが、芳香族環が好ましい。また、環状構造は、単環であっても多環であってもよい。環状構造は、５～８員環を含むことが好ましく、５または６員環を含むことがより好ましい。また、環状構造は、単環であっても複素環であってもよい。環状構造が複素環である場合、複素環を構成するヘテロ原子としては、窒素原子、酸素原子、硫黄原子等が挙げられる。
　具体的に、Ｒ1は炭素数３～２２の脂環炭化水素基または炭素数６～２２の芳香族炭化水素基を有することが好ましく、炭素数６～２２の芳香族炭化水素基を有することがより好ましく、炭素数６～１２の芳香族炭化水素基を有することがさらに好ましい。 <Polyamic acid having a repeating unit represented by the general formula (1)>
In general formula (1), R 1 is a group derived from an acid anhydride and represents an n + divalent linking group. The polyamic acid having a repeating unit represented by the general formula (1) also functions as a dispersant for dispersing PG58 in the colored resin composition. It also functions as a thermosetting agent.
R 1 is preferably an n + divalent linking group having 2 to 22 carbon atoms. Specifically, R 1 is n + 2 consisting of a hydrocarbon group or a combination of a hydrocarbon group and at least one of —CO—, —NR—, —O—, —SO 2 —, and —S—. A valent linking group is preferable, and a hydrocarbon group or an n + divalent linking group composed of a combination of a hydrocarbon group and —CO— is more preferable. R 1 may be an n + divalent linking group comprising a combination of one hydrocarbon group and —CO—, —NR—, —O—, —SO 2 —, or —S—, N + divalent linking group comprising a combination of two or more hydrocarbon groups and two or more groups selected from —CO—, —NR—, —O—, —SO 2 —, and —S—. May be. When R 1 is an n + divalent linking group comprising a combination of a hydrocarbon group and at least one of —CO—, —NR—, —SO 2 —, —O— and —S—, -, -NR-, -O-, -SO 2- , and -S- are preferably not adjacent to each other.
R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom. The hydrocarbon group contained in the n + divalent linking group may be linear, branched or cyclic, but is preferably cyclic.
R 1 preferably includes a cyclic structure, and preferably includes a cyclic hydrocarbon group. The cyclic structure may be an alicyclic ring or an aromatic ring, but is preferably an aromatic ring. The cyclic structure may be monocyclic or polycyclic. The cyclic structure preferably contains a 5- to 8-membered ring, and more preferably contains a 5- or 6-membered ring. Further, the cyclic structure may be monocyclic or heterocyclic. When the cyclic structure is a heterocyclic ring, examples of the hetero atom constituting the heterocyclic ring include a nitrogen atom, an oxygen atom, and a sulfur atom.
Specifically, R 1 preferably has an alicyclic hydrocarbon group having 3 to 22 carbon atoms or an aromatic hydrocarbon group having 6 to 22 carbon atoms, and preferably has an aromatic hydrocarbon group having 6 to 22 carbon atoms. And more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms.
　一般式（１）中、Ｒ2はジアミンに由来する基であり、２価の連結基を表す。Ｒ2は、炭素数１～２２の２価の連結基であることが好ましい。具体的に、Ｒ2は、炭化水素基、または、炭化水素基と－Ｓｉ（Ｒ2A）2－、－ＣＯ－、－ＮＲ－、－Ｏ－、－ＳＯ2－、－Ｓ－から選択される少なくとも１種との組み合わせからなる基を含む２価の連結基が好ましい。
Ｒ2は、１つの炭化水素基と、－Ｓｉ（Ｒ2A）2－、－ＣＯ－、－ＮＲ－、－Ｏ－、－ＳＯ2－、または－Ｓ－との組み合わせからなる２価の連結基であってもよいし、２つ以上の炭化水素基と、－Ｓｉ（Ｒ2A）2－、－ＣＯ－、－ＮＲ－、－Ｏ－、－ＳＯ2－、および－Ｓ－から選択される２つ以上の基との組み合わせからなる２価の連結基であってもよい。
　Ｒ2Aはそれぞれ独立して炭素数１～６のアルキル基を表し、炭素数１～３のアルキル基がより好ましく、メチル基がさらに好ましい。－ＮＲ－におけるＲは、水素原子または炭素数１～６のアルキル基を表す。炭化水素基は、直鎖状、分岐鎖状または環状のいずれであってもよい。
　Ｒ2は、環状構造を含むことが好ましく、環状の炭化水素基を含むことが好ましい。環状構造は、上述した一般式（１）中のＲ1が有していてもよい環状構造と同義であり、好ましい範囲も同様である。
　Ｒ2は、炭素数３～２２の脂環炭化水素骨格または炭素数６～２２の芳香族炭化水素骨格を有する２価の連結基がより好ましく、炭素数６～１８の芳香族炭化水素骨格を有する２価の連結基がさらに好ましく、フェニレン基を有する２価の連結基が特に好ましい。
　一般式（１）中、ｎは１または２を表し、２が好ましい。２とすることにより、本発明の効果がより効果的に発揮される。 In general formula (1), R 2 is a group derived from diamine and represents a divalent linking group. R 2 is preferably a divalent linking group having 1 to 22 carbon atoms. Specifically, R 2 is selected from a hydrocarbon group, or a hydrocarbon group and —Si (R 2A ) 2 —, —CO—, —NR—, —O—, —SO 2 —, —S—. A divalent linking group containing a group composed of a combination with at least one kind is preferred.
R 2 is a divalent linkage comprising a combination of one hydrocarbon group and —Si (R 2A ) 2 —, —CO—, —NR—, —O—, —SO 2 —, or —S—. Or a group selected from two or more hydrocarbon groups and —Si (R 2A ) 2 —, —CO—, —NR—, —O—, —SO 2 —, and —S—. It may be a divalent linking group comprising a combination of two or more groups.
R 2A each independently represents an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group. R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The hydrocarbon group may be linear, branched or cyclic.
R 2 preferably contains a cyclic structure, and preferably contains a cyclic hydrocarbon group. The cyclic structure is synonymous with the cyclic structure that R 1 in the general formula (1) may have, and the preferred range is also the same.
R 2 is more preferably a divalent linking group having an alicyclic hydrocarbon skeleton having 3 to 22 carbon atoms or an aromatic hydrocarbon skeleton having 6 to 22 carbon atoms, and an aromatic hydrocarbon skeleton having 6 to 18 carbon atoms. A divalent linking group having a phenylene group is particularly preferable.
In general formula (1), n represents 1 or 2, and 2 is preferable. By setting it to 2, the effect of the present invention is more effectively exhibited.
　本発明で用いられるポリアミック酸は、一般式（１）中のＲ2が環状構造を含む繰り返し単位（繰り返し単位Ａ）を有することが好ましい。また、本発明で用いられるポリアミック酸は、一般式（１）中のＲ2が炭化水素基と上述した－Ｓｉ（Ｒ2A）2－の部分構造を含む繰り返し単位（繰り返し単位Ｂ）をさらに有していてもよい。ポリアミック酸が、－Ｓｉ（Ｒ2A）2－の部分構造を含む繰り返し単位を有することにより、着色樹脂組成物を用いて硬化膜を形成したときに、基板との接着性をより向上させることができる。
　一般式（１）で表される繰り返し単位の総量を１００モル％とした場合、含んでいてもよい繰り返し単位Ｂの量は、０．５～１５モル％が好ましく、１～１０モル％がより好ましく、３～７モル％がさらに好ましい。 The polyamic acid used in the present invention preferably has a repeating unit (repeating unit A) in which R 2 in the general formula (1) includes a cyclic structure. In addition, the polyamic acid used in the present invention further has a repeating unit (repeating unit B) in which R 2 in the general formula (1) includes a hydrocarbon group and the partial structure of —Si (R 2A ) 2 — described above. You may do it. When the polyamic acid has a repeating unit including a partial structure of —Si (R 2A ) 2 —, the adhesion to the substrate can be further improved when a cured film is formed using the colored resin composition. it can.
When the total amount of the repeating unit represented by the general formula (1) is 100 mol%, the amount of the repeating unit B that may be contained is preferably 0.5 to 15 mol%, more preferably 1 to 10 mol%. Preferably, 3 to 7 mol% is more preferable.
　一般式（１）で表される繰り返し単位を有するポリアミック酸は、公知の方法、例えば酸無水物とジアミンを選択的に組み合わせ、溶媒中で反応させることにより合成することができる。
　酸無水物としては、トリカルボン酸無水物やテトラカルボン酸無水物を用いることができ、テトラカルボン酸無水物を用いることが好ましい。
　トリカルボン酸無水物としては、トリメリット酸無水物、シクロヘキサン－１，２，４－トリカルボン酸－１，２－無水物、１，２，４－ナフタレントリカルボン酸－１，２－無水物、１，３，８－ナフタレントリカルボン酸－１，８－無水物などが挙げられる。
　テトラカルボン酸無水物としては、３,３´,４,４´－ベンゾフェノンテトラカルボン酸二無水物、ピロメリット酸無水物、３,３´,４,４´－ビフェニルトリフルフォロプロパンテトラカルボン酸二無水物、３,４,９,１０－ペリレンテトラカルボン酸二無水物、１,２,５,６－ナフタレンテトラカルボン酸二無水物、３,３″,４,４″－パラタ－フェニルテトラカルボン酸二無水物、３,３″,４,４″－メタタ－フェニルテトラカルボン酸二無水物、１,２,３,４－シクロブタンテトラカルボン酸二無水物、１,２,３,４－シクロペンタンテトラカルボン酸二無水物、１,２,３,５－シクロペンタンテトラカルボン酸二無水物、１,２,４,５－ビシクロヘキセンテトラカルボン酸二無水物、１,２,４,５－シクロヘキサンテトラカルボン酸二無水物、２,３,５－トリカルボキシシクロペンチル酢酸二無水物、４,４´－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、１,３,３ａ,４,５,９ｂ－ヘキサヒドロ－５－（テトラヒドロ－２,５－ジオキソ－３－フラニル）－ナフト［１,２－Ｃ］フラン－１,３－ジオンなどが挙げられる。 The polyamic acid having a repeating unit represented by the general formula (1) can be synthesized by a known method, for example, by selectively combining an acid anhydride and a diamine and reacting them in a solvent.
As the acid anhydride, tricarboxylic acid anhydride or tetracarboxylic acid anhydride can be used, and tetracarboxylic acid anhydride is preferably used.
Tricarboxylic acid anhydrides include trimellitic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, 1,2,4-naphthalene tricarboxylic acid-1,2-anhydride, 1, 3,8-naphthalenetricarboxylic acid-1,8-anhydride and the like.
Examples of tetracarboxylic acid anhydrides include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltrifluoropropanetetracarboxylic acid Anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -para-phenyltetracarboxylic Acid dianhydride, 3,3 ″, 4,4 ″ -metha-phenyltetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclo Pentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexene tetracarboxylic dianhydride, 1,2,4,5- Cyclohexanetetracarboxylic dianhydride, 2,3,5-tri Carboxycyclopentyl acetic acid dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-C] furan-1,3-dione.
　ジアミンの例としては、４,４´－ジアミノジフェニルエーテル、４,４´（または３，３’）－ジアミノジフェニルスルホン、４，４’－ジアミノベンズアニリド、３,３´－（または４,４´）ジアミノジフェニルメタン、４,４´－ジアミノジフェニルサルファイド、２,５－ジアミノトルエン、ｏ－トリジン、３,３´－ジメチル－４,４´－ジアミノジフェニルメタン、４,４´－ビス（４－アミノフェノキシ）ビフェニル、２,２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、ビス［４－（４－アミノフェノキシ）フェニル］エ－テル、２,２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン１,３－（または１,４）ジアミノシクロヘキサン、４,４´－ジアミノ－３,３´－ジメチルジシクロヘキシルメタン、４,４´－ジアミノ－３,３´－ジメチルジシクロヘキシル、３,３´－ジアミノジフェニルエーテル、３,４´－ジアミノジフェニルエーテルなどが挙げられる。 Examples of diamines include 4,4'-diaminodiphenyl ether, 4,4 '(or 3,3')-diaminodiphenyl sulfone, 4,4'-diaminobenzanilide, 3,3'- (or 4,4 ' ) Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,5-diaminotoluene, o-tolidine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) ) Biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] hexafluoropropane 1,3- (or 1,4) diaminocyclohexane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane 4,4'-diamino-3,3'-dimethyl dicyclohexyl, 3,3'-diaminodiphenyl ether, 3,4' like diaminodiphenyl ether and the like.
　ジアミン成分としては、本発明の効果を損なわない範囲で、上述した繰り返し単位Ｂを構成するモノマー（例えば、（３－アミノプロピル）テトラメチルジシロキサン（シロキサンジアミン））を併用してもよい。シロキサンジアミンの量は、全ジアミン中の１～２０モル％とするのが好ましい。シロキサンジアミンは、１種単独で用いてもよく、２種以上を用いてもよい。 As the diamine component, a monomer constituting the above-mentioned repeating unit B (for example, (3-aminopropyl) tetramethyldisiloxane (siloxane diamine)) may be used in combination as long as the effects of the present invention are not impaired. The amount of siloxane diamine is preferably 1 to 20 mol% in the total diamine. Siloxane diamine may be used individually by 1 type, and may use 2 or more types.
　一般式（１）で表される繰り返し単位を有するポリアミック酸を合成する際に用いることができる溶媒としては、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミドなどのアミド系極性溶媒、また、ラクトン系極性溶媒を混合して使用することができる。ラクトン類以外の溶媒としては、上記アミド系極性溶媒の他に、メチルセルソルブ、エチルセルソルブ、メチルカルビトール、エチルカルビトールなどを挙げることができる。ラクトン類とは、脂肪族環状エステルで炭素数３～１２の化合物をいう。具体的な例として、β－プロピオラクトン、γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン、γ－カプロラクトン、ε－カプロラクトンなどが挙げられるがこれらに限定されない。とくにポリアミック酸の溶解性の点で、γ－ブチロラクトンが好ましい。 Examples of the solvent that can be used for synthesizing the polyamic acid having the repeating unit represented by the general formula (1) include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and the like. These amide polar solvents and lactone polar solvents can be used in admixture. Examples of solvents other than lactones include methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol and the like in addition to the amide polar solvent. Lactones are aliphatic cyclic esters having 3 to 12 carbon atoms. Specific examples include, but are not limited to, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and the like. In particular, γ-butyrolactone is preferred from the viewpoint of solubility of polyamic acid.
　一般式（１）で表される繰り返し単位を有するポリアミック酸は、上述した酸無水物およびジアミン以外の他の酸成分または他のアミン成分を用いて、ポリアミック酸の分子量等を調製してもよい。他の酸成分および他のジアミン成分としては、例えば、単官能性の酸およびアミン成分が挙げられる。単官能性の酸またはアミン成分の例として、モノカルボン酸、カルボン酸二無水物、モノアミン等が挙げられる。具体例として、安息香酸、無水フタル酸、テトラクロロ無水フタル酸、無水マレイン酸、アニリンなどが挙げられるが、これらに限定されない。
　他の酸成分もしくは他のアミン成分の量は、ポリアミック酸の合成に使用するカルボン酸二無水物およびジアミンおよび他の酸成分および他のアミン成分の総モル数を基準として、０．５～５モル％が好ましく、０．７～３モル％がより好ましく、０．９～２モル％がさらに好ましい。 The polyamic acid having the repeating unit represented by the general formula (1) may be prepared by using the acid anhydride or diamine other than the above-described acid anhydride or other amine component to adjust the molecular weight of the polyamic acid. . Examples of the other acid component and the other diamine component include a monofunctional acid and an amine component. Examples of the monofunctional acid or amine component include monocarboxylic acid, carboxylic dianhydride, monoamine and the like. Specific examples include, but are not limited to, benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, aniline, and the like.
The amount of the other acid component or other amine component is 0.5 to 5 based on the total number of moles of carboxylic dianhydride and diamine and other acid components and other amine components used in the synthesis of the polyamic acid. The mol% is preferable, 0.7 to 3 mol% is more preferable, and 0.9 to 2 mol% is more preferable.
　一般式（１）で表される繰り返し単位を有するポリアミック酸の重量平均分子量は、５０００以上が好ましく、６，０００～１００，０００がより好ましく、８，０００～５０，０００がさらに好ましい。
　一般式（１）で表される繰り返し単位を有するポリアミック酸の分散度（質量平均分子量／数平均分子量）は、１．１～４．０が好ましく、１．５～３．０がより好ましく、１．７～２．５がさらに好ましい。 The weight average molecular weight of the polyamic acid having a repeating unit represented by the general formula (1) is preferably 5000 or more, more preferably 6,000 to 100,000, and further preferably 8,000 to 50,000.
The dispersity (mass average molecular weight / number average molecular weight) of the polyamic acid having a repeating unit represented by the general formula (1) is preferably 1.1 to 4.0, more preferably 1.5 to 3.0, More preferably, it is 1.7 to 2.5.
　着色樹脂組成物中における一般式（１）で表される繰り返し単位を有するポリアミック酸の含有量は、着色樹脂組成物の全固形分に対して、５～５０質量％が好ましく、７～４０質量％がより好ましく、９～３０質量％がさらに好ましい。
　着色樹脂組成物中に含まれる樹脂成分の総質量に対する、一般式（１）で表される繰り返し単位を有するポリアミック酸の量は、９０質量％とすることもでき、９５～１００質量％とすることもできる。
　着色樹脂組成物は、一般式（１）で表される繰り返し単位を有するポリアミック酸を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、その合計量が上記含有量に相当することが好ましい。 The content of the polyamic acid having the repeating unit represented by the general formula (1) in the colored resin composition is preferably 5 to 50% by mass, and preferably 7 to 40% by mass with respect to the total solid content of the colored resin composition. % Is more preferable, and 9 to 30% by mass is further preferable.
The amount of the polyamic acid having the repeating unit represented by the general formula (1) with respect to the total mass of the resin components contained in the colored resin composition can be 90% by mass, or 95 to 100% by mass. You can also.
The colored resin composition may contain only one type of polyamic acid having a repeating unit represented by the general formula (1), or may contain two or more types. When 2 or more types are included, the total amount thereof preferably corresponds to the above content.
