WO2020017576A1 - Photosensitive colored resin composition, cured product, image display device, and illumination - Google Patents

Photosensitive colored resin composition, cured product, image display device, and illumination Download PDF

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Publication number
WO2020017576A1
WO2020017576A1 PCT/JP2019/028195 JP2019028195W WO2020017576A1 WO 2020017576 A1 WO2020017576 A1 WO 2020017576A1 JP 2019028195 W JP2019028195 W JP 2019028195W WO 2020017576 A1 WO2020017576 A1 WO 2020017576A1
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PCT/JP2019/028195
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French (fr)
Japanese (ja)
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利光　恵理子
紫陽 平岡
良尚 沢井
和裕 中谷
恵子 斎藤
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三菱ケミカル株式会社
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Priority to JP2020531355A priority Critical patent/JP7435445B2/en
Priority to CN201980042006.6A priority patent/CN112313579A/en
Priority to KR1020207037264A priority patent/KR102706032B1/en
Publication of WO2020017576A1 publication Critical patent/WO2020017576A1/en

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    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/17—Passive-matrix OLED displays

Definitions

  • the present invention relates to a photosensitive colored resin composition, and more particularly, to a cured product obtained by curing the photosensitive colored resin composition, and an image display device and an illumination including the cured product.
  • an organic electroluminescent element included in an organic electric field display or an organic electric field lighting is formed by forming a partition (bank) on a substrate and then laminating various functional layers in a region surrounded by the partition. Being manufactured.
  • a method for easily forming such a partition a method for forming the partition by a photolithography method using a photosensitive resin composition is known.
  • an ink containing a material constituting the functional layer is prepared, and then the prepared ink is placed in a region surrounded by the partition (pixel region).
  • a method for injecting into is known.
  • an ink-jet method is often employed because a predetermined amount of ink can be accurately injected into a predetermined location.
  • Patent Document 1 discloses a partition having both a fine line pattern and a fine contact hole by using a negative photosensitive resin composition containing two specific alkali-soluble resins and having a solid content acid value of a specific range.
  • Patent Document 2 discloses that by using a negative photosensitive resin composition containing a specific ink repellent agent and a specific photopolymerization initiator, the ink repellency is improved even in the mirror projection (MPA) method, and the mask line is improved. It describes that the reproduction of the width is good.
  • the present inventors have studied and found that it is difficult to achieve both high ink repellency and a good tapered shape in a thick-film partition wall in the photosensitive colored resin composition described in Patent Document 1. Was done. On the other hand, with the photosensitive colored resin composition described in Patent Document 2, it has been found that the surface of the coating film is excessively hardened as compared with the lower portion of the coating film, and does not have a vertical tapered shape.
  • the present invention has been made in view of the above circumstances, that is, to provide a photosensitive colored resin composition which has high ink repellency and is capable of forming a partition having a good tapered shape.
  • the purpose is to:
  • Another object of the present invention is to provide a cured product obtained by curing the photosensitive colored resin composition, an image display device including the cured product, and illumination.
  • the gist of the present invention is as follows.
  • a photosensitive colored resin composition containing (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent. , (A) an oxime ester-based photopolymerization initiator (A1), wherein the photopolymerization initiator has an absorbance at a wavelength of 400 nm of 20% or more with respect to the absorbance at a maximum absorption wavelength ( ⁇ max ) of 300 to 400 nm.
  • An oxime ester-based photopolymerization initiator (A2) whose absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm, (E)
  • the photosensitive colored resin composition, wherein the liquid repellent comprises a fluorine atom-containing resin having a crosslinking group.
  • the oxime ester-based photopolymerization initiator (A2) contains a compound represented by the following general formula (A2-1).
  • R 13A represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 14A represents an alkyl group or an aromatic ring group.
  • R 15A represents a monovalent substituent.
  • n represents 0 or 1.
  • h represents an integer of 0 to 2.
  • a photosensitive colored resin composition containing (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent.
  • the oxime ester-based photopolymerization initiator (A3) wherein the photopolymerization initiator (A) has an absorbance at a wavelength of 400 nm of 8 to 30% of an absorbance at a maximum absorption wavelength ( ⁇ max ) of 300 to 400 nm.