＜ＰＧ５８＞
　着色樹脂組成物は、ＰＧ５８を含む。ＰＧ５８は、例えば特開２００７－２８４５９２号公報の段落００８４～００８５の記載の方法で合成することができ、この内容は本明細書に組み込まれる。
　本発明で用いられるＰＧ５８の平均一次粒子サイズは、１０ｎｍ以上が実際的である。上限としては、より良好なコントラストを得る観点から、１μｍ以下が好ましく、５００ｎｍ以下がより好ましく、２００ｎｍ以下がさらに好ましく、１００ｎｍ以下がさらに好ましく、５０ｎｍ以下が特に好ましい。また、粒子の単分散性を表す指標として、本発明においては、特に断りのない限り、体積平均粒径（Ｍｖ）と数平均粒径（Ｍｎ）の比（Ｍｖ／Ｍｎ）を用いる。顔料微粒子（一次粒子）の単分散性、つまりＭｖ／Ｍｎは、１．０～２．０であることが好ましく、１．０～１．８であることがより好ましく、１．０～１．５であることが特に好ましい。なお、本発明において粒子の平均一次粒径は、透過型電子顕微鏡により観察した画像から、円相当直径を求め、その５００個の平均値とする。 <PG58>
The colored resin composition contains PG58. PG58 can be synthesized, for example, by the method described in paragraphs 0084 to 0085 of JP-A-2007-284592, the contents of which are incorporated herein.
The average primary particle size of PG58 used in the present invention is practically 10 nm or more. The upper limit is preferably 1 μm or less, more preferably 500 nm or less, further preferably 200 nm or less, further preferably 100 nm or less, and particularly preferably 50 nm or less from the viewpoint of obtaining better contrast. In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of the pigment fine particles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1. 5 is particularly preferred. In the present invention, the average primary particle diameter of the particles is obtained by obtaining the equivalent circle diameter from an image observed with a transmission electron microscope, and taking the average value of the 500 particles.
　ＰＧ５８の粒子の調製方法としては通常の方法によればよく、例えば、ミリングにより粉砕して調製しても（ブレイクダウン法）、良溶媒と貧溶媒を用いて析出により調製（ビルドアップ法）してもよい。前者（ブレイクダウン法）については、ビーズミルなどを用いて定法により顔料粒子を微細化することができる。例えば、日本画像学会誌，第４５巻，第５号（２００６）１２－２１頁の「機械的解砕」の項に記載された説明を参照することができる。後者（ビルドアップ法）については再沈法などとも呼ばれ、例えば、特開２０１１－０２６４５２号公報、特開２０１１－０１２２１４号公報、特開２０１１－００１５０１号公報、特開２０１０－２３５８９５号公報、特開２０１０－２０９１号公報、特開２０１０－２０９１６０号公報などを参照することができる。 The PG58 particles may be prepared by ordinary methods, for example, by pulverizing by milling (breakdown method) or by precipitation using a good solvent and a poor solvent (buildup method). May be. About the former (breakdown method), a pigment particle can be refined | miniaturized by a usual method using bead mill etc. For example, it is possible to refer to the description described in the section “Mechanical Disintegration” in Journal of the Imaging Society of Japan, Vol. 45, No. 5 (2006), pages 12-21. The latter (build-up method) is also referred to as a reprecipitation method and the like. For example, JP 2011-026452 A, JP 2011-012214 A, JP 2011-001501 A, JP 2010-235895 A, Reference can be made to JP 2010-2091 A, JP 2010-209160 A, and the like.
＜他の着色剤＞
　着色樹脂組成物は、ＰＧ５８以外の他の着色剤を含んでいてもよいし、含んでいなくてもよい。他の着色剤は、１種単独で用いてもよく、２種以上併用してもよい。
　着色樹脂組成物は、他の着色剤として．黄色の着色剤を含んでいてもよい。黄色の着色剤としては、黄色顔料が好ましく、Ｃ．Ｉ．ピグメントイエロー１２９、Ｃ．Ｉ．ピグメントイエロー１３９、Ｃ．Ｉ．ピグメントイエロー１５０およびＣ．Ｉ．ピグメントイエロー１８５から選択される少なくとも１種がより好ましく、Ｃ．Ｉ．ピグメントイエロー１２９がさらに好ましい。このような構成とすることにより、本発明の効果をより向上させることができる。
　本発明の着色樹脂組成物は、Ａｌ、Ｔｉ、Ｆｅ、Ｓｎ、Ｐｂ、Ｇａ、Ｖ、Ｍｏ、Ｔａ、および、Ｎｂからなる群から選ばれる１種を中心金属として有するハロゲン化フタロシアニン顔料、および、中心金属を有さないハロゲン化フタロシアニン顔料から選ばれる１種以上のフタロシアニン顔料をさらに含んでいてもよい。このような構成とすることにより、本発明の効果に優れるとともに、他色の混色が生じにくい硬化膜を形成することができる。上記フタロシアニン顔料の含有量は、着色樹脂組成物中のＰＧ５８の含有量に対して、５質量％以下が好ましく、０．５～２質量％がより好ましい。 <Other colorants>
The colored resin composition may or may not contain a colorant other than PG58. Other colorants may be used alone or in combination of two or more.
The colored resin composition is used as another colorant. It may contain a yellow colorant. As the yellow colorant, a yellow pigment is preferable. I. Pigment yellow 129, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. More preferably at least one selected from CI Pigment Yellow 185; I. Pigment Yellow 129 is more preferable. By setting it as such a structure, the effect of this invention can be improved more.
The colored resin composition of the present invention includes a halogenated phthalocyanine pigment having, as a central metal, one selected from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta, and Nb, and One or more phthalocyanine pigments selected from halogenated phthalocyanine pigments having no central metal may be further included. By setting it as such a structure, while being excellent in the effect of this invention, the hardened | cured film which cannot produce other color mixing easily can be formed. The content of the phthalocyanine pigment is preferably 5% by mass or less, more preferably 0.5 to 2% by mass with respect to the content of PG58 in the colored resin composition.
　本発明の着色樹脂組成物に適宜添加できる他の有機顔料としては、上述したＰＧ５８および黄色顔料以外の他の有機顔料、無機顔料、染料等を用いることができる。
　本発明の着色樹脂組成物に適宜添加できる他の有機顔料としては、例えば、
Ｃ．Ｉ．ピグメントイエロー１１，２４，３１，５３，８３，９３，９９，１０８，１０９，１１０，１３８，１４７，１５１，１５４，１５５，１６７，１８０，１９９，；
Ｃ．Ｉ．ピグメントオレンジ３６，３８，４３，７１；
Ｃ．Ｉ．ピグメントレッド８１，１０５，１２２，１４９，１５０，１５５，１７１，１７５，１７６，２０９，２２０，２２４，２４２，２５５，２６４，２７０；
Ｃ．Ｉ．ピグメントバイオレット１９，２３，３２，３９；
Ｃ．Ｉ．ピグメントブルー１，２，１５，１５：１，１５：３，１５：６，１６，２２，６０，６６；
Ｃ．Ｉ．ピグメントグリーン７，３６，３７；
Ｃ．Ｉ．ピグメントブラウン２５，２８；
Ｃ．Ｉ．ピグメントブラック１；
等を挙げることができる。 As other organic pigments that can be appropriately added to the colored resin composition of the present invention, organic pigments other than the above-described PG58 and yellow pigments, inorganic pigments, dyes, and the like can be used.
Examples of other organic pigments that can be appropriately added to the colored resin composition of the present invention include:
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,147,151,154,155,167,180,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,209,220,224,242,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1;
Etc.
　本発明の着色樹脂組成物に適宜添加できる無機顔料としては、金属酸化物、金属錯塩等で示される金属化合物を挙げることができ、具体的には、鉄、コバルト、アルミニウム、カドミウム、鉛、銅、チタン、マグネシウム、クロム、亜鉛、アンチモン等の金属酸化物、および上記金属の複合酸化物、カーボンブラック、チタンブラック等の黒色顔料を挙げることができる。 Examples of the inorganic pigment that can be appropriately added to the colored resin composition of the present invention include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper And metal oxides such as titanium, magnesium, chromium, zinc, and antimony, and black pigments such as composite oxides of the above metals, carbon black, and titanium black.
　本発明の着色樹脂組成物に適宜添加できる公知の染料としては、例えば特開昭６４－９０４０３号公報、特開昭６４－９１１０２号公報、特開平１－９４３０１号公報、特開平６－１１６１４号公報、特登２５９２２０７号、米国特許４８０８５０１号明細書、米国特許５６６７９２０号明細書、米国特許５０５９５０号明細書、米国特許５６６７９２０号明細書、特開平５－３３３２０７号公報、特開平６－３５１８３号公報、特開平６－５１１１５号公報、特開平６－１９４８２８号公報等に開示されている色素を使用できる。化学構造として区分すると、ピラゾールアゾ化合物、ピロメテン化合物、アニリノアゾ化合物、トリフェニルメタン化合物、アントラキノン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、ピロロピラゾールアゾメチン化合物等を使用できる。また、染料としては色素多量体を用いてもよい。色素多量体としては、特開２０１１－２１３９２５号公報、特開２０１３－０４１０９７号公報に記載されている化合物が挙げられる。 Known dyes that can be appropriately added to the colored resin composition of the present invention include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614. No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat.No. 505950, U.S. Pat. The dyes disclosed in JP-A-6-51115 and JP-A-6-194828 can be used. When classified as a chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.
　着色樹脂組成物中のＰＧ５８の含有量は、着色樹脂組成物の全固形分に対して、２０～８０質量％が好ましく、３０～７０質量％がより好ましく、４０～６０質量％がさらに好ましい。
　着色樹脂組成物が黄色の着色剤をさらに含む場合、着色樹脂組成物中の黄色の着色剤の含有量は、ＰＧ５８（１００質量部）に対して、１０～１００質量部が好ましく、２０～８５質量部がより好ましい。また、着色樹脂組成物に含まれる黄色の着色剤の総量に対する、Ｃ．Ｉ．ピグメントイエロー１２９、Ｃ．Ｉ．ピグメントイエロー１５０およびＣ．Ｉ．ピグメントイエロー１８５の量は、８５質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５～１００質量％であることがさらに好ましい。 The content of PG58 in the colored resin composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass with respect to the total solid content of the colored resin composition.
When the colored resin composition further contains a yellow colorant, the content of the yellow colorant in the colored resin composition is preferably 10 to 100 parts by mass, preferably 20 to 85 parts with respect to PG58 (100 parts by mass). Part by mass is more preferable. Moreover, C.I. with respect to the total amount of the yellow colorant contained in the colored resin composition. I. Pigment yellow 129, C.I. I. Pigment yellow 150 and C.I. I. The amount of CI Pigment Yellow 185 is preferably 85% by mass or more, more preferably 90% by mass or more, and further preferably 95 to 100% by mass.
＜顔料誘導体＞
　本発明の組成物は、顔料誘導体をさらに含んでいてもよい。顔料誘導体としては、分子内に顔料母核構造とアミノ基とを有する化合物（以下、特定顔料誘導体ともいう。）を用いることが好ましい。
　特定顔料誘導体を用いることで、特定顔料誘導体中の顔料母核構造とＰＧ５８との間において相互作用が形成されて両者の吸着性をより効果的に確保することができる。 <Pigment derivative>
The composition of the present invention may further contain a pigment derivative. As the pigment derivative, it is preferable to use a compound having a pigment mother nucleus structure and an amino group in the molecule (hereinafter also referred to as a specific pigment derivative).
By using the specific pigment derivative, an interaction is formed between the pigment core structure in the specific pigment derivative and PG58, and the adsorptivity of both can be more effectively ensured.
　特定顔料誘導体は、下記一般式（Ａ）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000006
 The specific pigment derivative is preferably a compound represented by the following general formula (A).
Figure JPOXMLDOC01-appb-C000006
　一般式（Ａ）中、Ｒ1およびＲ2は、各々独立に水素原子又は１価の有機基を表し、好ましくは炭素数１～２０の飽和又は不飽和アルキル基、炭素数３～２０の飽和又は不飽和シクロアルキル基又はアリール基である。これらの有機基は、さらに置換基を有していてもよい。さらに有していてもよい置換基としては、ハロゲン原子、水酸基、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、シクロアルキニル基、アリール基、ヘテロ環基、シアノ基、アルコキシ基、アリーロキシ基、チオアルコキシ基、チオアリーロキシ基、カルボキシル基、アルコキシカルボニル基、スルホ基、スルホンアミド基、ウレア基、チオウレア基、アミノ基、アミド基、カルボニル基、ニトロ基或いはこれらの基を有する置換基が挙げられる。
　また、Ｒ1およびＲ2は互いに結合して環を形成してもよい。 In the general formula (A), R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group, preferably a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, or a saturated group having 3 to 20 carbon atoms. Or an unsaturated cycloalkyl group or an aryl group. These organic groups may further have a substituent. Further, the substituents that may have are halogen atoms, hydroxyl groups, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups. , Aryloxy group, thioalkoxy group, thioaryloxy group, carboxyl group, alkoxycarbonyl group, sulfo group, sulfonamido group, urea group, thiourea group, amino group, amide group, carbonyl group, nitro group or these groups A substituent is mentioned.
R 1 and R 2 may be bonded to each other to form a ring.
　特に、一般式（Ａ）で表される化合物は、分子内にアミド構造及びウレア構造の少なくとも１つを有する化合物であることが好ましい。また、一般式（Ａ）で表される化合物は、ヘテロ環構造を有する化合物であることが好ましい。 In particular, the compound represented by the general formula (A) is preferably a compound having at least one of an amide structure and a urea structure in the molecule. Moreover, it is preferable that the compound represented by general formula (A) is a compound which has a heterocyclic structure.
　一般式（Ａ）中、Ｘは顔料母核構造を含むｍ価の基である。ここで、顔料母核構造としては、有機顔料における発色原子団、その類似構造、或いは部分構造であり、具体的には、アゾ基を有する骨格、ウレア構造を有する骨格、アミド構造を有する骨格、環状アミド構造を有する骨格、ヘテロ原子含有５員環を有する芳香族環、及び、ヘテロ原子含有６員環を有する芳香族環から選択される１種以上の部分構造を含む構造等が挙げられる。Ｘは、これらの顔料母核構造を含む置換基である。
　一般式（Ａ）中のＸとしては、顔料母核構造又は顔料母核構造と芳香環、或いは含窒素芳香環、或いは含酸素芳香環、或いは含硫黄芳香環を有し、アミノ基が顔料母核構造、芳香環、含窒素芳香環、含酸素芳香環、含硫黄芳香環のいずれかに直接或いは連結基により結合されていることが好ましい。特に、顔料母核構造と芳香環、或いは含窒素芳香環を有し、アミノ基と２価の連結基で結合されていることが好ましい。
　一般式（Ａ）中、ｍは、１～８の整数であり、分散性、分散液の保存安定性の観点から１～６が好ましく、１または２がより好ましい。 In general formula (A), X is an m-valent group containing a pigment mother nucleus structure. Here, the pigment mother nucleus structure is a chromogenic group in an organic pigment, a similar structure, or a partial structure. Specifically, a skeleton having an azo group, a skeleton having a urea structure, a skeleton having an amide structure, Examples thereof include a structure containing one or more partial structures selected from a skeleton having a cyclic amide structure, an aromatic ring having a heteroatom-containing 5-membered ring, and an aromatic ring having a heteroatom-containing 6-membered ring. X is a substituent containing these pigment mother nucleus structures.
X in the general formula (A) has a pigment mother nucleus structure or a pigment mother nucleus structure and an aromatic ring, a nitrogen-containing aromatic ring, an oxygen-containing aromatic ring, or a sulfur-containing aromatic ring, and an amino group is a pigment mother structure. It is preferably bonded directly or via a linking group to any one of the core structure, aromatic ring, nitrogen-containing aromatic ring, oxygen-containing aromatic ring and sulfur-containing aromatic ring. In particular, it preferably has a pigment mother nucleus structure and an aromatic ring or a nitrogen-containing aromatic ring and is bonded to an amino group by a divalent linking group.
In the general formula (A), m is an integer of 1 to 8, preferably 1 to 6, and more preferably 1 or 2, from the viewpoint of dispersibility and storage stability of the dispersion.
　以下に、本発明に用いられる顔料誘導体の好ましい具体例を示すが、これらに限定されるものではない。下記に示す顔料誘導体の中でも、顔料母核構造としてベンズイミダゾール骨格を有する誘導体が好ましい。具体的には、下記に示す顔料誘導体のうち、(1)～(12)で表されるベンズイミダゾール骨格含有の顔料誘導体が好ましく、(7)～(12)で表されるベンズイミダゾール骨格含有の顔料誘導体が特に好ましい。 Hereinafter, preferred specific examples of the pigment derivative used in the present invention are shown, but the invention is not limited thereto. Among the pigment derivatives shown below, derivatives having a benzimidazole skeleton as the pigment nucleus structure are preferable. Specifically, among the pigment derivatives shown below, pigment derivatives containing a benzimidazole skeleton represented by (1) to (12) are preferable, and those containing a benzimidazole skeleton containing (7) to (12) are preferable. Pigment derivatives are particularly preferred.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　特に、本発明の組成物に用いられる顔料誘導体として、以下の化合物が好ましい。
　下記に示す顔料誘導体の中でも、カルボン酸基もしくはスルホン酸基もしくはこれらの金属塩・アンモニウム塩を置換基として有する顔料誘導体が好ましい。具体的には、下記に示す顔料誘導体の中でも、（Ａ）～（Ｉ）で表される顔料誘導体を用いる事が好ましく、（Ａ）、（Ｂ）、（Ｉ）で表される顔料誘導体が特に好ましい。
Figure JPOXMLDOC01-appb-C000028
 In particular, the following compounds are preferred as the pigment derivative used in the composition of the present invention.
Among the pigment derivatives shown below, a pigment derivative having a carboxylic acid group or a sulfonic acid group or a metal salt / ammonium salt thereof as a substituent is preferable. Specifically, among the pigment derivatives shown below, the pigment derivatives represented by (A) to (I) are preferably used, and the pigment derivatives represented by (A), (B), and (I) are preferably used. Particularly preferred.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　色素誘導体の含有量は、着色樹脂組成物中におけるＰＧ５８を含む全顔料１００質量部に対して、０．５～５０質量部が好ましく、１～２５質量部がより好ましく、５～１５質量部がさらに好ましい。
　色素誘導体は、着色樹脂組成物中に１種のみ含まれていてもよいし、２種以上含まれていてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 The content of the pigment derivative is preferably 0.5 to 50 parts by mass, more preferably 1 to 25 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the total pigment including PG58 in the colored resin composition. Further preferred.
Only 1 type of pigment derivative may be contained in the colored resin composition, and may be contained 2 or more types. When two or more types are included, the total amount is preferably within the above range.
＜一般式（２）で表されるジアミン化合物＞
　本発明の組成物は、一般式（２）で表されるジアミン化合物をさらに含むことが好ましい。
Figure JPOXMLDOC01-appb-C000031
 一般式（２）中、Ｒ3は２価の連結基を表す。 <Diamine compound represented by the general formula (2)>
It is preferable that the composition of this invention further contains the diamine compound represented by General formula (2).
Figure JPOXMLDOC01-appb-C000031
 In general formula (2), R 3 represents a divalent linking group.
　上記構成とすることにより、本発明の効果をより効果的に達成することができる。このメカニズムは推定であるが、一般的にポリアミック酸を含む塗膜を高温加熱すると、下記式（ａ）に示す反応機構でポリアミック酸が脱水反応を伴うイミド環化を起こし、塗膜が硬化する。この際、アミン化合物が塗膜に含まれていると、下記式（ｂ）に示すような反応機構によってアミン化合物（下記式（ｂ）中のＲ3－ＮＨ2）が塩基触媒として働き、イミド環化による塗膜の硬化が促進される。こうして、塗膜の硬化が促進されることによって、ＰＧ５８がより強固にポリイミド膜中に保持されるため、得られるカラーフィルタの高温加熱時の針状異物の発生を抑制できる。 By setting it as the said structure, the effect of this invention can be achieved more effectively. Although this mechanism is presumed, generally, when a coating film containing polyamic acid is heated at a high temperature, the polyamic acid undergoes imide cyclization accompanied by a dehydration reaction by the reaction mechanism represented by the following formula (a), and the coating film is cured. . In this case, if the amine compound is contained in the coating film, the amine compound (R 3 —NH 2 in the following formula (b)) acts as a base catalyst by the reaction mechanism shown in the following formula (b), and the imide Curing of the coating film by cyclization is promoted. Thus, since hardening of a coating film is accelerated | stimulated, since PG58 is hold | maintained more firmly in a polyimide film, generation | occurrence | production of the acicular foreign material at the time of high temperature heating of the color filter obtained can be suppressed.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　一般式（２）中、Ｒ3はジアミンに由来する基であり、２価の連結基を表す。Ｒ3は、炭素数１～２２の２価の連結基であることが好ましい。具体的に、Ｒ3は炭化水素基、または、炭化水素基と－ＣＯ－、－ＮＲ－、－Ｏ－との組み合わせからなる基を含む２価の連結基が好ましい。－ＮＲ－におけるＲは、水素原子または炭素数１～６のアルキル基を表す。炭化水素基は、直鎖状、分岐鎖状または環状のいずれであってもよい。
　Ｒ3は、環状構造を含むことが好ましく、環状の炭化水素基を含むことが好ましい。環状構造は、上述した一般式（１）中のＲ2が有していてもよい環状構造と同義である。また、Ｒ3の好ましい範囲は、上述した一般式（１）のＲ2と同様である。
　また、一般式（２）中のＲ3は、一般式（１）中のＲ2と同一の骨格を含む２価の連結基が好ましい。一般式（２）中のＲ3として、一般式（１）中のＲ2と同一の骨格を含む２価の連結基を有するジアミン化合物は、一般式（１）で表されるポリアミック酸との相溶性に優れるため、一般式（１）で表されるポリアミック酸の熱硬化反応の触媒としてより有効になり、本発明の効果をより効果的に達成することができる。
　ここで、Ｒ2と同一の骨格とは、２価の連結基を構成する原子の少なくとも一部が共通していることをいう。例えば、Ｒ2がフェニレン基である場合、Ｒ3はフェニレン基であってもよいし、フェニレン基が置換されていてもよいし、フェニレン基と－Ｏ－との組み合わせからなる基であってもよい。特に、Ｒ3は、一般式（１）中のＲ2と同一の部分構造を有することが好ましく、一般式（１）中のＲ2と同一の構造であることがより好ましい。
　一般式（２）で表されるジアミン化合物の具体例としては、上述したポリアミック酸を合成する際に用いることができるジアミンが挙げられる。 In general formula (2), R 3 is a group derived from diamine and represents a divalent linking group. R 3 is preferably a divalent linking group having 1 to 22 carbon atoms. Specifically, R 3 is preferably a hydrocarbon group or a divalent linking group containing a group composed of a combination of a hydrocarbon group and —CO—, —NR—, and —O—. R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The hydrocarbon group may be linear, branched or cyclic.
R 3 preferably includes a cyclic structure, and preferably includes a cyclic hydrocarbon group. The cyclic structure is synonymous with the cyclic structure that R 2 in the general formula (1) may have. Further, preferred ranges of R 3 is the same as R 2 of the above-mentioned general formula (1).
In addition, R 3 in the general formula (2) is preferably a divalent linking group containing the same skeleton as R 2 in the general formula (1). As R 3 in the general formula (2), a diamine compound having a divalent linking group containing the same skeleton as R 2 in the general formula (1) is a polyamic acid represented by the general formula (1). Since it is excellent in compatibility, it becomes more effective as a catalyst for the thermosetting reaction of the polyamic acid represented by the general formula (1), and the effects of the present invention can be achieved more effectively.
Here, the same skeleton as R 2 means that at least a part of atoms constituting the divalent linking group is common. For example, when R 2 is a phenylene group, R 3 may be a phenylene group, a phenylene group may be substituted, or a group consisting of a combination of a phenylene group and —O—. Good. In particular, R 3 preferably has the same partial structure as R 2 in general formula (1), and more preferably has the same structure as R 2 in general formula (1).
Specific examples of the diamine compound represented by the general formula (2) include diamines that can be used when synthesizing the polyamic acid described above.
　着色樹脂組成物中における一般式（２）で表されるジアミン化合物の含有量は、着色樹脂組成物の全固形分に対して、０．０１～１０質量％が好ましく、０．１～２質量％がより好ましく、０．３～０．８質量％がさらに好ましく、０．４～０．７質量％が特に好ましい。
　一般式（２）で表されるジアミン化合物は、１種単独で用いてもよく、２種以上併用してもよい。２種以上用いる場合、その合計量が上記含有量に相当することが好ましい。 The content of the diamine compound represented by the general formula (2) in the colored resin composition is preferably 0.01 to 10% by mass, and preferably 0.1 to 2% by mass with respect to the total solid content of the colored resin composition. % Is more preferable, 0.3 to 0.8% by mass is further preferable, and 0.4 to 0.7% by mass is particularly preferable.
The diamine compound represented by the general formula (2) may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount corresponds to the said content.
＜有機溶剤＞
　本発明の組成物は、有機溶剤をさらに含有してもよい。
　有機溶剤は、各成分の溶解性や着色樹脂組成物の塗布性を満足すれば基本的には特に限定されない。 <Organic solvent>
The composition of the present invention may further contain 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 colored resin composition are satisfied.
　有機溶剤としては、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸シクロヘキシル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、オキシ酢酸アルキル（例：オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－オキシプロピオン酸アルキルエステル類（例：３－オキシプロピオン酸メチル、３－オキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、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等））、２－オキシプロピオン酸アルキルエステル類（例：２－オキシプロピオン酸メチル、２－オキシプロピオン酸エチル、２－オキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－オキシ－２－メチルプロピオン酸メチルおよび２－オキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル、γ－ブチロラクトン等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン等、並びに、芳香族炭化水素類として、例えば、トルエン、キシレン、並びに、アルコール類として、例えば３－メチル－３－メトキシブタノール等が好適に挙げられる。 Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )) 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy- Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-oxobutanoic acid Ethyl, γ-butyrolactone, etc. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether , Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like, and ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbons, Example If, toluene, xylene, and, as alcohols, such as 3-methyl-3-methoxybutanol and the like are preferably exemplified.
　有機溶剤の着色樹脂組成物中における含有量は、塗布性の観点から、組成物の全固形分濃度が５質量％～８０質量％になる量とすることが好ましく、５質量％～６０質量％がさらに好ましく、１０質量％～５０質量％が特に好ましい。
　本発明の組成物は、有機溶剤を、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 The content of the organic solvent in the colored resin composition is preferably such that the total solid concentration of the composition is 5% by mass to 80% by mass from the viewpoint of applicability. Is more preferable, and 10% by mass to 50% by mass is particularly preferable.
The composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.
＜その他の成分＞
　本発明の着色樹脂組成物は、上述した成分以外の他の成分として、顔料分散剤、重合性化合物、重合開始剤、アルカリ可溶性樹脂、界面活性剤、アルカリ土類金属イオン等を含有していてもよい。 <Other ingredients>
The colored resin composition of the present invention contains a pigment dispersant, a polymerizable compound, a polymerization initiator, an alkali-soluble resin, a surfactant, an alkaline earth metal ion, and the like as components other than the components described above. Also good.
（顔料分散剤）
　本発明の組成物は、上述したポリアミック酸が顔料分散剤としても機能するため、顔料分散剤を実質的に含有しなくてもよいが、顔料分散剤をさらに含有してもよい。
　顔料分散剤としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、及び、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、アルカノールアミン等の界面活性剤、及び、顔料誘導体等を挙げることができる。　高分子分散剤は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、ブロック型高分子に分類することができる。
　顔料分散剤については、例えば特開２０１３－２９７６０号公報の段落０２１６～０２２２の記載を参酌することができ、この内容は本願明細書に組み込まれる。
　着色樹脂組成物において、顔料分散剤をさらに含有する場合、顔料分散剤の総含有量としては、ＰＧ５８を含む顔料１００質量部に対して、１質量部～８０質量部とすることもでき、５質量部～７０質量部とすることもでき、１０質量部～６０質量部とすることもできる。
　本発明の組成物が顔料分散剤を実質的に含有しない場合、顔料分散剤の含有量は、ＰＧ５８を含む顔料１００質量部に対して、５質量部以下とすることもでき、１質量部以下とすることもでき、０質量部とすることもできる。
（重合性化合物）
　本発明の組成物は、上述したポリアミック酸が熱硬化剤としても機能するため、重合性化合物を実質的に含有しなくてもよいが、重合性化合物をさらに含有してもよい。
　重合性化合物は、例えば、特開２０１１－１３７１２５号公報段落０１２９～０１３６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。
　本発明の組成物が重合性化合物を含有する場合、重合性化合物の含有量は、本発明の組成物の全固形分に対し、１～１０質量％とすることができ、０．１～３質量％とすることもできる。
　本発明の組成物が重合性化合物を実質的に含有しない場合、重合性化合物の含有量は、本発明の組成物の全固形分に対し、１質量％以下とすることができ、０．１質量％以下とすることもでき、０質量％とすることもできる。 (Pigment dispersant)
In the composition of the present invention, since the above-described polyamic acid also functions as a pigment dispersant, the pigment dispersant may not be substantially contained, but may further contain a pigment dispersant.
Examples of the pigment dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic. -Based copolymers, naphthalenesulfonic acid formalin condensates], surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like. The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
With respect to the pigment dispersant, for example, the description in paragraphs 0216 to 0222 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
When the colored resin composition further contains a pigment dispersant, the total content of the pigment dispersant may be 1 to 80 parts by mass with respect to 100 parts by mass of the pigment containing PG58. The mass may be from 70 parts by mass, and may be from 10 to 60 parts by mass.
When the composition of the present invention does not substantially contain a pigment dispersant, the content of the pigment dispersant can be 5 parts by mass or less with respect to 100 parts by mass of the pigment containing PG58, and 1 part by mass or less. Or 0 parts by mass.
(Polymerizable compound)
Since the polyamic acid mentioned above functions also as a thermosetting agent, the composition of this invention does not need to contain a polymeric compound substantially, but may contain a polymeric compound further.
As for the polymerizable compound, for example, the description in paragraphs 0129 to 0136 of JP2011-137125A can be referred to, and the contents thereof are incorporated in the present specification.
When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound can be 1 to 10% by mass with respect to the total solid content of the composition of the present invention, 0.1 to 3 It can also be made into the mass%.
When the composition of the present invention does not substantially contain a polymerizable compound, the content of the polymerizable compound can be 1% by mass or less based on the total solid content of the composition of the present invention. It can also be made into the mass% or less, and can also be 0 mass%.
（重合開始剤）
　本発明の組成物は、重合開始剤を含有してもよいが、重合開始剤を実質的に含有しなくてもよい。特に本発明の組成物をドライエッチングプロセスに用いる場合、光重合開始剤を実質的に含有しないことが好ましい。
　重合開始剤としては、例えば、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。光重合開始剤は１種のみでもよいし、２種類以上を併用してもよい。
　重合開始剤としては、例えば、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もの、オキサジアゾール骨格を有するもの、など）、アシルホスフィンオキサイド等の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、オキシム誘導体等のオキシム化合物、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、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノンなどが挙げられる。
　オキシム化合物としては、例えば、特開２０１２－２０８４９４号公報段落０５１３（対応する米国特許出願公開第２０１２／２３５０９９号明細書の[０６３２]）以降の式（ＯＸ－１）または（ＯＸ－２）で表される化合物の説明を参酌でき、これらの内容は本明細書に組み込まれる。
　また、重合開始剤としては、ＴＲＯＮＬＹ ＴＲ－ＰＢＧ－３０４、ＴＲＯＮＬＹ ＴＲ－ＰＢＧ－３０９、ＴＲＯＮＬＹ ＴＲ－ＰＢＧ－３０５（常州強力電子新材料有限公司社（CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO.,LTD）製）などの市販品を用いることもできる。
　本発明の組成物が、重合開始剤を含有する場合、重合開始剤の含有量は、本発明の組成物の全固形分に対し、１～５質量％とすることができ、０．１～１質量％とすることもできる。
　本発明の組成物が重合開始剤を実質的に含有しない場合、重合開始剤の含有量は、本発明の組成物の全固形分に対し、１質量％以下とすることができ、０．１質量％以下とすることもでき、０質量％とすることもできる。 (Polymerization initiator)
Although the composition of this invention may contain a polymerization initiator, it does not need to contain a polymerization initiator substantially. In particular, when the composition of the present invention is used in a dry etching process, it is preferable that the photopolymerization initiator is not substantially contained.
As a polymerization initiator, it can select suitably from well-known photoinitiators, for example. Only one type of photopolymerization initiator may be used, or two or more types may be used in combination.
Examples of the polymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.
Examples of the oxime compound include those represented by the following formula (OX-1) or (OX-2) in paragraph 0513 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/235099, [0632]). Reference may be made to the description of the compounds represented, the contents of which are incorporated herein.
In addition, as polymerization initiators, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) Commercial products such as can also be used.
When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator can be 1 to 5% by mass relative to the total solid content of the composition of the present invention, and 0.1 to It can also be 1 mass%.
When the composition of the present invention does not substantially contain a polymerization initiator, the content of the polymerization initiator can be 1% by mass or less based on the total solid content of the composition of the present invention. It can also be made into the mass% or less, and can also be 0 mass%.
（アルカリ可溶性樹脂）
　アルカリ可溶性樹脂としては、線状有機高分子重合体であって、分子（好ましくは、アクリル系共重合体、スチレン系共重合体を主鎖とする分子）中に少なくとも１つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。
アルカリ可溶性樹脂は、特開２０１２－２０８４９４号公報段落０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の[０６８５]～[０７００]）以降の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
　本発明の着色樹脂組成物がアルカリ可溶性樹脂を含有する場合、アルカリ可溶性樹脂の含有量は、本発明の組成物の全固形分中、０．０１～１０質量％とすることができ、１～５質量％とすることもできる。 (Alkali-soluble resin)
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group.
For the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. It is incorporated herein.
When the colored resin composition of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin can be 0.01 to 10% by mass in the total solid content of the composition of the present invention. It can also be 5 mass%.
（界面活性剤）
　本発明の組成物は、塗布性をより向上させる観点から、各種の界面活性剤をさらに含有していてもよい。
　界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。特に、本発明の組成物は、フッ素系界面活性剤を含有することで、塗布液として調製したときの液特性（特に、流動性）がより向上させることができ、塗布厚の均一性や省液性をより改善することができる。
　即ち、フッ素系界面活性剤を含有する組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力を低下させることにより、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、少量の液量で数μｍ程度の薄膜を形成した場合であっても、厚みムラの小さい均一厚の膜形成をより好適に行える点で有効である。
　フッ素系界面活性剤中のフッ素含有率は、３質量％～４０質量％が好適であり、より好ましくは５質量％～３０質量％であり、特に好ましくは７質量％～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、組成物中における溶解性も良好である。 (Surfactant)
The composition of the present invention may further contain various surfactants from the viewpoint of further improving applicability.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. In particular, the composition of the present invention can further improve liquid properties (particularly fluidity) when it is prepared as a coating solution by containing a fluorosurfactant, and can improve uniformity of coating thickness and saving. Liquidity can be further improved.
That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. Is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、同Ｆ７８１（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）等が挙げられる。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
　ノニオン系界面活性剤として具体的には、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およ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、グリセリンエトキシレート等）、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（ＢＡＳＦ社製のプルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１）、ソルスパース２００００（日本ルーブリゾール（株））等が挙げられる。 Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, 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 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like.
　カチオン系界面活性剤として具体的には、フタロシアニン誘導体（商品名：ＥＦＫＡ－７４５、森下産業（株）製）、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株）製）等が挙げられる。 Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
　アニオン系界面活性剤として具体的には、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）社製）等が挙げられる。 Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
　シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング（株）製「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」、モメンティブ・パフォーマンス・マテリアルズ社製「ＴＳＦ－４４４０」、「ＴＳＦ－４３００」、「ＴＳＦ－４４４５」、「ＴＳＦ－４４６０」、「ＴＳＦ－４４５２」、信越シリコーン株式会社製「ＫＰ３４１」、「ＫＦ６００１」、「ＫＦ６００２」、ビックケミー社製「ＢＹＫ３０７」、「ＢＹＫ３２３」、「ＢＹＫ３３０」等が挙げられる。
　本発明の組成物に界面活性剤を含有する場合、界面活性剤の含有量は、本発明の組成物の全質量に対して、０．００１質量％～２．０質量％が好ましく、より好ましくは０．００５質量％～１．０質量％である。
　本発明の組成物は、界面活性剤を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
When a surfactant is contained in the composition of the present invention, the content of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably based on the total mass of the composition of the present invention. Is 0.005 mass% to 1.0 mass%.