  • the colorant (D) contains at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and purple pigments, [1] to The photosensitive colored resin composition according to any one of [6].
  • the colorant (D) is selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound.
  • the photosensitive colored resin composition according to any one of [1] to [7], comprising an organic black pigment containing at least one kind.
  • R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • FIG. 1 is an explanatory diagram of the evaluation of the perpendicularity of the taper of the linear pattern.
  • (meth) acryl means “one or both of acryl and methacryl”
  • total solid content means a solvent in the photosensitive colored resin composition. Means all components other than.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • the “(co) polymer” means including both a homopolymer and a copolymer, and further includes “(acid) anhydride”, “ (Anhydrous) ... acid "means to include both an acid and its anhydride.
  • the partition material means a bank material, a wall material, and a wall material, and similarly, the partition material means a bank, a wall, and a wall.
  • the weight average molecular weight means a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
  • the acid value represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
  • the partition is, for example, for partitioning a functional layer (organic layer) in an active drive type organic electroluminescent element, and is a material for forming the functional layer in a partitioned region (pixel region). It is used to form pixels comprising a functional layer and partition walls by discharging and drying a certain ink.
  • Photosensitive colored resin composition comprises (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) It may contain a liquid repellent as an essential component, and may further contain other components as necessary, for example, may contain a solvent or the like.
  • the photosensitive colored resin composition according to the first aspect of the present invention comprises (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E).
  • % Of an oxime ester-based photopolymerization initiator (A1) and an oxime ester-based photopolymerization wherein the absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm. It contains an initiator (A2), and the liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.
  • the photosensitive colored resin composition according to the second aspect of the present invention comprises (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E).
  • a photosensitive colored resin composition containing a liquid-repellent agent wherein the (A) photopolymerization initiator has an absorbance at a wavelength of 400 nm of 8 to an absorbance at a maximum absorption wavelength ( ⁇ max ) of 300 to 400 nm. It contains an oxime ester-based photopolymerization initiator (A3) in an amount of up to 30%, and the liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.
  • the “photosensitive colored resin composition of the present invention” includes both the photosensitive colored resin composition according to the first aspect and the photosensitive colored resin composition according to the second aspect. Point to.
  • the photosensitive colored resin composition of the present invention contains (A) a photopolymerization initiator.
  • the photopolymerization initiator (A) is not particularly limited as long as it is a compound that polymerizes the photopolymerizable compound (C) with actinic rays, for example, a compound that polymerizes the ethylenically unsaturated bond of the photopolymerizable compound (C).
  • the photopolymerization initiator (A) in the photosensitive colored resin composition according to the first embodiment of the present invention has an absorbance at a wavelength of 400 nm which is 20 times the absorbance at the maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm.
  • % Of the oxime ester-based photopolymerization initiator (A1) (hereinafter sometimes abbreviated as “oxime ester-based photopolymerization initiator (A1)”) at a wavelength of 400 nm between 300 and 400 nm.
  • oxime ester-based photopolymerization initiator (A2) (hereinafter, may be abbreviated as “oxime ester-based photopolymerization initiator (A2)”) having an absorbance of 10% or less with respect to the absorbance at the maximum absorption wavelength ( ⁇ max ). ).
  • oxime ester-based photopolymerization initiators having an absorption band at i-line those which can also use h-line, that is, oxime ester-based light having sufficiently high absorbance at a wavelength of 400 nm
  • a method using a polymerization initiator (A1) is exemplified.
  • the oxime ester-based photopolymerization initiator (A1) When the oxime ester-based photopolymerization initiator (A1) is used alone, although the ink repellency increases due to the improvement in the curability at the top of the coating film, most of the h-rays start the oxime ester-based photopolymerization at the top of the coating film.
  • the h-line that is absorbed by the agent (A1) and reaches the lower part of the coating film is reduced, the pattern width of the lower part of the coating film becomes narrower than that of the upper part of the coating film, and the perpendicularity of the taper on the side wall of the partition is further impaired.
  • the h in the upper part of the coating film is higher than when the oxime ester-based photopolymerization initiator (A1) is used alone.
  • the line absorptivity can be relatively lowered, that is, h-line can be transmitted to the lower part of the coating film, and curing using h-line near the glass substrate is promoted by the oxime ester-based photopolymerization initiator (A1). It is considered that the verticality of the taper on the side wall of the partition is improved.
  • Oxime ester photopolymerization initiator (A1) The oxime ester-based photopolymerization initiator (A1) has an absorption maximum at a wavelength of 300 to 400 nm, and the absorbance at a wavelength of 400 nm is higher than the absorbance at a maximum absorption wavelength ( ⁇ max ) of 300 to 400 nm. 20% or more. As described above, the oxime ester-based photopolymerization initiator (A1) has a sufficient absorbance at a wavelength of 400 nm, and is cured by sufficiently utilizing not only the i-line but also the h-line among the ultraviolet rays emitted from the high-pressure mercury lamp. It is believed that the reaction can be accelerated.
  • the absorbance of the oxime ester-based photopolymerization initiator (A1) at a wavelength of 400 nm is not particularly limited as long as it is 20% or more with respect to the absorbance at a maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm, but 25% or more. It is preferably at least 30%, more preferably at least 32%, still more preferably at least 35%, particularly preferably at least 40%, preferably at most 80%, more preferably at most 70%, and at most 60%. More preferably, it is still more preferably 50% or less, particularly preferably 40% or less.
  • the absorbance of the oxime ester-based photopolymerization initiator (A1) at a wavelength of 400 nm is preferably from 20 to 80%, more preferably from 25 to 70%, with respect to the absorbance at a maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm.
  • ⁇ max maximum absorption wavelength
  • it is more preferably from 30 to 60%, still more preferably from 30 to 50%, particularly preferably from 32 to 40%.
  • the maximum absorption wavelength ( ⁇ max ) of the oxime ester-based photopolymerization initiator (A1) between 300 and 400 nm is not particularly limited, but is preferably 320 nm or more, more preferably 340 nm or more, still more preferably 360 nm or more. 390 nm or less, more preferably 380 nm or less, and particularly preferably 370 nm or less.
  • the amount is not less than the lower limit, the ink repellency tends to be high, and when the amount is not more than the upper limit, the tapered shape of the side wall of the partition tends to be good.
  • the maximum absorption wavelength ( ⁇ max ) of the oxime ester-based photopolymerization initiator (A1) between 300 and 400 nm is preferably from 320 to 390 nm, more preferably from 340 to 380 nm, and still more preferably from 360 to 370 nm.
  • the measurement of the absorbance and the maximum absorption wavelength of the oxime ester-based photopolymerization initiator (A1) was performed by first preparing a 0.01% by mass PGMEA (propylene glycol monomethyl ether acetate) solution of the oxime ester-based photopolymerization initiator (A1). It can be obtained by irradiating it with light having a wavelength of 300 to 400 nm with a spectrophotometer, and measuring the light every 1 nm.
  • the spectrophotometer include, but are not limited to, UV-3000 series (manufactured by Shimadzu Corporation) and V-700 series (manufactured by JASCO Corporation).
  • As the measurement cell a 1 cm square quartz cell can be used.
  • the oxime ester-based photopolymerization initiator (A1) has an absorbance at a wavelength of 400 nm of at least 20% of the absorbance at a maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm, but has a high absorbance at a wavelength of 400 nm.
  • Examples thereof include those having an electron-withdrawing group such as a nitro group bonded to a fluorene skeleton or a carbazole skeleton, and an oxime ester-based photopolymerization initiator having a nitro group and a carbazole skeleton is preferable.
  • the chemical structure of the oxime ester-based photopolymerization initiator (A1) is not particularly limited, but may be a compound having a chemical structure represented by the following general formula (A1-1) from the viewpoint of ink repellency and tapered shape. preferable.
  • R 1A , R 3A , R 4A , R 5A , R 6A and R 8A each independently represent a hydrogen atom, a nitro group, an alkyl group, or an aromatic ring group.