The composition of the present invention may contain only one type of surfactant or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
（アルカリ土類金属イオン）
　本発明の着色樹脂組成物は、アルカリ土類金属イオン（例えばカルシウムイオン等）をさらに含有していてもよい。このような構成とすることにより、本発明の効果に優れるとともに、溶融した亜鉛フタロシアニンと銅フタロシアニンとの混晶による針状異物の発生をより効果的に抑制することができる。例えば、ＰＧ５８の質量に対するアルカリ土類金属イオンの含有量は、３０～３００質量ｐｐｍとすることができる。 (Alkaline earth metal ions)
The colored resin composition of the present invention may further contain alkaline earth metal ions (such as calcium ions). With such a configuration, the effects of the present invention are excellent, and the generation of needle-like foreign matters due to a mixed crystal of molten zinc phthalocyanine and copper phthalocyanine can be more effectively suppressed. For example, the content of alkaline earth metal ions relative to the mass of PG58 can be 30 to 300 ppm by mass.
　上記のほか、着色樹脂組成物には、必要に応じて、各種添加物、例えば、充填剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加物としては、特開２００４－２９５１１６号公報の段落０１５５～０１５６に記載のものを挙げることができ、これらの内容は本願明細書に組み込まれる。
　本発明の組成物は、特開２００４－２９５１１６号公報の段落００７８に記載の増感剤や光安定剤、同公報の段落００８１に記載の熱重合防止剤を含有していてもよい。 In addition to the above, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended with the colored resin composition as necessary. Examples of these additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
The composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the publication.
＜着色樹脂組成物の製造方法＞
　本発明の組成物は、上述した各成分を混合することで調製することができる。
　なお、本発明の組成物の調製に際しては、着色樹脂組成物を構成する各成分を一括配合してもよいし、各成分を溶剤に溶解・分散した後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解・分散して着色樹脂組成物を調製してもよいし、必要に応じては、各成分を適宜２つ以上の溶液・分散液としておいて、使用時（塗布時）にこれらを混合して組成物として調製してもよい。
　本発明の組成物は、ＰＧ５８を分散剤によって分散させたものを他の成分に配合することが好ましい。 <Method for producing colored resin composition>
The composition of this invention can be prepared by mixing each component mentioned above.
In preparing the composition of the present invention, the components constituting the colored resin composition may be combined at once, or may be sequentially mixed after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, a colored resin composition may be prepared by simultaneously dissolving and dispersing all components in a solvent, and if necessary, each component may be suitably used as two or more solutions / dispersions at the time of use ( These may be mixed at the time of application) to prepare as a composition.
In the composition of the present invention, it is preferable that PG58 dispersed with a dispersant is blended with other components.
　本発明の組成物は、異物の除去や欠陥の低減などの目的で、フィルタで濾過することが好ましい。
　フィルタろ過に用いるフィルタとしては、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。
　フィルタの材質の例としては、ＰＴＦＥ（ポリテトラフルオロエチレン）等のフッ素樹脂；ナイロン－６、ナイロン－６，６等のポリアミド系樹脂；ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量を含む）；等が挙げられる。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）が好ましい。 The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
As a filter used for filter filtration, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
Examples of filter materials include: fluororesins such as PTFE (polytetrafluoroethylene); polyamide resins such as nylon-6 and nylon-6, 6; polyolefin resins such as polyethylene and polypropylene (PP) (high density, super Including high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.
　フィルタの孔径には特に限定はないが、例えば０．０１～２０．０μｍ程度であり、好ましくは０．０１～５μｍ程度であり、さらに好ましくは０．０１～２．０μｍ程度である。
　フィルタの孔径を上記範囲とすることにより、微細な粒子をより効果的に取り除くことができ、濁度をより低減することができる。
　ここで、フィルタの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。 The pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 μm, preferably about 0.01 to 5 μm, and more preferably about 0.01 to 2.0 μm.
By setting the pore diameter of the filter in the above range, fine particles can be more effectively removed and turbidity can be further reduced.
Here, the pore size of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
　フィルタろ過では、２種以上のフィルタを組み合わせて用いてもよい。
　例えば、まず第１のフィルタを用いてろ過を行い、次に、第１のフィルタとは孔径が異なる第２のフィルタを用いてろ過を行うことができる。
　その際、第１のフィルタでのフィルタリング及び第２のフィルタでのフィルタリングは、それぞれ、１回のみでもよいし、２回以上行ってもよい。
　第２のフィルタは、上述した第１のフィルタと同様の材料等で形成されたものを使用することができる。 In filter filtration, two or more filters may be used in combination.
For example, filtration can be performed first using a first filter, and then using a second filter having a pore diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.
＜用途＞
　本発明の組成物を硬化させて得られる硬化膜は、表面に他の色が混色し難いため、カラーフィルタの着色パターンを形成するために好適に用いられる。また、本発明の組成物は、固体撮像素子（例えば、ＣＣＤ、ＣＭＯＳ等）や、液晶表示装置（ＬＣＤ）などの画像表示装置に用いられるカラーフィルタなどの着色パターン形成用として好適に用いることができる。なかでも、ＣＣＤおよびＣＭＯＳ等の固体撮像素子用のカラーフィルタを作製用途として好適に用いることができる。また、本発明の組成物は、ドライエッチング用着色樹脂組成物として好ましく用いることができる。 <Application>
The cured film obtained by curing the composition of the present invention is preferably used for forming a colored pattern of a color filter because other colors are unlikely to be mixed on the surface. In addition, the composition of the present invention is preferably used for forming a colored pattern such as a color filter used in a solid-state imaging device (for example, CCD, CMOS, etc.) or an image display device such as a liquid crystal display device (LCD). it can. In particular, a color filter for a solid-state imaging device such as a CCD and a CMOS can be suitably used as a production application. Further, the composition of the present invention can be preferably used as a colored resin composition for dry etching.
＜硬化膜、パターン形成方法、カラーフィルタおよびカラーフィルタの製造方法＞
　次に、本発明の硬化膜、パターン形成方法およびカラーフィルタについて、その製造方法を通じて詳述する。また、本発明のパターン形成方法を用いたカラーフィルタの製造方法についても説明する。
　本発明の硬化膜は、本発明の組成物を硬化してなる。かかる硬化膜はカラーフィルタに好ましく用いられる。 <Curing film, pattern forming method, color filter, and color filter manufacturing method>
Next, the cured film, pattern forming method and color filter of the present invention will be described in detail through the manufacturing method. A method for producing a color filter using the pattern forming method of the present invention will also be described.
The cured film of the present invention is formed by curing the composition of the present invention. Such a cured film is preferably used for a color filter.
　本発明のパターン形成方法は、本発明の組成物を支持体上に適用して着色樹脂組成物層を形成し、不要部分を除去して、着色パターンを形成する。
　本発明のパターン形成方法は、カラーフィルタが有する着色パターン（画素）の形成に好適に適用することができる。
　本発明の着色樹脂組成物は、ドライエッチング法によってパターンを形成してもよいし、いわゆるフォトリソグラフィ法でパターン形成によって、カラーフィルタを製造してもよい。
　すなわち、本発明のパターン形成方法の第一の実施形態として、着色樹脂組成物を支持体上に適用して着色樹脂組成物層を形成し、硬化して着色層を形成する工程、着色層上にフォトレジスト層を形成する工程、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程、およびレジストパターンをエッチングマスクとして着色層をドライエッチングする工程を含む、パターン形成方法が例示される。
　また、本発明のパターン形成方法の第二の実施形態として、着色樹脂組成物を支持体上に適用して着色樹脂組成物層を形成する工程と、着色樹脂組成物層をパターン状に露光する工程と、未露光部を現像除去して着色パターンを形成する工程とを含むパターン形成方法が例示される。
　このようなパターン形成方方法は、カラーフィルタの着色層の製造に用いられる。すなわち、本発明では、本発明のパターン形成方法を含むカラーフィルタの製造方法についても開示する。
　以下、これらの詳細を述べる。 In the pattern forming method of the present invention, the colored resin composition layer is formed by applying the composition of the present invention on a support, and unnecessary portions are removed to form a colored pattern.
The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) included in a color filter.
The colored resin composition of the present invention may form a pattern by a dry etching method, or may produce a color filter by pattern formation by a so-called photolithography method.
That is, as a first embodiment of the pattern forming method of the present invention, a step of applying a colored resin composition on a support to form a colored resin composition layer and curing to form a colored layer, on the colored layer A pattern forming method includes a step of forming a photoresist layer on the substrate, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask. Is done.
In addition, as a second embodiment of the pattern forming method of the present invention, a step of forming a colored resin composition layer by applying the colored resin composition on a support, and exposing the colored resin composition layer in a pattern shape The pattern formation method including a process and the process of developing and removing an unexposed part and forming a colored pattern is illustrated.
Such a pattern forming method is used for manufacturing a colored layer of a color filter. That is, the present invention also discloses a method for manufacturing a color filter including the pattern forming method of the present invention.
These details will be described below.
　以下、本発明のパターン形成方法における各工程については、固体撮像素子用カラーフィルタの製造方法を通じて詳細に説明するが、本発明はこの方法に限定されるものではない。以下、固体撮像素子用カラーフィルタを単に「カラーフィルタ」ということがある。
　本発明のカラーフィルタの製造方法は、着色樹脂組成物を基板上に塗布して着色膜（着色層）を形成する工程、基板上に塗布された着色膜を１５０～３５０℃で加熱し、硬化させる工程、硬化された着色膜の上にフォトレジストを塗布する工程、フォトレジストをパターン露光した後、アルカリ現像することによって、フォトレジストをパターニングする工程、パターニングされたフォトレジストをエッチングマスクとして、フォトレジストの下層の着色膜をドライエッチングによりパターニングする工程、パターニング後のフォトレジストを除去する工程を含むことが好ましい。
　以下、本発明のカラーフィルタの製造方法について、図１～９を用い、具体例を挙げて説明する。 Hereinafter, although each process in the pattern formation method of this invention is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method. Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.
The method for producing a color filter of the present invention comprises a step of applying a colored resin composition onto a substrate to form a colored film (colored layer), and heating the colored film applied on the substrate at 150 to 350 ° C. to cure. A step of applying a photoresist on the cured colored film, a step of patterning the photoresist after pattern exposure, and a step of patterning the photoresist by alkali development, and a photo process using the patterned photoresist as an etching mask. It is preferable to include a step of patterning the colored film under the resist by dry etching and a step of removing the patterned photoresist.
Hereinafter, the manufacturing method of the color filter of the present invention will be described with reference to specific examples with reference to FIGS.
＜＜＜第１の着色画素を形成する工程＞＞＞
　第１の着色画素を形成する工程では、ドライエッチングにより第１の着色画素を形成することが好ましい。
　本発明のカラーフィルタの製造方法においては、先ず、図１の概略断面図に示すように、着色樹脂組成物として、第１の着色樹脂組成物によって第１の着色層１１を形成する（工程（Ａ））。第１の着色樹脂組成物は、上述した本発明の着色樹脂組成物を用いることができる。
　第１の着色層１１は、緑色透過層であることが好ましい。第１の着色層１１を緑色透過層とすることにより、色感度をより向上させることができる。 <<< Step of Forming First Colored Pixel >>>
In the step of forming the first colored pixel, it is preferable to form the first colored pixel by dry etching.
In the method for producing a color filter of the present invention, first, as shown in the schematic cross-sectional view of FIG. 1, a first colored layer 11 is formed from a first colored resin composition as a colored resin composition (step ( A)). As the first colored resin composition, the above-described colored resin composition of the present invention can be used.
The first colored layer 11 is preferably a green transmission layer. By making the first colored layer 11 a green transmissive layer, color sensitivity can be further improved.
　第１の着色層１１は、例えば、着色樹脂組成物を支持体上に回転塗布、スリット塗布、スプレー塗布、スピンコート法、回転塗布、流延塗布、ロール塗布等の塗布方法により塗布し、乾燥させて着色層を形成することにより形成できる。特に、スピンコート法により塗布することが好ましい。
　支持体としては、シリコン基板のほか、カラーフィルタに用いられるものであれば特に制限はなく、例えば、液晶表示素子等に用いられるソーダガラス、ホウケイ酸ガラス、石英ガラスおよびこれらに透明導電膜を付着させたものや、固体撮像素子等に用いられる光電変換素子基板、例えば酸化膜、窒化シリコン等が挙げられる。また、これら支持体とカラーフィルタとの間には本発明を損なわない限り中間層などを設けてもよい。
　乾燥後の第１の着色層１１の厚みとしては、０．３～２．０μｍの範囲が好ましく、０．３５～１．５μｍの範囲がより好ましく、０．３５～１．２μｍの範囲がより好ましい。 The first colored layer 11 is applied, for example, by applying a colored resin composition onto a support by a coating method such as spin coating, slit coating, spray coating, spin coating, spin coating, cast coating, roll coating, and the like. And forming a colored layer. In particular, it is preferable to apply by spin coating.
The support is not particularly limited as long as it is used for a color filter in addition to a silicon substrate. For example, soda glass, borosilicate glass, quartz glass, and a transparent conductive film attached to these are used for liquid crystal display elements. And a photoelectric conversion element substrate used for a solid-state imaging device, such as an oxide film or silicon nitride. Further, an intermediate layer or the like may be provided between the support and the color filter as long as the present invention is not impaired.
The thickness of the first colored layer 11 after drying is preferably in the range of 0.3 to 2.0 μm, more preferably in the range of 0.35 to 1.5 μm, and more preferably in the range of 0.35 to 1.2 μm. preferable.
　第１の着色層１１は、ホットプレート、オーブン等の加熱装置により加熱して、硬化させることが好ましい。加熱温度は、９０℃～２５０℃であることが好ましく、１００℃～２３０℃であることがより好ましい。加熱時間は、加熱手段により異なるが、ホットプレート上で加熱する場合、通常２～３０分間程度であり、オーブン中で加熱する場合、通常、３０～９０分間程度である。
　また、第１の着色層１１は、さらに加熱処理（ポストベーク）を行うことが好ましい。ポストベークの加熱温度は、１５０℃～３５０℃が好ましく、２００℃～２５０℃がより好ましい。加熱時間は、加熱手段により異なるが、通常、２０～９０分間程度である。 The first colored layer 11 is preferably cured by heating with a heating device such as a hot plate or an oven. The heating temperature is preferably 90 ° C to 250 ° C, more preferably 100 ° C to 230 ° C. The heating time varies depending on the heating means, but when heated on a hot plate, it is usually about 2 to 30 minutes, and when heated in an oven, it is usually about 30 to 90 minutes.
The first colored layer 11 is preferably further subjected to heat treatment (post-bake). The heating temperature for post baking is preferably 150 ° C. to 350 ° C., more preferably 200 ° C. to 250 ° C. The heating time varies depending on the heating means, but is usually about 20 to 90 minutes.
　次いで、第１の着色層１１に除去部群が形成されるようにドライエッチングによりパターニングする（工程（Ｂ））。これにより第１の着色パターンを形成する。この手法によれば、第１の着色樹脂組成物により第１の着色層を形成し、第１の着色層を露光、現像することによって除去部群を設ける場合と比較して、所望の形状（特に矩形状）の除去部群をより確実に設けることができる。 Next, patterning is performed by dry etching so that a removal portion group is formed in the first colored layer 11 (step (B)). Thereby, a first colored pattern is formed. According to this technique, the first colored layer is formed with the first colored resin composition, and a desired shape (as compared with the case where the removal portion group is provided by exposing and developing the first colored layer) In particular, the removal portion group having a rectangular shape can be provided more reliably.
　ドライエッチングは、第１の着色層１１を、パターニングされたフォトレジスト層をマスクとしてエッチングガスを用いて行うことができる。例えば、図２の概略断面図に示すように、先ず、第１の着色層１１の上にフォトレジスト層５１を形成する。 Dry etching can be performed on the first colored layer 11 using an etching gas using the patterned photoresist layer as a mask. For example, as shown in the schematic sectional view of FIG. 2, first, a photoresist layer 51 is formed on the first colored layer 11.
　具体的には、第１の着色層１１上にポジまたはネガ型のフォトレジストを塗布し、これを乾燥させることによりフォトレジスト層を形成する。フォトレジスト層５１の形成においては、更にプリベーク処理を施すことが好ましい。特に、フォトレジストの形成プロセスとしては、露光後の加熱処理（ＰＥＢ）、現像後の加熱処理（ポストベーク処理）を実施する形態が望ましい。 Specifically, a positive or negative photoresist is applied on the first colored layer 11 and dried to form a photoresist layer. In forming the photoresist layer 51, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure (PEB) and heat treatment after development (post-bake treatment) are desirable.
　フォトレジストとしては、例えば、ポジ型のフォトレジストが用いられる。このポジ型のフォトレジストとしては、紫外線（ｇ線、ｈ線、ｉ線）、エキシマレーザー等を含む遠紫外線、電子線、イオンビームおよびＸ線等の放射線に感応するポジ型フォトレジスト用に好適なポジ型レジスト組成物が使用できる。放射線のうち、ｇ線、ｈ線、ｉ線が好ましく、中でもｉ線が好ましい。
　具体的には、ポジ型のフォトレジストとして、キノンジアジド化合物およびアルカリ可溶性樹脂を含有する組成物が好ましい。キノンジアジド化合物としては、ナフトキノンジアジド化合物が挙げられる。
　乾燥後のフォトレジスト層５１の厚みとしては、０．１～３μｍが好ましく、０．２～２．５μｍが好ましく、０．３～２μｍが更に好ましい。なお、フォトレジスト層５１の塗布は、第１の着色層１１における塗布方法を用いて好適に行なえる。 As the photoresist, for example, a positive type photoresist is used. This positive photoresist is suitable for positive photoresists sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A positive resist composition can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable as a positive photoresist. Examples of the quinonediazide compound include a naphthoquinonediazide compound.
The thickness of the dried photoresist layer 51 is preferably 0.1 to 3 μm, more preferably 0.2 to 2.5 μm, and still more preferably 0.3 to 2 μm. Note that the application of the photoresist layer 51 can be suitably performed using the application method for the first colored layer 11.