  • R 2A and R 7A are each independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, a nitro group, or a compound represented by the following general formula (A1-2)
  • R 2A and R 7A are a monovalent group represented by the following general formula (A1-2).
  • At least one of R 1A to R 8A is a nitro group.
  • R 9A represents a hydrogen atom or an alkyl group.
  • m and n each independently represent 0 or 1.
  • R 11A represents an alkyl group or an aromatic ring group.
  • R 12A represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • the alkyl group represented by R 1A , R 3A , R 4A , R 5A , R 6A and R 8A in the above formula (A1-1) may be a straight-chain, branched-chain, or cyclic-alkyl group. There may be.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 8 or less, more preferably 6 or less.
  • the alkyl group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, from the viewpoint of ink repellency, a methyl group, It is preferably an ethyl group or a propyl group, and more preferably a methyl group.
  • Examples of the aromatic ring group represented by R 1A , R 3A , R 4A , R 5A , R 6A and R 8A in the formula (A1-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is not particularly limited, it is usually 4 or more, preferably 6 or more, more preferably 20 or less, and more preferably 12 or less.
  • the aromatic ring group preferably has 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms.
  • aromatic ring group examples include a phenyl group, a naphthyl group, an anthracenyl group, a thienyl group, a furyl group, a benzothienyl group, and a benzofuryl group.
  • a phenyl group is preferred from the viewpoint of ink repellency. Is more preferable.
  • R 1A , R 3A , R 4A , R 5A , R 6A and R 8A are each independently preferably a hydrogen atom or a nitro group, and more preferably a hydrogen atom. preferable.
  • the alkyl group for R 2A and R 7A in the above formula (A1-1) may be linear, branched, cyclic, or a combination thereof.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 8 or less, more preferably 6 or less.
  • the alkyl group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, from the viewpoint of ink repellency, a methyl group, It is preferably an ethyl group or a propyl group, and more preferably a methyl group.
  • the substituent which the alkyl group may have include a hydroxyl group and a carboxyl group, and a hydroxyl group is preferable from the viewpoint of developability.
  • Examples of the aromatic ring group for R 2A and R 7A in the formula (A1-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is not particularly limited, but is usually 4 or more, preferably 6 or more, more preferably 10 or more, and preferably 20 or less, more preferably 12 or less.
  • the aromatic ring group preferably has 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms.
  • aromatic ring group examples include a phenyl group, a naphthyl group, an anthracenyl group, a thienyl group, a furyl group, a benzothienyl group and a benzofuryl group.
  • a phenyl group and a naphthyl group are more preferable from the viewpoint of ink repellency.
  • substituent which the aromatic ring group may have include a hydroxyl group and an alkyl group, and an alkyl group is preferable from the viewpoint of developability.
  • R 2A and R 7A is a monovalent group represented by the general formula (A1-2).
  • the alkyl group for R 11A in the formula (A1-2) may be linear, branched, cyclic, or a combination thereof.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 5 or less, more preferably 3 or less. When the content is not more than the upper limit, the sensitivity tends to be good.
  • the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a pentyl group. Among them, a methyl group is preferable from the viewpoint of ink repellency.
  • Examples of the aromatic ring group for R 11A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.
  • the solubility in a solvent tends to be good
  • the tapered shape tends to be good.
  • the number of carbon atoms in the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, and even more preferably 5 to 12.
  • aromatic ring group examples include a phenyl group, a naphthyl group, a thienyl group, a furyl group, and the like. Among them, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of a tapered shape.
  • R 11A is preferably an alkyl group, more preferably a methyl group, from the viewpoint of ink repellency.
  • the alkyl group for R 12A may be linear, branched, cyclic, or a combination thereof.
  • the carbon number of the alkyl group is not particularly limited, but is usually 1 or more, preferably 3 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and more preferably 10 or less. It is still more preferably 8 or less, further preferably 7 or less.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 3 to 15, more preferably 5 to 10, still more preferably 5 to 8, and particularly preferably 5 to 7.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, a cyclopentyl group, and a cyclohexyl group.
  • An isopentyl group, a hexyl group, and a heptyl group are preferable, and a heptyl group is more preferable.
  • Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, and the like. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • Examples of the aromatic ring group for R 12A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more. Further, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less. When the content is not less than the lower limit, solubility in a solvent tends to be good, and when the content is not more than the upper limit, developability tends to be good.
  • the number of carbon atoms in the aromatic ring group is preferably from 4 to 30, more preferably from 4 to 20, still more preferably from 4 to 12, and even more preferably from 5 to 12.
  • aromatic ring group examples include a phenyl group, a naphthyl group, a thienyl group, and a furyl group. Of these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of developability.
  • substituent which the aromatic ring group may have include a hydroxyl group, an alkyl group, an alkoxy group, an alkoxy group substituted with an alkoxy group, an alkoxy group substituted with a hydroxyl group, and the like.
  • an alkoxy group substituted with an alkyl group or an alkoxy group, or an alkoxy group substituted with a hydroxyl group is preferable from the viewpoint of developability.
  • the alkyl group in the substituent which the aromatic ring group may have include alkyl having 1 to 6 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, and more preferably alkyl having 1 to 3 carbon atoms. And methyl are particularly preferred.
  • the alkoxy group in the substituent which the aromatic ring group optionally has and the alkoxy group which is substituted on the alkoxy group in the substituent which the aromatic ring group may have may be an alkoxy group having 1 to 8 carbon atoms.
  • the alkoxy having 1 to 6 carbon atoms is preferable, and the alkoxy having 1 to 4 carbon atoms is more preferable.
  • m and n each independently represent 0 or 1, but 0 is preferable from the viewpoint of the contact angle, and 1 is preferable from the viewpoint of the tapered shape.
  • R 2A and R 7A are each independently a nitro group or a monovalent group represented by formula (A1-2), and R 2A is a nitro group. And R 7A is more preferably a monovalent group represented by the general formula (A1-2).
  • R 1A to R 8A At least one of R 1A to R 8A is a nitro group.
  • the number of nitro groups among R 1A to R 8A is not particularly limited, but is usually 1 or more, preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less. When the content is not more than the upper limit, the developability tends to be good.
  • the number of nitro groups is preferably from 1 to 4, more preferably from 1 to 3, and even more preferably from 1 to 2.
  • R 2A or R 7A is a nitro group from the viewpoint of ink repellency.
  • R 4A and R 5A is a nitro group, more preferably R 4A and R 5A is a nitro group.
  • the alkyl group for R 9A in the above formula (A1-1) may be linear, branched, cyclic, or a combination thereof.
  • the carbon number of the alkyl group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less.
  • the carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 2 to 6.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, from the viewpoint of ink repellency, a methyl group, It is preferably an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and further preferably an ethyl group.
  • oxime ester-based photopolymerization initiators (A1) compounds having a chemical structure represented by the formula (A1-11) are preferable from the viewpoint of the tapered shape.
  • Oxime ester photopolymerization initiator (A2) The oxime ester-based photopolymerization initiator (A2) has an absorption maximum at a wavelength of 300 to 400 nm, and the absorbance at a wavelength of 400 nm is higher than the absorbance at a maximum absorption wavelength ( ⁇ max ) of 300 to 400 nm. 10% or less. As described above, the oxime ester-based photopolymerization initiator (A2) has a sufficiently low absorbance at a wavelength of 400 nm, and is hardened mainly by using i-line among ultraviolet rays emitted from a high-pressure mercury lamp without using h-line so much.
  • the absorption rate of h-rays in the upper part of the coating film can be reduced, the h-rays can be transmitted to the vicinity of the glass substrate in the lower part of the coating film, and coating using an oxime ester-based photopolymerization initiator (A1) can be performed. It is considered that the curing at the lower part of the film can be promoted, and the perpendicularity of the obtained pattern is improved.
  • the absorbance of the oxime ester-based photopolymerization initiator (A2) at a wavelength of 400 nm is not particularly limited as long as it is 10% or less with respect to the absorbance at a maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm, but is preferably 5% or less. It is preferably 3% or less, more preferably 1% or less, further preferably 0.01% or more, more preferably 0.05% or more, still more preferably 0.1% or more, and more preferably 0.3% or more. Even more preferably, it is particularly preferably 0.5% or more.