　次いで、図３の概略断面図に示すように、フォトレジスト層５１を露光、現像することにより、レジスト除去部群５１Ａが設けられたレジストパターン（パターニングされたフォトレジスト層）５２を形成する。
　レジストパターン５２の形成は、特に制限なく、従来公知のフォトリソグラフィの技術を用いることができる。露光、現像によりフォトレジスト層５１に、レジスト除去部群５１Ａが設けられることによって、次のエッチングで用いられるエッチングマスクとしてのレジストパターン５２が、第１の着色層１１上に設けられる。
　フォトレジスト層５１の露光は、所定のマスクパターンを介して、ポジ型またはネガ型のフォトレジストに、ｇ線、ｈ線、ｉ線等、好ましくはｉ線で露光を施すことにより行なうことができる。露光後は、現像液で現像処理することにより、着色パターンを形成しようとする領域に合わせてフォトレジストが除去される。
　上記現像液としては、着色剤を含む第１の着色層には影響を与えず、ポジレジストの露光部およびネガレジストの未硬化部を溶解するものであればいずれも使用可能であり、例えば、種々の有機溶剤の組み合わせやアルカリ性の水溶液を用いることができる。
　アルカリ性の水溶液としては、アルカリ性化合物を濃度が０．００１～１０質量％、好ましくは０．０１～５質量％となるように溶解して調製されたアルカリ性水溶液が好適である。アルカリ性化合物は、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム，硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセン等が挙げられる。尚、アルカリ性水溶液を現像液として用いた場合は、一般に現像後に水で洗浄処理が施される。 Next, as shown in the schematic cross-sectional view of FIG. 3, the photoresist layer 51 is exposed and developed to form a resist pattern (patterned photoresist layer) 52 provided with a resist removal portion group 51A.
The formation of the resist pattern 52 is not particularly limited, and a conventionally known photolithography technique can be used. By providing the resist removal portion group 51 </ b> A in the photoresist layer 51 by exposure and development, a resist pattern 52 as an etching mask used in the next etching is provided on the first colored layer 11.
The exposure of the photoresist layer 51 can be performed by exposing a positive or negative photoresist to g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. . After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.
As the developer, any can be used as long as it does not affect the first colored layer containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. Combinations of various organic solvents and alkaline aqueous solutions can be used.
As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Examples thereof include ammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.
　次に、図４の概略断面図に示すように、レジストパターン５２をエッチングマスクとして、第１の着色層１１に除去部群１２０が形成されるようにドライエッチングによりパターニングする。これにより、第１の着色パターン１２が形成される。ここで、除去部群１２０は、第１の除去部群１２１と第２の除去部群１２２とを有している。
　除去部群１２０は、第１の着色層１１に、市松状に設けられている。よって、第１の着色層１１に除去部群１２０が設けられてなる第１の着色パターン１２は、複数の四角形状の第１の着色画素を市松状に有している。
　具体的には、ドライエッチングは、レジストパターン５２をエッチングマスクとして、第１の着色層１１をドライエッチングする。ドライエッチングの代表的な例としては、特開昭５９－１２６５０６号、特開昭５９－４６６２８号、同５８－９１０８号、同５８－２８０９号、同５７－１４８７０６号、同６１－４１１０２号などの公報に記載の方法が挙げられ、これらの内容は本願明細書に組み込まれる。 Next, as shown in the schematic cross-sectional view of FIG. 4, the resist pattern 52 is used as an etching mask, and patterning is performed by dry etching so that the removal portion group 120 is formed in the first colored layer 11. Thereby, the 1st coloring pattern 12 is formed. Here, the removal unit group 120 includes a first removal unit group 121 and a second removal unit group 122.
The removal unit group 120 is provided on the first colored layer 11 in a checkered pattern. Therefore, the 1st coloring pattern 12 in which the removal part group 120 is provided in the 1st coloring layer 11 has a some square 1st coloring pixel in checkered form.
Specifically, in the dry etching, the first colored layer 11 is dry etched using the resist pattern 52 as an etching mask. Representative examples of dry etching include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, and the like. And the contents thereof are incorporated herein by reference.
　ドライエッチングとしては、パターン断面をより矩形に近く形成する観点や支持体へのダメージをより低減する観点から、以下の形態で行なうのが好ましい。
　フッ素系ガスと酸素ガス（Ｏ2）との混合ガスを用い、支持体が露出しない領域（深さ）までエッチングを行なう第１段階のエッチングと、この第１段階のエッチングの後に、窒素ガス（Ｎ2）と酸素ガス（Ｏ2）との混合ガスを用い、好ましくは支持体が露出する領域（深さ）付近までエッチングを行なう第２段階のエッチングと、支持体が露出した後に行なうオーバーエッチングとを含む形態が好ましい。以下、ドライエッチングの具体的手法、並びに第１段階のエッチング、第２段階のエッチング、およびオーバーエッチングについて説明する。 Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O 2 ), the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N 2 ) and oxygen gas (O 2 ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. The form containing these is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.
　ドライエッチングは、下記手法により事前にエッチング条件を求めて行なう。
（１）第１段階のエッチングにおけるエッチングレート（ｎｍ／ｍｉｎ）と、第２段階のエッチングにおけるエッチングレート（ｎｍ／ｍｉｎ）とをそれぞれ算出する。
（２）第１段階のエッチングで所望の厚さをエッチングする時間と、第２段階のエッチングで所望の厚さをエッチングする時間とをそれぞれ算出する。
（３）上記（２）で算出したエッチング時間に従って第１段階のエッチングを実施する。
（４）上記（２）で算出したエッチング時間に従って第２段階のエッチングを実施する。あるいはエンドポイント検出でエッチング時間を決定し、決定したエッチング時間に従って第２段階のエッチングを実施してもよい。
（５）上記（３）、（４）の合計時間に対してオーバーエッチング時間を算出し、オーバーエッチングを実施する。 Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
(2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
(3) The first stage etching is performed according to the etching time calculated in (2) above.
(4) The second stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
(5) Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.
　上記第１段階のエッチング工程で用いる混合ガスとしては、被エッチング膜である有機材料を矩形に加工する観点から、フッ素系ガスおよび酸素ガス（Ｏ2）を含むことが好ましい。また、第１段階のエッチング工程は、支持体が露出しない領域までエッチングする形態にすることで、支持体のダメージを回避することができる。
　また、上記第２段階のエッチング工程および上記オーバーエッチング工程は、第１段階のエッチング工程でフッ素系ガスおよび酸素ガスの混合ガスにより支持体が露出しない領域までエッチングを実施した後、支持体のダメージ回避の観点から、窒素ガスおよび酸素ガスの混合ガスを用いてエッチング処理を行なうのが好ましい。 The mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O 2 ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In addition, the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed.
The second etching step and the over-etching step are performed in the first etching step after etching to a region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas. From the viewpoint of avoidance, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.
　第１段階のエッチング工程でのエッチング量と、第２段階のエッチング工程でのエッチング量との比率は、第１段階のエッチング工程でのエッチング処理による矩形性を損なわないように決定することが重要である。なお、全エッチング量（第１段階のエッチング工程でのエッチング量と第２段階のエッチング工程でのエッチング量との総和）中における後者の比率は、０％より大きく５０％以下である範囲が好ましく、１０～２０％がより好ましい。エッチング量とは、被エッチング膜の残存する膜厚とエッチング前の膜厚との差から算出される量のことをいう。 It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.
　また、エッチングは、オーバーエッチング処理を含むことが好ましい。オーバーエッチング処理は、オーバーエッチング比率を設定して行なうことが好ましい。また、オーバーエッチング比率は、初めに行なうエッチング処理時間より算出することが好ましい。オーバーエッチング比率は任意に設定できるが、フォトレジストのエッチング耐性と被エッチングパターンの矩形性維持の点で、エッチング工程におけるエッチング処理時間の３０％以下であることが好ましく、５～２５％であることがより好ましい。 Further, the etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable.
　次いで、図５の概略断面図に示すように、エッチング後に残存するレジストパターン（すなわちエッチングマスク）５２を除去する。レジストパターン５２の除去は、レジストパターン５２上に剥離液または溶剤を付与して、レジストパターン５２を除去可能な状態にする工程と、レジストパターン５２を洗浄水を用いて除去する工程とを含むことが好ましい。例えば、剥離液または溶剤を少なくともレジストパターン５２上に付与し、所定の時間停滞させてパドル現像する工程を挙げることができる。剥離液または溶剤を停滞させる時間としては、特に制限はないが、数十秒から数分であることが好ましい。また、例えば、スプレー式またはシャワー式の噴射ノズルからレジストパターン５２に洗浄水を噴射して、レジストパターン５２を除去するようにしてもよい。
　洗浄水としては、純水を好ましく用いることができる。また、噴射ノズルとしては、その噴射範囲内に支持体全体が包含される噴射ノズルや、可動式の噴射ノズルであってその可動範囲が支持体全体を包含する噴射ノズルを挙げることができる。 Next, as shown in the schematic cross-sectional view of FIG. 5, the resist pattern (that is, etching mask) 52 remaining after the etching is removed. The removal of the resist pattern 52 includes a step of applying a stripping solution or a solvent to the resist pattern 52 so that the resist pattern 52 can be removed, and a step of removing the resist pattern 52 using cleaning water. Is preferred. For example, a step of applying a stripping solution or a solvent on at least the resist pattern 52 and stagnating for a predetermined time to perform paddle development can be included. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes. Further, for example, the resist pattern 52 may be removed by spraying cleaning water onto the resist pattern 52 from a spray type or shower type spray nozzle.
As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support.
＜＜＜第２の着色画素を形成する工程＞＞＞
　第２の着色画素を形成する工程では、第２着色感放射線性組成物を用いて、第１の着色画素に隣接する第２の着色画素をフォトリソグラフィにより形成する。本発明では、フォトリソグラフィにより第２の着色画素を形成することにより、全ての工程をドライエッチングで行う場合と比較して、工程数を削減することができる。 <<< Step of Forming Second Colored Pixel >>>
In the step of forming the second colored pixel, the second colored pixel adjacent to the first colored pixel is formed by photolithography using the second colored radiation-sensitive composition. In the present invention, by forming the second colored pixel by photolithography, the number of steps can be reduced as compared with the case where all steps are performed by dry etching.
　第２の着色画素を形成する工程では、図６の概略断面図に示すように、第１の除去部群１２１および第２の除去部群１２２における各除去部の内部に第２着色感放射線性組成物を埋設させて、第１の着色層（すなわち、第１の着色層１１に除去部群１２０が形成されてなる第１の着色パターン１２）上に第２着色感放射線性組成物により第２着色感放射線性層２１を積層する（工程（Ｃ））。これにより、第１の着色層１１の除去部群１２０の中に、複数の第２の着色画素を有する第２の着色パターン２２が形成される。ここで、第２の着色画素は、四角形状の画素となっていることが好ましい。第２着色感放射線性層２１の形成は、上述した第１着色層１１を形成する方法と同様にして行える。
　ポストベーク後の第２着色感放射線性層２１の厚みとしては、０．１～１．５μｍであることが好ましく、０．１～１．０μｍであることがより好ましい。 In the step of forming the second colored pixels, as shown in the schematic cross-sectional view of FIG. 6, the second colored radiation-sensitive property is formed inside each removed portion in the first removed portion group 121 and the second removed portion group 122. The composition is embedded, and the second colored radiation-sensitive composition is used to form the first colored layer (that is, the first colored pattern 12 in which the removal portion group 120 is formed on the first colored layer 11). Two colored radiation-sensitive layers 21 are laminated (step (C)). Thereby, the 2nd coloring pattern 22 which has a some 2nd coloring pixel in the removal part group 120 of the 1st coloring layer 11 is formed. Here, the second colored pixel is preferably a square pixel. The second colored radiation sensitive layer 21 can be formed in the same manner as the method for forming the first colored layer 11 described above.
The thickness of the second colored radiation-sensitive layer 21 after post-baking is preferably 0.1 to 1.5 μm, and more preferably 0.1 to 1.0 μm.
　そして、第２着色感放射線性層２１の、第１の着色層１１に設けられた第１の除去部群１２１に対応する位置２１Ａを露光し、現像することによって、第２着色感放射線性層２１と、第２の除去部群１２２の各除去部の内部に設けられた複数の第２の着色画素２２Ｒとを除去する（工程（Ｄ））（図７の概略断面図を参照）。
　露光に際して用いることができる放射線（光）としては、特に、ｇ線、ｉ線等の紫外線が好ましく（特に好ましくはｉ線）用いられる。照射量（露光量）は３０ｍＪ／ｃｍ2～３０００ｍＪ／ｃｍ2が好ましく５０ｍＪ／ｃｍ2～２５００ｍＪ／ｃｍ2がより好ましく、１００ｍＪ／ｃｍ2～５００ｍＪ／ｃｍ2が特に好ましい。
　現像液としては、上述した第１の着色画素を形成する工程で説明した現像液と同義である。
　現像方法としては、例えば、現像液が満たされた槽中に基板を一定時間浸漬する方法（ディップ法）、基板表面に現像液を表面張力によって盛り上げて一定時間静止することで現像する方法（パドル法）、基板表面に現像液を噴霧する方法（スプレー法）、一定速度で回転している基板上に一定速度で現像液吐出ノズルをスキャンしながら現像液を吐出しつづける方法（ダイナミックディスペンス法）などを適用することができ、特に、パドル方が好ましい。
　現像時間は、未露光部の着色層が十分に溶解する時間であれば特に制限はなく、通常は１０秒～３００秒であり。好ましくは、２０秒～１２０秒である。
　現像液の温度は０℃～５０℃が好ましく、１５℃～３５℃が更に好ましい。 Then, the second colored radiation-sensitive layer 21 is exposed and developed at a position 21A corresponding to the first removal portion group 121 provided in the first colored layer 11 of the second colored radiation-sensitive layer 21. 21 and the plurality of second colored pixels 22R provided inside each removal portion of the second removal portion group 122 are removed (step (D)) (see the schematic cross-sectional view of FIG. 7).
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure dose) is more preferably 30mJ / cm 2 ~ 3000mJ / cm 2 is preferably 50mJ / cm 2 ~ 2500mJ / cm 2, 100mJ / cm 2 ~ 500mJ / cm 2 is particularly preferred.
The developer is synonymous with the developer described in the step of forming the first colored pixels described above.
As a development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) The paddle method is particularly preferable.
The development time is not particularly limited as long as the colored layer in the unexposed area is sufficiently dissolved, and is usually 10 seconds to 300 seconds. Preferably, it is 20 seconds to 120 seconds.
The temperature of the developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C.
＜＜＜第３の着色画素を形成する工程＞＞＞
　本発明のカラーフィルタの製造方法は、第２の着色画素を形成する工程の後に、さらに第３の着色画素を形成する工程を有していてもよい。
　第３の着色画素を形成する工程では、図８の概略断面図に示すように、第２の除去部群１２２における各除去部の内部に第３の着色感放射線性組成物を埋設させて、複数の第３の着色画素が形成されるように、第１の着色層（すなわち、第１の除去部群１２１の中に第２の着色パターン２２が形成されてなる第１の着色パターン１２）上に第３の着色感放射線性組成物により第３着色感放射線性層３１を形成する（工程（Ｅ））。これにより、第１の着色層１１の第２の除去部群１２２の中に、複数の第３の着色画素を有する第３の着色パターン３２が形成される。ここで、第３の着色画素は、四角形状の画素となっていることが好ましい。第３着色感放射線性層３１の形成は、上述した第１の実施の形態における着色樹脂組成物を用いて着色層を形成する工程と同様にして行なえる。
　ポストベーク後の第３の着色樹脂組成物層３１の厚みとしては、０．１～１μｍの範囲が好ましく、０．２～０．８の範囲がより好ましく、０．３～０．６μｍの範囲がより好ましい。 <<< Step of Forming Third Colored Pixel >>>
The method for manufacturing a color filter of the present invention may further include a step of forming a third colored pixel after the step of forming the second colored pixel.
In the step of forming the third colored pixel, as shown in the schematic cross-sectional view of FIG. 8, the third colored radiation-sensitive composition is embedded in each removed portion in the second removed portion group 122, The first colored layer (that is, the first colored pattern 12 in which the second colored pattern 22 is formed in the first removal portion group 121) so that a plurality of third colored pixels are formed. A third colored radiation-sensitive layer 31 is formed on the third colored radiation-sensitive composition (step (E)). Thereby, the 3rd coloring pattern 32 which has a some 3rd coloring pixel in the 2nd removal part group 122 of the 1st coloring layer 11 is formed. Here, the third colored pixel is preferably a square pixel. The formation of the third colored radiation-sensitive layer 31 can be performed in the same manner as the step of forming the colored layer using the colored resin composition in the first embodiment described above.
The thickness of the third colored resin composition layer 31 after post-baking is preferably in the range of 0.1 to 1 μm, more preferably in the range of 0.2 to 0.8, and in the range of 0.3 to 0.6 μm. Is more preferable.
　そして、第３着色感放射線性層３１の、第１の着色層１１に設けられた第２の除去部群１２２に対応する位置３１Ａを露光し、現像することによって、第３着色感放射線性層３１を除去することで、図９の概略断面図に示すように、第１の着色パターン１２と、第２の着色パターン２２と、第３の着色パターン３２とを有するカラーフィルタ１００が製造される（工程（Ｆ））。 Then, the third colored radiation-sensitive layer 31 is exposed and developed at a position 31A corresponding to the second removal portion group 122 provided in the first colored layer 11 of the third colored radiation-sensitive layer 31. By removing 31, as shown in the schematic cross-sectional view of FIG. 9, the color filter 100 having the first colored pattern 12, the second colored pattern 22, and the third colored pattern 32 is manufactured. (Step (F)).
　上述した第２着色感放射線性組成物、及び、第３着色感放射線性組成物は、それぞれ、着色剤を含有する。着色剤は、本発明の着色組成物において上述したものを同様に挙げることができるが、第２着色画素及び第３着色画素の一方が青色透過部であり、他方が赤色透過部であることが好ましい。青色透過部を形成するための着色組成物に含有される着色剤は、Ｃ．Ｉ．ピグメントバイオレット　１，１９，２３，２７，３２，３７，４２、及び、Ｃ．Ｉ．ピグメントブルー　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０から選択される１種以上であることが好ましい。赤色透過部を形成するための着色組成物に含有される着色剤は、特開２０１２－１７２００３号公報の段落番号００３７、００３９に記載のものから選択される１種以上であることが好ましく、これらの内容は本願明細書に組み込まれる。 The second colored radiation-sensitive composition and the third colored radiation-sensitive composition described above each contain a colorant. Examples of the colorant may include those described above in the coloring composition of the present invention, but one of the second colored pixel and the third colored pixel is a blue transmissive portion, and the other is a red transmissive portion. preferable. The colorant contained in the coloring composition for forming the blue transmission part is C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 or more It is preferable. The colorant contained in the coloring composition for forming the red transmitting part is preferably at least one selected from those described in paragraph numbers 0037 and 0039 of JP2012-172003A. Is incorporated herein by reference.
　第２着色感放射線性組成物、及び、第３着色感放射線性組成物の各々において、着色剤の組成物の全固形分に対する含有量は、３０質量％以上であることが好ましく、３５質量％以上であることがより好ましく、４０質量％以上であることが更に好ましい。また、着色剤の組成物の全固形分に対する含有量は、通常、９０質量％以下であり、８０質量％以下であることが好ましい。 In each of the second colored radiation-sensitive composition and the third colored radiation-sensitive composition, the content of the colorant composition with respect to the total solid content is preferably 30% by mass or more, and 35% by mass. More preferably, it is more preferably 40% by mass or more. Moreover, content with respect to the total solid of the composition of a coloring agent is 90 mass% or less normally, and it is preferable that it is 80 mass% or less.
　また、第２着色感放射線性組成物、及び、第３着色感放射線性組成物は、それぞれ、ネガ型の感放射線性組成物が用いられることが好ましい。このネガ型の感放射線性組成物としては、紫外線（ｇ線、ｈ線、ｉ線）、エキシマレーザー等を含む遠紫外線、電子線、イオンビームおよびＸ線等の放射線に感応するネガ型感放射線性組成物が使用できる。放射線のうち、ｇ線、ｈ線、ｉ線が好ましく、中でもｉ線が好ましい。 Also, it is preferable that a negative radiation sensitive composition is used for each of the second colored radiation sensitive composition and the third colored radiation sensitive composition. This negative radiation sensitive composition includes negative radiation sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer laser, electron beams, ion beams and X rays. Sex compositions can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
　具体的には、ネガ型の感放射線性組成物として、光重合開始剤、重合成分（重合性化合物）、及び、バインダー樹脂（アルカリ可溶性樹脂等）などを含有する組成物が好ましく、例えば、特開２００５－３２６４５３号公報の段落番号００１７～００６４に記載のものを挙げることができ、この内容は本願明細書に組み込まれる。このようなネガ型の感放射線性組成物は、放射線の照射により、光重合開始剤が、重合性化合物の重合反応を開始させ、結果として、アルカリ可溶状態から、アルカリ不溶性になることを利用するものである。 Specifically, the negative radiation-sensitive composition is preferably a composition containing a photopolymerization initiator, a polymerization component (polymerizable compound), a binder resin (alkali-soluble resin, etc.) and the like. Examples described in paragraph Nos. 0017 to 0064 of Kaikai 2005-326453 may be mentioned, the contents of which are incorporated herein. Such a negative radiation sensitive composition utilizes the fact that the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound upon irradiation with radiation, and as a result, the alkali soluble state becomes alkali insoluble. To do.
＜着色樹脂組成物層をウェットエッチング法でパターン形成する方法＞
　本発明のカラーフィルタの製造方法では、ウェットエッチング法でパターン形成することもできる。以下にウェットエッチング法でパターン形成する方法の一例を示す。
　基板上に、上述した着色樹脂組成物を塗布して着色膜を形成する。
　基板としては通常、ソーダガラス、無アルカリガラス、ホウケイ酸ガラス、石英ガラスなどを用いることができる。塗布は、スピンナー、スプレー塗布、浸漬、ロールコーティング、バーコーティング、ダイコーティングなどの方法が用いられる。塗布した着色樹脂組成物の乾燥は、オーブン、ホットプレート、赤外線を使用し、５０～１８０℃の範囲で数秒～数時間行なうのが好ましい。
　上記着色膜上にパターン形成用のフォトレジストを塗布し、フォトレジスト層を形成する。フォトレジスト層の厚さは、０．１～３μｍが好ましく、０．２～２．５μｍが好ましく、０．３～２μｍが更に好ましい
　続いて、露光装置を用い、フォトレジスト層被膜上にマスクを置き、化学線を照射し、露光する。化学線としては紫外線、可視光線、電子線、Ｘ線が例として挙げられ、紫外線、可視光線が好ましい。ポジ型フォトレジストを用いた場合には、露光後、ポジ型フォトレジストの現像液で、フォトレジスト層の現像、着色膜のエッチングを同時に行う。エッチング後不要となったフォトレジスト層を剥離する。通常、剥離はアセトン、セロソルブ系などの溶剤が使用される。着色膜を熱処理し、着色膜のパターン加工を終える。熱処理は、温度を選び、段階的に昇温するかある温度範囲を選び連続的に昇温しながら５分～５時間実施する。この熱処理温度は、１８０～４００℃が好ましく、１８０～３５０℃がより好ましい。例えば、１３０℃、２００℃、３００℃で各々３０分熱処理する。また、室温から３００℃まで２時間かけて直線的に昇温してもよい。
　以上の工程を赤、緑、青の３色の着色組成物、または、黄、シアン、マゼンダおよび必要に応じてブラックマトリクス（黒）について繰り返す。必要に応じてアクリルポリマー、ポリシロキサン、ポリイミドなどからなるオーバーコート膜を形成し、ＩＴＯなどの金属酸化膜をスパッタすることにより、カラーフィルタを作成できる。 <Method for patterning colored resin composition layer by wet etching>
In the method for producing a color filter of the present invention, a pattern can be formed by a wet etching method. An example of a method for forming a pattern by the wet etching method is shown below.
On the substrate, the colored resin composition described above is applied to form a colored film.
As the substrate, soda glass, alkali-free glass, borosilicate glass, quartz glass, or the like can be usually used. For the coating, methods such as spinner, spray coating, dipping, roll coating, bar coating, and die coating are used. The applied colored resin composition is preferably dried in the range of 50 to 180 ° C. for several seconds to several hours using an oven, a hot plate, and infrared rays.
A photoresist for pattern formation is applied on the colored film to form a photoresist layer. The thickness of the photoresist layer is preferably from 0.1 to 3 μm, preferably from 0.2 to 2.5 μm, more preferably from 0.3 to 2 μm. Subsequently, using an exposure apparatus, a mask is formed on the photoresist layer coating. Place, irradiate with actinic radiation and expose. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays and visible rays are preferable. When a positive photoresist is used, after the exposure, the development of the photoresist layer and the etching of the colored film are simultaneously performed with a positive photoresist developer. The photoresist layer that has become unnecessary after etching is removed. Usually, a solvent such as acetone or cellosolve is used for peeling. The colored film is heat-treated to finish the patterning of the colored film. The heat treatment is performed for 5 minutes to 5 hours while selecting the temperature and raising the temperature stepwise or selecting a temperature range and continuously raising the temperature. The heat treatment temperature is preferably 180 to 400 ° C, and more preferably 180 to 350 ° C. For example, heat treatment is performed at 130 ° C., 200 ° C., and 300 ° C. for 30 minutes. Further, the temperature may be increased linearly from room temperature to 300 ° C. over 2 hours.
The above steps are repeated for red, green, and blue colored compositions, or yellow, cyan, magenta, and optionally a black matrix (black). A color filter can be formed by forming an overcoat film made of acrylic polymer, polysiloxane, polyimide, or the like as necessary, and sputtering a metal oxide film such as ITO.
＜着色樹脂組成物層をフォトリソグラフィ法でパターン形成する方法＞
　本発明のカラーフィルタの製造方法では、着色樹脂組成物層をフォトリソグラフィ法でパターン形成することもできる。フォトリソグラフィ法の詳細については、特開２０１３－２２７４９７号公報の段落番号０１７３～０１８５を参照でき、これらの内容は本願明細書に組み込まれる。 <Method for patterning colored resin composition layer by photolithography>
In the method for producing a color filter of the present invention, the colored resin composition layer can be patterned by a photolithography method. For details of the photolithography method, reference can be made to paragraph numbers 0173 to 0185 of JP2013-227497A, the contents of which are incorporated herein.
　本発明のカラーフィルタは、着色剤濃度の高い着色樹脂組成物により形成されるため、着色パターンの厚みを極めて薄くできる（例えば、０．７μｍ以下）。また、表面に他色が残留しにくく、混色が生じにくいため、クロストーク（光の混色）が抑制されたカラーフィルタとすることができる。 Since the color filter of the present invention is formed of a colored resin composition having a high colorant concentration, the thickness of the colored pattern can be extremely reduced (for example, 0.7 μm or less). In addition, since other colors hardly remain on the surface and color mixing does not easily occur, a color filter in which crosstalk (light color mixing) is suppressed can be obtained.
　本発明のカラーフィルタは、ＣＣＤ、ＣＭＯＳ等の固体撮像素子に好適に用いることができ、特に１００万画素を超えるような高解像度のＣＣＤやＣＭＯＳ等に好適である。本発明の固体撮像素子用カラーフィルタは、例えば、ＣＣＤまたはＣＭＯＳを構成する各画素の受光部と、集光するためのマイクロレンズと、の間に配置されるカラーフィルタとして用いることができる。 The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter for a solid-state imaging device of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.
　本発明のカラーフィルタにおける着色パターン（着色画素）の膜厚としては、０．１～１．０μｍが好ましく、０．１～０．８μｍがより好ましい。
　また、着色パターン（着色画素）のサイズ（パターン幅）としては、２．５μｍ以下とすることができ、２．０μｍ以下とすることもでき、０.９～１.４μｍとすることもできる。特に、ドライエッチング法を用いることにより、上記サイズの着色パターンを効率的に作製することができる。 The thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably from 0.1 to 1.0 μm, more preferably from 0.1 to 0.8 μm.
Further, the size (pattern width) of the colored pattern (colored pixel) can be 2.5 μm or less, can be 2.0 μm or less, and can be 0.9 to 1.4 μm. In particular, by using a dry etching method, a colored pattern having the above size can be efficiently produced.
＜固体撮像素子＞
　本発明の固体撮像素子は、既述の本発明のカラーフィルタを備える。本発明の固体撮像素子の構成としては、本発明におけるカラーフィルタが備えられた構成であり、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 imaging device>
The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .
　支持体上に、固体撮像素子（ＣＣＤイメージセンサー、ＣＭＯＳイメージセンサー、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、上記フォトダイオードおよび上記転送電極上にフォトダイオードの受光部のみ開口したタングステン等からなる遮光膜を有し、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、上記デバイス保護膜上に、本発明の固体撮像素子用カラーフィルタを有する構成である。
　さらに、上記デバイス保護層上であってカラーフィルタの下（支持体に近い側）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。 A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support. A light-shielding film made of tungsten or the like having an opening only in the light-receiving portion of the photodiode, and a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter Etc.
＜画像表示装置＞
　本発明のカラーフィルタは、上記固体撮像素子のみならず、液晶表示装置や有機ＥＬ表示装置などの、画像表示装置に用いることができ、特に液晶表示装置の用途に好適である。本発明のカラーフィルタを備えた液晶表示装置は、表示画像の色合いが良好で表示特性に優れた高画質画像を表示することができる。 <Image display device>
The color filter of the present invention can be used not only for the solid-state imaging device but also for image display devices such as liquid crystal display devices and organic EL display devices, and is particularly suitable for use in liquid crystal display devices. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.
　表示装置の定義や各表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木　昭夫著、（株）工業調査会　１９９０年発行）」、「ディスプレイデバイス（伊吹　順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、（株）工業調査会　１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。 For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
　本発明のカラーフィルタは、カラーＴＦＴ方式の液晶表示装置に用いてもよい。カラーＴＦＴ方式の液晶表示装置については、例えば「カラーＴＦＴ液晶ディスプレイ（共立出版（株）１９９６年発行）」に記載されている。さらに、本発明はＩＰＳなどの横電界駆動方式、ＭＶＡなどの画素分割方式などの視野角が拡大された液晶表示装置や、ＳＴＮ、ＴＮ、ＶＡ、ＯＣＳ、ＦＦＳ、およびＲ－ＯＣＢ等にも適用できる。
　また、本発明におけるカラーフィルタは、明るく高精細なＣＯＡ（Color-filter On Array）方式にも供することが可能である。ＣＯＡ方式の液晶表示装置にあっては、カラーフィルタ層に対する要求特性は、前述のような通常の要求特性に加えて、層間絶縁膜に対する要求特性、すなわち低誘電率および剥離液耐性が必要とされることがある。本発明のカラーフィルタにおいては、色相に優れた色素を用いることから、色純度、光透過性などが良好で着色パターン(画素）の色合いに優れるので、解像度が高く長期耐久性に優れたＣＯＡ方式の液晶表示装置を提供することができる。なお、低誘電率の要求特性を満足するためには、カラーフィルタ層の上に樹脂被膜を設けてもよい。
　これらの画像表示方式については、例えば、「ＥＬ、ＰＤＰ、ＬＣＤディスプレイ－技術と市場の最新動向－（東レリサーチセンター調査研究部門　２００１年発行）」の４３ページなどに記載されている。 The color filter of the present invention may be used in a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. Sometimes. In the color filter of the present invention, since a dye having excellent hue is used, the color purity, light transmittance, etc. are good and the color of the colored pattern (pixel) is excellent. Therefore, the COA method has high resolution and excellent long-term durability. A liquid crystal display device can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)".
　本発明におけるカラーフィルタを備えた液晶表示装置は、本発明におけるカラーフィルタ以外に、電極基板、偏光フィルム、位相差フィルム、バックライト、スペーサ、視野角保障フィルムなど様々な部材から構成される。本発明のカラーフィルタは、これらの公知の部材で構成される液晶表示装置に適用することができる。これらの部材については、例えば、「'９４液晶ディスプレイ周辺材料・ケミカルズの市場（島　健太郎　（株）シーエムシー　１９９４年発行）」、「２００３液晶関連市場の現状と将来展望（下巻）（表良吉（株）富士キメラ総研、２００３年発行）」に記載されている。
　バックライトに関しては、SID meeting Digest 1380（2005）（A.Konno et.al）や、月刊ディスプレイ　２００５年１２月号の１８～２４ページ（島 康裕）、同２５～３０ページ（八木隆明）などに記載されている。 In addition to the color filter of the present invention, the liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.
　本発明におけるカラーフィルタを液晶表示装置に用いると、従来公知の冷陰極管の三波長管と組み合わせたときに高いコントラストを実現できるが、さらに、赤、緑、青のＬＥＤ光源（ＲＧＢ－ＬＥＤ）をバックライトとすることによって輝度が高く、また、色純度の高い色再現性の良好な液晶表示装置を提供することができる。 When the color filter according to the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.
　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。なお、特に断りのない限り、「％」および「部」は質量基準である。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate 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. Unless otherwise specified, “%” and “parts” are based on mass.
＜ポリアミック酸ＰＡ－１～ＰＡ－３の合成＞
＜＜合成例１＞＞
　三口丸底フラスコに温度計、窒素ガス導入管、撹拌機を取り付けた反応容器に、４，４’－ジアミノジフェニルエーテル１５．０ｇ（７５ｍｍｏｌ）、３，３’－ジアミノジフェニルスルホン５．０ｇ（２０ｍｍｏｌ）、ビス－３－（アミノプロピル）テトラメチルジシロキサン１．２ｇ（５ｍｍｏｌ）をγ－ブチロラクトン２８０ｇと共に仕込み、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物１６．１ｇ（５０ｍｍｏｌ）、ピロメリット酸無水物１０．７ｇ（４９ｍｍｏｌ）を添加して６０℃で５時間反応させた後、無水マレイン酸０．２ｇ（２ｍｍｏｌ）を添加して、更に６０℃で１時間反応させて、固形分濃度２０質量％のポリアミック酸溶液ＰＡ－１を得た。 <Synthesis of polyamic acids PA-1 to PA-3>
<< Synthesis Example 1 >>
In a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube and a stirrer in a three-necked round bottom flask, 15.0 g (75 mmol) of 4,4′-diaminodiphenyl ether and 5.0 g (20 mmol) of 3,3′-diaminodiphenylsulfone Bis-3- (aminopropyl) tetramethyldisiloxane 1.2 g (5 mmol) was charged together with 280 g of γ-butyrolactone, and 16.1 g (50 mmol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Then, 10.7 g (49 mmol) of pyromellitic anhydride was added and reacted at 60 ° C. for 5 hours, then 0.2 g (2 mmol) of maleic anhydride was added, and further reacted at 60 ° C. for 1 hour. A polyamic acid solution PA-1 having a solid content concentration of 20% by mass was obtained.
＜＜合成例２～３＞＞
　ポリアミック酸の合成時に使用する原料の種類と量を下記の表１に示すように変更すること以外は、上記合成例１と同様の方法で固形分濃度２０質量％のポリアミック酸ＰＡ－２～ＰＡ－３を得た。
Figure JPOXMLDOC01-appb-T000033
 << Synthesis Examples 2 to 3 >>
Polyamic acid PA-2 to PA having a solid content concentration of 20% by mass in the same manner as in Synthesis Example 1 except that the type and amount of raw materials used in the synthesis of polyamic acid are changed as shown in Table 1 below. -3 was obtained.
Figure JPOXMLDOC01-appb-T000033
　上記表１における各略号は下記を意味する。
ＤＡＥ：４，４’－ジアミノジフェノルエーテル（東京化成（株）製）
ＤＤＳ：３，３’－ジアミノジフェノルスルホン（和光純薬（株）製）
ＤＢＡ：４，４’－ジアミノベンズアニリド（東京化成（株）製）
ＨＡＤ：ヘキサメチレンジアミン（東京化成（株）製）
Ｓｉ－ＤＡ：ビス（３－アミノプロピル）テトラメチルジシロキサン（東京化成（株）製）
ＢＴＤＡ：３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物（和光純薬（株）社製）
ＰＭＤＡ：ピロメリット酸無水物（和光純薬（株）製）
ＢＴＣＡ：１，２，３，４－ブタンテトラカルボン酸二無水物（新日本理化（株）製、リカシッドＢＴ－１００）
ＭＡ：無水マレイン酸（東京化成（株）製）
ＰＡ：無水フタル酸（東京化成（株）製） Each abbreviation in Table 1 means the following.
DAE: 4,4′-diaminodiphenol ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
DDS: 3,3′-diaminodiphenol sulfone (manufactured by Wako Pure Chemical Industries, Ltd.)
DBA: 4,4′-diaminobenzanilide (manufactured by Tokyo Chemical Industry Co., Ltd.)
HAD: Hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Si-DA: Bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.)
BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (Wako Pure Chemical Industries, Ltd.)