  • the absorbance of the oxime ester-based photopolymerization initiator (A2) at a wavelength of 400 nm is preferably 0.01 to 10% with respect to the absorbance at a maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm, and is preferably 0.05 to 10%. 5% is more preferable, 0.1 to 3% is further preferable, 0.3 to 3% is still more preferable, and 0.5 to 1% is particularly preferable.
  • the maximum absorption wavelength ( ⁇ max ) of the oxime ester photopolymerization initiator (A2) between 300 and 400 nm is not particularly limited, but is preferably 310 nm or more, more preferably 320 nm or more, still more preferably 325 nm or more. , 350 nm or less, more preferably 340 nm or less, even more preferably 330 nm or less.
  • the curability at the i-line tends to be good
  • the tapered shape of the side wall of the partition tends to be good.
  • the maximum absorption wavelength ( ⁇ max ) of the oxime ester-based photopolymerization initiator (A2) between 300 and 400 nm is preferably 310 to 350 nm, more preferably 320 to 340 nm, and still more preferably 325 to 340 nm.
  • PGMEA propylene glycol monomethyl ether acetate
  • the oxime ester-based photopolymerization initiator (A2) has an absorbance at a wavelength of 400 nm of 10% or less of the absorbance at a maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm, but has a low absorbance at a wavelength of 400 nm.
  • Examples thereof include oxime ester-based photopolymerization initiators having no electron withdrawing group such as a nitro group in the skeleton of diphenyl sulfide, carbazole, fluorene, etc., for example, oxime ester-based initiators having no substituent in these skeletons
  • Examples thereof include photopolymerization initiators and oxime ester-based photopolymerization initiators having a substituent such as an arylcarbonyl group or an alkoxy group on their skeleton.
  • the chemical structure of the oxime ester-based photopolymerization initiator (A2) is not particularly limited, but preferably contains a compound represented by the following general formula (A2-1) from the viewpoint of a tapered shape.
  • R 13A represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 14A represents an alkyl group or an aromatic ring group.
  • R 15A represents a monovalent substituent.
  • n represents 0 or 1.
  • h represents an integer of 0 to 2.
  • the alkyl group for R 13A in the above formula (A2-1) may be linear, branched, cyclic, or a combination thereof.
  • the carbon number of the alkyl group is not particularly limited, it is usually 1 or more, preferably 4 or more, more preferably 6 or more, also preferably 20 or less, more preferably 10 or less, still more preferably 8 or less, and 7 or less. Even more preferred.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 7, and particularly preferably 4 to 7.
  • alkyl group examples include methyl, ethyl, propyl, butyl, pentyl, isopentyl, hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl
  • a methyl group, a hexyl group, an isopentyl group, a hexyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group are preferable, and a hexyl group and a cyclopentylmethyl group are more preferable.
  • alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, and the like. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • Examples of the aromatic ring group for R 13A in the above formula (A2-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is usually preferably 4 or more, 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.
  • the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 12, and particularly preferably 5 to 12.
  • aromatic ring group examples include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group.
  • a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable, from the viewpoint of developability.
  • substituent which the aromatic ring group may have include a hydroxyl group and an alkyl group, and an alkyl group is preferable from the viewpoint of developability.
  • R 13A is preferably an alkyl group which may have a substituent.
  • the alkyl group for R 14A in the above formula (A2-1) may be linear, branched, cyclic, or a combination thereof.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 5 or less, more preferably 3 or less. When the content is not more than the upper limit, the sensitivity tends to be good.
  • the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, and a pentyl group.
  • a methyl group is preferable from the viewpoint of a tapered shape.
  • Examples of the aromatic ring group for R 14A in the above formula (A2-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.
  • the solubility in the solvent tends to be good
  • the content is not more than the upper limit, the sensitivity tends to be good.
  • the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 12, and particularly preferably 5 to 12.
  • aromatic ring group examples include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and the like. Among them, from the viewpoint of a tapered shape, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • R 14A in the formula (A2-1) an aromatic ring group is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is more preferable, from the viewpoint of a contact angle.
  • a methyl group is preferable.