PMDA: pyromellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)
BTCA: 1,2,3,4-butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid BT-100)
MA: Maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
PA: phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
＜緑色着色樹脂組成物Ｇ－１～Ｇ－３４の調製＞
　下記の組成の混合物を均一に攪拌混合した後、ビーズミルにより３時間混合・分散して緑色着色樹脂組成物Ｇ－１を調製した。
　ポリハロゲン化亜鉛フタロシアニン顔料
（Ｃ．Ｉ．ピグメントグリーン５８、ＤＩＣ社製）　　　　７．７０質量部
　ニッケルアゾ系黄色顔料
（Ｃ．Ｉ．ピグメントイエロー１５０）　　　　　　　　　６．３０質量部
　ポリアミック酸ＰＡ－１　　　　　　６．００質量部（不揮発分として）
　γ－ブチロラクトン　　　　　　　　　　　　　　　　４０．００質量部
　３－メチル－３－メトキシブタノール　　　　　　　　４０．００質量部 <Preparation of Green Colored Resin Compositions G-1 to G-34>
A mixture having the following composition was uniformly stirred and mixed, and then mixed and dispersed by a bead mill for 3 hours to prepare a green colored resin composition G-1.
Polyhalogenated zinc phthalocyanine pigment (CI Pigment Green 58, manufactured by DIC Corporation) 7.70 parts by mass Nickel azo yellow pigment (CI Pigment Yellow 150) 6.30 parts by mass Polyamic acid PA-1 6.00 Part by mass (as non-volatile content)
γ-butyrolactone 40.00 parts by mass 3-methyl-3-methoxybutanol 40.00 parts by mass
　緑色着色樹脂組成物Ｇ－１の組成を下記表２に記載した組成に変更したこと以外は、緑色着色樹脂組成物Ｇ－１と同様の方法で、緑色着色樹脂組成物Ｇ－２～Ｇ－３４を調製した。 The green colored resin compositions G-2 to G- were prepared in the same manner as the green colored resin composition G-1, except that the composition of the green colored resin composition G-1 was changed to the composition shown in Table 2 below. 34 was prepared.
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
　上記表２における各略号は以下の化合物を指す。
ＰＧ５８：Ｃ．Ｉ．ピグメントグリーン５８（ポリハロゲン化亜鉛フタロシアニン緑色顔料、ＤＩＣ社製）
ＰＹ１２９：Ｃ．Ｉ．ピグメントイエロー１２９（銅アゾメチン系黄色顔料）
ＰＹ１５０：Ｃ．Ｉ．ピグメントイエロー１５０（ニッケルアゾ系黄色顔料）
ＰＹ１８５：Ｃ．Ｉ．ピグメントイエロー１８５（イソインドリン系黄色顔料）
Ｄ－１：下記構造式の顔料誘導体（富士フイルム（株）製）
Figure JPOXMLDOC01-appb-C000035
 Ｄ－２：下記構造式の顔料誘導体（富士フイルム（株）製）
Figure JPOXMLDOC01-appb-C000036
 Ｄ－３：下記構造式の顔料誘導体（富士フイルム（株）製）
Figure JPOXMLDOC01-appb-C000037
 Ｃ－１：ｐ－フェニレンジアミン（和光純薬（株）製）
Ｃ－２：４，４’－ジアミノジフェニルエーテル（東京化成（株）製）
Ｃ－３：４，４’－ジアミノベンズアニリド（東京化成（株）製）
Ｃ－４：ヘキサメチレンジアミン（東京化成（株）製）
Ｆ－１：ＤＩＣ社製、メガファックＦ－７８１Ｆ（フッ素系界面活性剤）
ＢＬ：γ－ブチロラクトン
ＭＭＢ：３－メチル－３－メトキシブタノール
分散剤Ａ：下記構造式の高分子分散剤（富士フイルム（株）製）、下記式において、ａ＝３．５、ｂ＝２．５であり、酸価は３０ｍｇＫＯＨ／ｇ、重量平均分子量２０，０００のものを使用した）
Figure JPOXMLDOC01-appb-C000038
 エポキシ樹脂Ａ：下記構造式のエポキシ樹脂（ダイセル化学工業製、ＥＨＰＥ３１５０）
Figure JPOXMLDOC01-appb-C000039
 Each abbreviation in Table 2 indicates the following compound.
PG58: C.I. I. Pigment Green 58 (polyhalogenated zinc phthalocyanine green pigment, manufactured by DIC Corporation)
PY129: C.I. I. Pigment Yellow 129 (copper azomethine yellow pigment)
PY150: C.I. I. Pigment Yellow 150 (Nickel azo yellow pigment)
PY185: C.I. I. Pigment Yellow 185 (isoindoline-based yellow pigment)
D-1: Pigment derivative having the following structural formula (manufactured by FUJIFILM Corporation)
Figure JPOXMLDOC01-appb-C000035
 D-2: Pigment derivative having the following structural formula (manufactured by FUJIFILM Corporation)
Figure JPOXMLDOC01-appb-C000036
 D-3: Pigment derivative having the following structural formula (manufactured by FUJIFILM Corporation)
Figure JPOXMLDOC01-appb-C000037
 C-1: p-phenylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.)
C-2: 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-3: 4,4′-diaminobenzanilide (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-4: Hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
F-1: Made by DIC, MegaFuck F-781F (fluorine-based surfactant)
BL: γ-butyrolactone MMB: 3-methyl-3-methoxybutanol dispersant A: polymer dispersant having the following structural formula (manufactured by FUJIFILM Corporation), where a = 3.5, b = 2. 5 and an acid value of 30 mg KOH / g and a weight average molecular weight of 20,000 was used)
Figure JPOXMLDOC01-appb-C000038
 Epoxy resin A: Epoxy resin having the following structural formula (manufactured by Daicel Chemical Industries, EHPE3150)
Figure JPOXMLDOC01-appb-C000039
＜緑色着色樹脂組成物の評価＞
＜＜耐溶剤性の評価＞＞
　上記得られた緑色着色樹脂組成物Ｇ－１～Ｇ－３４を、ガラス基板上に乾燥後膜厚が０．６μｍになるようにスピンコーターを用いて塗布し、１００℃で１２０秒間プリベークして着色膜を得た。得られた着色膜を更に窒素雰囲気下で２４０℃３０分加熱（ポストベーク）し、塗膜の硬化処理を行った。この過程で、塗膜中のポリアミック酸が脱水縮合反応を起こしてポリイミドに変換される。
　硬化処理を行って得られた硬化塗膜をＮ－メチルピロリドンに６０秒間浸漬し、浸漬前後の硬化塗膜の分光透過率変化をＭＣＰＤ－３０００（大塚電子（株）製）で測定し、得られた色差ΔＥａｂによって耐溶剤性を評価した。ΔＥａｂが小さいほど、溶剤浸漬前後の分光透過率の変動が小さく、耐溶剤性に優れることを意味する。耐溶剤性の評価結果を表２にまとめて示す。 <Evaluation of green colored resin composition>
<< Evaluation of solvent resistance >>
The green colored resin compositions G-1 to G-34 obtained above were applied onto a glass substrate using a spin coater so that the film thickness after drying was 0.6 μm, and prebaked at 100 ° C. for 120 seconds. A colored film was obtained. The obtained colored film was further heated (post-baked) at 240 ° C. for 30 minutes in a nitrogen atmosphere, and the coating film was cured. In this process, the polyamic acid in the coating film undergoes a dehydration condensation reaction and is converted to polyimide.
The cured coating film obtained by the curing treatment was immersed in N-methylpyrrolidone for 60 seconds, and the change in spectral transmittance of the cured coating film before and after immersion was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The solvent resistance was evaluated by the obtained color difference ΔEab. The smaller ΔEab, the smaller the change in spectral transmittance before and after immersion in the solvent, and the better the solvent resistance. Table 2 summarizes the evaluation results of solvent resistance.
＜＜針状異物の評価＞＞
（青色顔料分散液Ｂ１の調製）
　顔料としてＣ．Ｉ．ピグメントブルー１５：６（９．５部）と、Ｃ．Ｉ．ピグメントバイオレット２３（２．４部）と、顔料分散剤としてＢＹＫ－１６１（ＢＹＫ社製、５．６部）と、ＰＧＭＥＡ（８２．５部）とからなる混合液を、ビーズミルにより１５時間混合・分散して、青色顔料分散液Ｂ１を調製した。 << Evaluation of acicular foreign matter >>
(Preparation of blue pigment dispersion B1)
As a pigment, C.I. I. Pigment blue 15: 6 (9.5 parts), C.I. I. A mixture of Pigment Violet 23 (2.4 parts), BYK-161 (5.6 parts made by BYK) as a pigment dispersant, and PGMEA (82.5 parts) was mixed for 15 hours using a bead mill. Dispersion was carried out to prepare a blue pigment dispersion B1.
（青色樹脂組成物Ｂ－ａの調製）
・顔料分散液：上記青色顔料分散液Ｂ１      　　　　　　　　５１．２部
・光重合開始剤：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０１（ＢＡＳＦ（株）製）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．８７部
・重合性化合物：ＫＡＹＡＲＡＤ　ＲＰ－１０４０（日本化薬（株）製）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４．７部
・バインダー：ＡＣＡ２３０ＡＡ　（ダイセル化学工業（株）製）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　７．４部
・重合禁止剤：ｐ－メトキシフェノール　　　　　　　　　　０．００２部
・ノニオン系界面活性剤：パイオニンＤ－６１１２－Ｗ（竹本油脂（株）製）　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１９部
・シランカップリング剤：ＫＢＭ－６０２（信越化学（株）製）のシクロヘキサノン０．９％溶液　　　　　　　　　　　　　　　　　　　１０．８部
・有機溶剤：ＰＧＭＥＡ　　　　　　　　　　　　　　　　　　１４．３部
・有機溶剤：シクロヘキサノン　　　　　　　　　　　　　　　　６．４部
・フッ素系界面活性剤：Ｆ－７８１（ＤＩＣ（株）製）のシクロヘキサノン０．２％溶液　　　　　　　　　　　　　　　　　　　　　　　　４．２部 (Preparation of blue resin composition Ba)
Pigment dispersion: 51.2 parts of the above blue pigment dispersion B1 Photopolymerization initiator: IRGACURE OX-01 (manufactured by BASF Corporation)
0.87 parts Polymerizable compound: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)
4.7 parts / Binder: ACA230AA (manufactured by Daicel Chemical Industries, Ltd.)
7.4 parts ・ Polymerization inhibitor: p-methoxyphenol 0.002 parts ・ Nonionic surfactant: Pionine D-6112-W (manufactured by Takemoto Yushi Co., Ltd.) 0.19 parts ・ Silane coupling agent: KBM- 10.8 parts of cyclohexanone 0.9% solution of 602 (manufactured by Shin-Etsu Chemical Co., Ltd.), organic solvent: 14.3 parts of PGMEA, organic solvent: 6.4 parts of cyclohexanone, fluorosurfactant: F-781 (DIC) 4.2 parts solution of cyclohexanone (manufactured by Co., Ltd.)
＜ドライエッチングによる緑色画素パターンの形成工程＞
（緑色層の形成）
　シリコンウエハ上にスピンコーターにて、上述した緑色着色樹脂組成物を塗布した後、１００℃１８０秒間ホットプレートで乾燥した後、窒素雰囲気下で２４０℃３０分加熱処理（ポストベーク）を行うことで、緑色着色膜を形成した。この緑色着色膜の膜厚は０．６μｍであった。 <Green pixel pattern formation process by dry etching>
(Formation of green layer)
After applying the above-mentioned green colored resin composition on a silicon wafer with a spin coater, drying on a hot plate at 100 ° C. for 180 seconds, and then performing a heat treatment (post bake) at 240 ° C. for 30 minutes in a nitrogen atmosphere. A green colored film was formed. The thickness of this green colored film was 0.6 μm.
（マスク用レジストの塗布）
　得られた緑色着色膜の上に、ポジ型フォトレジスト「ＦＨｉ６２２ＢＣ」（富士フイルムエレクトロニクスマテリアルズ社製）を塗布し、プリベークを実施し、膜厚０．８μｍのフォトレジスト層を形成した。 (Application of mask resist)
On the obtained green colored film, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied and prebaked to form a 0.8 μm-thick photoresist layer.
（マスク用レジストのパターン露光と現像）
　得られたフォトレジスト層を、ｉ線ステッパー（キャノン（株）製）を用いてパターン露光し、フォトレジスト層の温度又は雰囲気温度が９０℃となる温度で１分間、加熱処理を行なった。その後、現像液「ＦＨＤ－５」（富士フイルムエレクトロニクスマテリアルズ社製）で１分間の現像処理を行ない、さらに１１０℃で１分間のポストベーク処理を実施して、レジストパターンを形成した。このレジストパターンは、エッチング変換差（エッチングによるパターン幅の縮小）を考慮して、一辺１．２５μｍで形成された正方形状のレジスト膜が市松状に配列されてなるパターンである。 (Mask resist pattern exposure and development)
The obtained photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.) and subjected to heat treatment for 1 minute at a temperature at which the temperature of the photoresist layer or the atmospheric temperature was 90 ° C. Thereafter, development processing was performed with a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials) for 1 minute, and further post-baking processing was performed at 110 ° C. for 1 minute to form a resist pattern. This resist pattern is a pattern in which square-shaped resist films formed with a side of 1.25 μm are arranged in a checkered pattern in consideration of etching conversion difference (pattern width reduction by etching).
（ドライエッチング）
　得られたレジストパターンをエッチングマスクとして、緑色着色膜のドライエッチングを以下の手順で行った。
　ドライエッチング装置（日立ハイテクノロジーズ社製、Ｕ－６２１）にて、ＲＦパワー：８００Ｗ、アンテナバイアス：４００Ｗ、ウエハバイアス：２００Ｗ、チャンバーの内部圧力：４．０Ｐａ、基板温度：５０℃、混合ガスのガス種及び流量をＣＦ4：８０ｍＬ／ｍｉｎ．、Ｏ2：４０ｍＬ／ｍｉｎ．、Ａｒ：８００ｍＬ／ｍｉｎ．として、８０秒の第１段階のエッチング処理を実施した。
　このエッチング条件での緑色層の削れ量は５３４ｎｍ（８９％のエッチング量）となり、約５８ｎｍの残膜がある状態になった。
　次いで、同一のエッチングチャンバーにて、ＲＦパワー：６００Ｗ、アンテナバイアス：１００Ｗ、ウエハバイアス：２５０Ｗ、チャンバーの内部圧力：２．０Ｐａ、基板温度：５０℃、混合ガスのガス種及び流量をＮ2：５００ｍＬ／ｍｉｎ．、Ｏ2：５０ｍＬ／ｍｉｎ．、Ａｒ：５００ｍＬ／ｍｉｎ．とし（Ｎ2／Ｏ2／Ａｒ＝１０／１／１０）、エッチングトータルでのオーバーエッチング率を２０％として、第２段階エッチング処理、オーバーエッチング処理を実施した。
　第２段階のエッチング条件での緑色層のエッチングレートは６００ｎｍ／ｍｉｎ以上であって、緑色層の残膜をエッチングするのに約１０秒の時間を要した。第１段階のエッチング時間の８０秒と第２段階のエッチング時間１０秒を加算したものをエッチング時間と算出した。その結果、エッチング時間：８０＋１０＝９０秒、オーバーエッチング時間：９０×０．２＝１８秒になり、全エッチング時間は９０＋１８＝１０８秒に設定した。
　上記条件でドライエッチングを行った後、フォトレジスト剥離液「ＭＳ２３０Ｃ」（富士フイルムエレクトロニクスマテリアルズ社製）を使用して１２０秒間、剥離処理を実施してレジストパターンを除去し、更に純水による洗浄、スピン乾燥を実施した。その後、１００℃で２分間の脱水ベーク処理を行った。以上により、一辺１．２μｍの正方形状の緑色画素が市松状に配列されてなる緑色パターンを得た。このように、本発明の緑色樹脂組成物から形成された緑色着色膜をドライエッチングで加工することにより、固体撮像素子用のカラーフィルタに適する微細な画素パターンを形成できることが確認された。 (Dry etching)
Using the obtained resist pattern as an etching mask, dry etching of the green colored film was performed according to the following procedure.
RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, chamber internal pressure: 4.0 Pa, substrate temperature: 50 ° C., mixed gas in dry etching apparatus (Hitachi High Technologies, U-621) The gas type and flow rate were CF 4 : 80 mL / min. , O 2 : 40 mL / min. , Ar: 800 mL / min. As a result, the first stage etching process of 80 seconds was performed.
Under this etching condition, the amount of green layer scraping was 534 nm (89% etching amount), and there was a remaining film of about 58 nm.
Next, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., gas mixture type and flow rate of N 2 : 500 mL / min. , O 2 : 50 mL / min. , Ar: 500 mL / min. (N 2 / O 2 / Ar = 10/1/10), and the second etching process and the over-etching process were performed with the over-etching rate in the total etching being 20%.
The etching rate of the green layer under the second stage etching conditions was 600 nm / min or more, and it took about 10 seconds to etch the remaining film of the green layer. The sum of 80 seconds of the first stage etching time and 10 seconds of the second stage etching time was calculated as the etching time. As a result, the etching time was 80 + 10 = 90 seconds, the over-etching time was 90 × 0.2 = 18 seconds, and the total etching time was set to 90 + 18 = 108 seconds.
After performing dry etching under the above conditions, the resist pattern is removed for 120 seconds using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials), and the resist pattern is removed, followed by washing with pure water. Spin drying was performed. Thereafter, a dehydration baking process was performed at 100 ° C. for 2 minutes. As described above, a green pattern in which square green pixels having a side of 1.2 μm are arranged in a checkered pattern was obtained. Thus, it was confirmed that a fine pixel pattern suitable for a color filter for a solid-state imaging device can be formed by processing the green colored film formed from the green resin composition of the present invention by dry etching.
　上記＜ドライエッチングによる緑色画素パターンの形成工程＞において、各緑色着色樹脂組成物Ｇ－１～Ｇ－３４用いることにより作成した、一辺１．２μｍの正方形状の緑色画素が市松状に配列されてなる緑色パターンをそれぞれ準備し、この緑色パターンの各貫通孔の内部に青色樹脂組成物Ｂ－ａが埋設されるように、かつ、乾燥及びポストベーク後の厚みが０．４０μｍになるように、青色樹脂組成物Ｂ－ａを上記緑色パターン上に塗布し、緑色層上に青色感放射線性層が形成されてなる積層カラーフィルタを得た。
　このようにして得た積層カラーフィルタの青色感放射線性層に対して、ｉ線ステッパー（キャノン（株）製）を用いてパターン露光した。ここで、露光領域は、上記緑色パターンの市松模様において偶数列に位置する貫通孔に対応する領域である。
　次いで、露光後の積層カラーフィルタをスピン・シャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、ＣＤ－２０００（富士フイルムエレクトロニクスマテリアルズ（株）製）の６０％希釈液を用いて２３℃で６０秒間パドル現像を行った。その後、カラーフィルタを真空チャック方式で上記水平回転テーブルに固定し、回転装置によってカラーフィルタを回転数５０ｒｐｍで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行い、その後スプレー乾燥した。
　以上により、積層カラーフィルタにおける青色感放射線性層と、上記緑色パターンの市松模様において奇数列に位置する貫通孔の内部に設けられた青色画素とが除去されてなるカラーフィルタ前駆体を得た。
　このようにして得られたカラーフィルタ前駆体を、ホットプレート上で２３０℃３００秒加熱処理を行った。加熱処理後のカラーフィルタ前駆体を、走査型電子顕微鏡（日立製、Ｓ－９２６０）を用いて観察し、緑色画素と青色画素の境界領域に針状異物が発生しているかどうかを確認した。確認した結果、針状異物の発生状況に応じて、下記要領で評価を行った。評価結果を表２にまとめて示す。
　Ａ：針状異物が全く生じていない
　Ｂ：長さ０．１μｍ未満の小さな針状異物が僅かに観察されるが、問題無いレベル
　Ｃ：長さ０．１～０．２μｍの針状異物が僅かに観察されるが、問題無いレベル
　Ｄ：長さ０．２μｍを超える大きな針状異物が沢山観察された In the above <Green pixel pattern forming step by dry etching>, square green pixels having a side of 1.2 μm, which are created by using the green colored resin compositions G-1 to G-34, are arranged in a checkered pattern. Each green pattern is prepared, so that the blue resin composition Ba is embedded in each through hole of the green pattern, and the thickness after drying and post-baking is 0.40 μm. Blue resin composition Ba was applied on the green pattern to obtain a laminated color filter in which a blue radiation-sensitive layer was formed on the green layer.
The blue radiation sensitive layer of the multilayer color filter thus obtained was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.). Here, an exposure area | region is an area | region corresponding to the through-hole located in an even number row | line | column in the checkered pattern of the said green pattern.
Next, the layered color filter after exposure was placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). ) Was used for 60 seconds at 23 ° C. After that, the color filter is fixed to the horizontal rotary table by a vacuum chuck method, and the color filter is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is supplied from the ejection nozzle in a shower shape from above the rotation center to rinse. Treatment was followed by spray drying.
As described above, a color filter precursor obtained by removing the blue radiation-sensitive layer in the laminated color filter and the blue pixels provided in the through holes located in the odd rows in the checkered pattern of the green pattern was obtained.
The color filter precursor thus obtained was subjected to heat treatment at 230 ° C. for 300 seconds on a hot plate. The color filter precursor after the heat treatment was observed using a scanning electron microscope (Hitachi, S-9260), and it was confirmed whether needle-like foreign matters were generated in the boundary region between the green pixel and the blue pixel. As a result of the confirmation, the evaluation was performed in the following manner according to the state of occurrence of acicular foreign matter. The evaluation results are summarized in Table 2.
A: No acicular foreign matter is generated at all B: Small acicular foreign matters with a length of less than 0.1 μm are slightly observed, but there is no problem C: Acicular foreign matters with a length of 0.1 to 0.2 μm Slightly observed, but no problem level D: Many large needle-like foreign objects exceeding 0.2 μm in length were observed
比較例２（緑色顔料としてＰＧ３６を用いた場合の効果の検証）
　下記組成の混合物を均一に攪拌混合した後、ビーズミルにより３時間混合・分散する事によって、緑色顔料としてＣ．Ｉ．ピグメントグリーン３６を用い、硬化樹脂として上述したポリアミック酸ＰＡ－１を用いた緑色着色樹脂組成物Ｇ３６－ＰＡを調製した。
　ポリハロゲン化銅フタロシアニン顔料（Ｃ．Ｉ．ピグメントグリーン３６）　　　　　　　　　　　　　　　　　　　　　　　　　　７．７０質量部
　ニッケルアゾ系黄色顔料（Ｃ．Ｉ．ピグメントイエロー１５０）
　　　　　　　　　　　　　　　　　　　　　　　　　　　６．３０質量部
　ポリアミック酸ＰＡ－１　　　　　　６．００質量部（不揮発分として）
　γ－ブチロラクトン    　　　　　　　　　　　　　　４０．００質量部
　３－メチル－３－メトキシブタノール　　　　　　　　４０．００質量部 Comparative Example 2 (Verification of effects when PG36 is used as a green pigment)
A mixture having the following composition was stirred and mixed uniformly, and then mixed and dispersed by a bead mill for 3 hours, whereby C.I. I. Using Pigment Green 36, a green colored resin composition G36-PA using the above-described polyamic acid PA-1 as a cured resin was prepared.
Polyhalogenated copper phthalocyanine pigment (CI Pigment Green 36) 7.70 parts by mass Nickel azo yellow pigment (CI Pigment Yellow 150)
6.30 parts by mass Polyamic acid PA-1 6.00 parts by mass (as non-volatile content)
γ-butyrolactone 40.00 parts by mass 3-methyl-3-methoxybutanol 40.00 parts by mass
　更に、下記組成の混合物を均一に攪拌混合した後、ビーズミルにより３時間混合・分散する事によって、緑色顔料としてＣ．Ｉ．ピグメントグリーン３６を用い、硬化樹脂としてエポキシ樹脂を用いた緑色着色樹脂組成物Ｇ３６－ＥＰを調製した。
　ポリハロゲン化銅フタロシアニン顔料（Ｃ．Ｉ．ピグメントグリーン３６）　　　　　　　　　　　　　　　　　　　　　　　　　　７．７０質量部
　ニッケルアゾ系黄色顔料（Ｃ．Ｉ．ピグメントイエロー１５０）
　　　　　　　　　　　　　　　　　　　　　　　　　　　６．３０質量部
　上記分散剤Ａ　　　　　　　　　　　　　　　　　　　　４．２０質量部
　エポキシ樹脂Ａ（ダイセル化学工業製、ＥＨＰＥ３１５０）
　　　　　　　　　　　　　　　　　　　　　　　　　　　１．８０質量部
　γ－ブチロラクトン    　　　　　　　　　　　　　　４０．００質量部
　３－メチル－３－メトキシブタノール　　　　　　　　４０．００質量部 Further, a mixture having the following composition was uniformly stirred and mixed, and then mixed and dispersed by a bead mill for 3 hours, whereby C.I. I. A green colored resin composition G36-EP using Pigment Green 36 and an epoxy resin as a cured resin was prepared.
Polyhalogenated copper phthalocyanine pigment (CI Pigment Green 36) 7.70 parts by mass Nickel azo yellow pigment (CI Pigment Yellow 150)
6.30 parts by mass Dispersant A 4.20 parts by mass Epoxy resin A (manufactured by Daicel Chemical Industries, EHPE 3150)
1.80 parts by mass γ-butyrolactone 40.00 parts by mass 3-methyl-3-methoxybutanol 40.00 parts by mass
　上記の緑色着色樹脂組成物Ｇ３６－ＰＡ・Ｇ３６－ＥＰ各々について、上述した耐溶剤性および針状異物の評価方法と同様の方法で評価を行った。その結果、Ｇ３６－ＰＡ・Ｇ３６－ＥＰとの間で耐溶剤性と針状異物の評価結果に差が見られなかった。この結果から、緑色顔料としてＰＧ３６を用いた場合は、本発明で用いられるポリアミック酸を硬化樹脂として用いても、本発明の効果が見出せないことがわかった。 Each of the above green colored resin compositions G36-PA · G36-EP was evaluated by the same method as the solvent resistance and needle foreign matter evaluation methods described above. As a result, there was no difference between G36-PA and G36-EP in the solvent resistance and the evaluation results of needle-like foreign matters. From this result, it was found that when PG36 was used as the green pigment, the effect of the present invention could not be found even when the polyamic acid used in the present invention was used as the cured resin.
＜ウェットエッチングによる緑色画素パターンの形成＞
（緑色層の形成）
　ガラスウエハ上にスピンコーターにて、上述した緑色着色樹脂組成物Ｇ－１を塗布した後、１００℃１８０秒間ホットプレートで乾燥し、緑色着色膜を形成した。
（マスク用レジストの塗布）
　次いで、緑色着色膜の上に、ポジ型フォトレジスト「ＦＨｉ６２２ＢＣ」（富士フイルムエレクトロニクスマテリアルズ社製）を塗布し、プリベークを実施し、膜厚０．８μｍのフォトレジスト層を形成した。
（マスク用レジストのパターン露光とアルカリ現像によるウェットエッチング）
　続いて、フォトレジスト層を、ｉ線ステッパー（キヤノン（株）製）を用いてパターン露光し、フォトレジスト層の温度又は雰囲気温度が９０℃となる温度で１分間、加熱処理を行なった。その後、フォトレジスト上に現像液「ＦＨＤ－５」（富士フイルムエレクトロニクスマテリアルズ社製）を浸漬して、フォトレジストおよび下層の緑色着色膜の現像を同時に行った（これは、上層のフォトレジスト膜をマスクとした、下層の緑色着色膜のウェットエッチ工程に相当する）。エッチング後、不要となったフォトレジスト層をメチルセルソルブアセテートで剥離した。このようにして得られたポリイミド前駆体緑色着色膜を窒素雰囲気中２４０℃で３０分加熱（ポストベーク）処理し、膜厚１．２μｍの緑色画素パターンを得た。当緑色画素パターンは１２０μｍ×８０μｍの画素サイズを有していることを走査型電子顕微鏡（日立製、Ｓ－９２６０）で確認した。
　上記と同様の方法で、緑色着色樹脂組成物Ｇ－２～Ｇ－３０についてもウェットエッチングによるパターン形成を試みた結果、何れの組成物からも緑色画素パターンが問題無く形成されることを確認した。
　以上より、本発明の緑色着色樹脂組成物から形成された緑色着色膜をウェットエッチングで作製することにより、液晶表示装置や有機ＬＥＤ表示装置といった各種表示装置用のカラーフィルタに適した数十～数百μｍ程度のサイズを有する画素パターンを形成できることが確認された。 <Formation of green pixel pattern by wet etching>
(Formation of green layer)
The above-mentioned green colored resin composition G-1 was applied onto a glass wafer with a spin coater and then dried on a hot plate at 100 ° C. for 180 seconds to form a green colored film.
(Application of mask resist)
Next, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied on the green colored film and prebaked to form a 0.8 μm-thick photoresist layer.
(Pattern exposure of mask resist and wet etching by alkali development)
Subsequently, the photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.), and heat treatment was performed for 1 minute at a temperature at which the temperature of the photoresist layer or the atmospheric temperature was 90 ° C. Thereafter, a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was immersed in the photoresist, and the photoresist and the lower green colored film were developed at the same time (this is the upper photoresist film). This is equivalent to a wet etching process of the underlying green colored film using the After etching, the unnecessary photoresist layer was peeled off with methyl cellosolve acetate. The polyimide precursor green colored film thus obtained was heated (post-baked) at 240 ° C. for 30 minutes in a nitrogen atmosphere to obtain a green pixel pattern having a film thickness of 1.2 μm. The green pixel pattern was confirmed to have a pixel size of 120 μm × 80 μm with a scanning electron microscope (Hitachi, S-9260).
As a result of trying the pattern formation by wet etching for the green colored resin compositions G-2 to G-30 by the same method as above, it was confirmed that the green pixel pattern was formed from any composition without any problem. .
From the above, by producing a green colored film formed from the green colored resin composition of the present invention by wet etching, several tens to several numbers suitable for color filters for various display devices such as liquid crystal display devices and organic LED display devices. It was confirmed that a pixel pattern having a size of about 100 μm can be formed.
１１　第１の着色層、１２　第１の着色パターン、２１　第２着色感放射線性層、２１Ａ　第１の除去部群１２１に対応する位置、２２　第２の着色パターン、２２Ｒ　第２の除去部群１２２の各除去部の内部に設けられた複数の第２の着色画素、３１　第３着色感放射線性層、３１Ａ　第２の除去部群１２２に対応する位置、３２　第３の着色パターン、５１　フォトレジスト層、５１Ａ　レジスト除去部、５２　レジストパターン（パターニングされたフォトレジスト層）、１２０　除去部群、１２１　第１の除去部群、１２２　第２の除去部群 11 1st colored layer, 12 1st colored pattern, 21 2nd colored radiation sensitive layer, 21A, position corresponding to 1st removal part group 121, 22 2nd coloring pattern, 22R 2nd removal part group A plurality of second colored pixels provided in each removal portion of 122, 31 third colored radiation-sensitive layer, 31A position corresponding to second removal portion group 122, 32 third coloring pattern, 51 photo Resist layer, 51A resist removal portion, 52 resist pattern (patterned photoresist layer), 120 removal portion group, 121 first removal portion group, 122 second removal portion group

Claims (17)

  1. 下記一般式（１）で表される繰り返し単位を有するポリアミック酸およびＣ．Ｉ．ピグメントグリーン５８を含む、着色樹脂組成物；
    Figure JPOXMLDOC01-appb-C000001
     一般式（１）中、Ｒ1はｎ＋２価の連結基を表し、Ｒ2は２価の連結基を表し、ｎは１または２を表す。     A polyamic acid having a repeating unit represented by the following general formula (1) and C.I. I. A colored resin composition comprising CI Pigment Green 58;
    Figure JPOXMLDOC01-appb-C000001
     In general formula (1), R 1 represents an n + divalent linking group, R 2 represents a divalent linking group, and n represents 1 or 2.
  2. 下記一般式（２）で表されるジアミン化合物をさらに含む、請求項１に記載の着色樹脂組成物；
    Figure JPOXMLDOC01-appb-C000002
     一般式（２）中、Ｒ3は２価の連結基を表す。     The colored resin composition according to claim 1, further comprising a diamine compound represented by the following general formula (2);
    Figure JPOXMLDOC01-appb-C000002
     In general formula (2), R 3 represents a divalent linking group.
  3. 黄色の着色剤をさらに含む、請求項１または２に記載の着色樹脂組成物。 The colored resin composition according to claim 1 or 2, further comprising a yellow colorant.
  4. 前記黄色の着色剤として、Ｃ．Ｉ．ピグメントイエロー１２９を含む、請求項３に記載の着色樹脂組成物。 As the yellow colorant, C.I. I. The colored resin composition according to claim 3, comprising Pigment Yellow 129.
  5. 一般式（１）中、Ｒ1は炭素数２～２２のｎ＋２価の連結基を表す、請求項１～４のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 4, wherein, in the general formula (1), R 1 represents an n + divalent linking group having 2 to 22 carbon atoms.
  6. 一般式（１）中、Ｒ1は環状構造を含むｎ＋２価の連結基を表す、請求項１～４のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 4, wherein in the general formula (1), R 1 represents an n + divalent linking group containing a cyclic structure.
  7. 一般式（１Ａ）中、Ｒ2は炭素数１～２２の２価の連結基を表す、請求項１～６のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 6, wherein R 2 in the general formula (1A) represents a divalent linking group having 1 to 22 carbon atoms.
  8. 一般式（１）中、Ｒ2は炭化水素基、または、炭化水素基と－Ｓｉ（Ｒ2A）2－、－ＣＯ－、－ＮＲ－、－Ｏ－、－ＳＯ2－、および－Ｓ－から選択される少なくとも１種との組み合わせからなる基を含む２価の連結基を表す、請求項１～６のいずれか１項に記載の着色樹脂組成物；但し、Ｒ2Aはそれぞれ独立して炭素数１～６のアルキル基を表し、－ＮＲ－におけるＲは水素原子または炭素数１～６のアルキル基を表す。 In the general formula (1), R 2 is a hydrocarbon group, or a hydrocarbon group and —Si (R 2A ) 2 —, —CO—, —NR—, —O—, —SO 2 —, and —S—. The colored resin composition according to any one of claims 1 to 6, which represents a divalent linking group containing a group consisting of a combination with at least one selected from: R 2A independently Represents an alkyl group having 1 to 6 carbon atoms, and R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  9. 一般式（２）中、Ｒ3は炭素数１～２２の２価の連結基を表す、請求項１～８のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 8, wherein in the general formula (2), R 3 represents a divalent linking group having 1 to 22 carbon atoms.
  10. 一般式（２）中、Ｒ3は環状構造を含む２価の連結基を表す、請求項１～８のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 8, wherein, in the general formula (2), R 3 represents a divalent linking group containing a cyclic structure.
  11. 一般式（２）中のＲ3は、一般式（１）中のＲ2と同一の骨格を含む２価の連結基を表す、請求項１～８のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 8, wherein R 3 in the general formula (2) represents a divalent linking group containing the same skeleton as R 2 in the general formula (1). object.
  12. 固体撮像素子用に用いられる、請求項１～１１のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 11, which is used for a solid-state imaging device.
  13. 請求項１～１２のいずれか１項に記載の着色樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the colored resin composition according to any one of claims 1 to 12.
  14. 請求項１～１２のいずれか１項に記載の着色樹脂組成物を用いた着色層を有するカラーフィルタ。 A color filter having a colored layer using the colored resin composition according to any one of claims 1 to 12.
  15. 請求項１～１２のいずれか１項に記載の着色樹脂組成物を基板上に塗布して着色膜を形成する工程、
    前記着色膜を１５０～３５０℃で加熱し、硬化させる工程、
    前記硬化された着色膜の上にフォトレジストを塗布する工程、
    前記フォトレジストをパターン露光した後、アルカリ現像することによって、フォトレジストをパターニングする工程、
    前記パターニングされたフォトレジストをエッチングマスクとして、前記フォトレジストの下層の着色膜をドライエッチングによりパターニングする工程、
    前記パターニング後のフォトレジストを除去する工程、
    を含む、カラーフィルタの製造方法。     Applying the colored resin composition according to any one of claims 1 to 12 on a substrate to form a colored film;
    Heating and curing the colored film at 150 to 350 ° C .;
    Applying a photoresist on the cured colored film;
    A step of patterning the photoresist by performing alkali exposure after pattern exposure of the photoresist,
    Patterning the colored film under the photoresist by dry etching using the patterned photoresist as an etching mask;
    Removing the patterned photoresist.
    A method for producing a color filter, comprising:
  16. 請求項１４に記載のカラーフィルタまたは請求項１５に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する固体撮像素子。 The solid-state image sensor which has a color filter obtained by the manufacturing method of the color filter of Claim 14, or the color filter of Claim 15.
  17. 請求項１４に記載のカラーフィルタまたは請求項１５に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する画像表示装置。 An image display device comprising the color filter according to claim 14 or the color filter obtained by the method for producing a color filter according to claim 15.
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