  • R 16A examples include an alkyl group which may have a substituent and an aromatic ring group which may have a substituent.
  • the alkyl group for R 16A may be linear, branched, cyclic, or a combination thereof.
  • the carbon number of the alkyl group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 8 or less, more preferably 5 or less.
  • the alkyl group preferably has 1 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, and a pentyl group. Among them, from the viewpoint of solubility, a methyl group and an ethyl group are preferable, and an ethyl group is more preferable.
  • substituent which the alkyl group may have include a hydroxyl group and a carboxyl group, and a hydroxyl group is preferable from the viewpoint of developability.
  • Examples of the aromatic ring group for R 16A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.
  • the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 12, and particularly preferably 5 to 12.
  • aromatic ring group examples include a phenyl group, a naphthyl group, a thienyl group, a furyl group, a benzothienyl group and a benzofuryl group.
  • a benzothienyl group or a benzofuryl group is preferable, and a benzofuryl group is more preferable.
  • substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, a carboxyl group, and the like.
  • R 16A is a hydroxyl-substituted ethyl group, R 16A —O—, and R 16A is a benzofuryl group.
  • n represents 0 or 1. It is preferable that n is 1 from the viewpoint of the tapered shape, while it is preferable that n is 0 from the viewpoint of sensitivity.
  • h represents an integer of 0 to 2. From the viewpoint of the tapered shape, h is preferably 0 or 1, and more preferably 0. When h is an integer of 1 or more, the substitution position of R 15A is not particularly limited, but the o-position or the p-position is preferable from the viewpoint of synthesis, and the p-position is more preferable.
  • compounds having the chemical structure represented by the formula (A2-19) are preferable from the viewpoint of the tapered shape.
  • a compound having the chemical structure represented by the formula (A2-17) or (A2-18) is preferable.
  • the photopolymerization initiator (A) in the photosensitive colored resin composition according to the first embodiment of the present invention is a photopolymerization initiator other than the oxime ester photopolymerization initiator (A1) and the oxime ester photopolymerization initiator (A2).
  • An initiator hereinafter, may be referred to as “other photopolymerization initiator”
  • the other photopolymerization initiator may be an oxime ester compound, or may be other than the oxime ester compound.
  • photopolymerization initiators those usually used in this field can be used.
  • metallocene compounds containing titanocene compounds described in JP-A-59-152396 and JP-A-61-151197 hexaarylbiimidazole derivatives described in JP-A-2000-56118 N-aryl- ⁇ -amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in Japanese Patent Application Laid-Open No. 10-39503, N-aryl- ⁇ - Radical activators such as amino acid salts, N-aryl- ⁇ -amino acid esters, and ⁇ -aminoalkylphenone derivatives.
  • dicyclopentadienyl titanium dichloride dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl ), Dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium di ( 2,6-difluorophenyl), dicyclopentadienyl titanium di (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), Di (methylcyclopentadienyl) titanium bis (2,6-difluoro Phenyl), dicyclopentadienyl titanium [2,6-di - fluoro-3- (pyr
  • biimidazole derivatives examples include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.
  • halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5- [ ⁇ - (2'- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2 ′-(6 ′′ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.
  • halomethyl-s-triazine derivatives examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) —S-triazine and the like.
  • Examples of the ⁇ -aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo Ethate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- ( 4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. And the like
  • photopolymerization initiators may be used alone or in combination of two or more.
  • Oxime ester photopolymerization initiator (A3) As described above, the photopolymerization initiator (A) in the photosensitive colored resin composition according to the second aspect of the present invention has an absorbance at a wavelength of 400 nm, an absorbance at a maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm.
  • Oxime ester-based photopolymerization initiator (A3) (hereinafter sometimes abbreviated as “oxime ester-based photopolymerization initiator (A3)”) in an amount of 8 to 30% based on the total amount of the oxime ester-based photopolymerization initiator (A3).
  • the liquid repellent By containing the oxime ester-based photopolymerization initiator (A3) in this manner, the liquid repellent can be fixed by curing using h-rays at the upper part of the coating film, and a certain amount of h-rays can be transmitted to the lower part of the coating film. It is considered that by doing so, the hardening utilizing the h-line near the glass substrate is promoted, and the perpendicularity of the taper on the side wall of the partition is improved.
  • the oxime ester-based photopolymerization initiator (A3) may be a single type or a mixture of two or more types.
  • the mixture is a mixture of two or more types, for example, when the mixture is an oxime ester-based photopolymerization initiator (A3-1) and an oxime ester-based photopolymerization initiator (A3-2), the oxime ester-based photopolymerization initiator is used.
  • the absorbance of the oxime ester-based photopolymerization initiator (A3-1) at a wavelength of 400 nm and the absorbance of the oxime ester-based photopolymerization initiator (A3-2) at a wavelength of 400 nm are measured.
  • the weighted average is calculated based on the content ratio (by mass) of the oxime ester-based photopolymerization initiator (A3-1) and the oxime ester-based photopolymerization initiator (A3-2) in the photosensitive colored resin composition. Can be calculated. The same applies to three or more types.
  • the absorbance of the oxime ester-based photopolymerization initiator (A3) at a wavelength of 400 nm is not particularly limited as long as it is 8 to 30% of the absorbance at a maximum absorption wavelength ( ⁇ max ) of 300 to 400 nm, but is 10% or more. Is preferably 15% or more, more preferably 20% or more, even more preferably 23% or more, and preferably 28% or less, more preferably 27% or less, and even more preferably 26% or less. When the amount is not less than the lower limit, the ink repellency tends to be high, and when the amount is not more than the upper limit, the tapered shape of the side wall of the partition tends to be good.
  • the absorbance of the oxime ester-based photopolymerization initiator (A3) at a wavelength of 400 nm is preferably from 8 to 28%, more preferably from 10 to 28%, relative to the absorbance at the maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm.
  • ⁇ max maximum absorption wavelength
  • it is more preferably from 15 to 28%, further preferably from 20 to 27%, particularly preferably from 23 to 26%.
  • the photopolymerization initiator (A) in the photosensitive colored resin composition according to the second aspect of the present invention may contain a photopolymerization initiator other than the oxime ester-based photopolymerization initiator.
  • a photopolymerization initiator other than the oxime ester-based photopolymerization initiator include those described above as other photopolymerization initiators.
  • the photopolymerization initiator in the photosensitive colored resin composition of the present invention may be blended with a sensitizing dye according to the wavelength of the image exposure light source, a polymerization accelerator.
  • a sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, and JP-A-5-289335.
  • sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone , Benzophenone-based compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminobenz
  • polymerization accelerator examples include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, and aliphatic amines such as n-butylamine and N-methyldiethanolamine.
  • aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate
  • aliphatic amines such as n-butylamine and N-methyldiethanolamine.
  • One type of polymerization accelerator may be used alone, or two or more types may be used in combination.
  • chain transfer agent include a mercapto group-containing compound and carbon tetrachloride. It is more preferable to use a mercapto group-containing compound because the chain transfer effect tends to be high. This is considered to be because bond breaking is likely to occur due to a small SH bond energy, and a hydrogen abstraction reaction and a chain transfer reaction are likely to occur
  • a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are preferable, and an aliphatic mercapto group-containing compound is more preferable.
  • the mercapto group-containing compound having an aromatic ring include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -Quinazoline, ⁇ -mercaptonaphthalene, 1,4-dimethylmercaptobenzene and the like, and from the viewpoint of high sensitivity, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred.
  • Aliphatic mercapto group-containing compounds include hexanedithiol, decanedithiol, butanediol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis (3-mercaptopropionate), ethylene Glycol bisthioglycolate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol Tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane Squirrel (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercapto
  • trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) 3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, more preferably pentane Erythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferred.
  • the chain transfer agent may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (A) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 0.1% by mass or more, preferably 1% by mass, in the total solid content of the photosensitive colored resin composition. % By mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. It is. When the content is equal to or more than the lower limit, sufficient ink repellency tends to be generated, and when the content is equal to or less than the upper limit, developability tends to be improved.
  • the content of the photopolymerization initiator (A) in the total solid content of the photosensitive colored resin composition is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, and more preferably 2 to 8% by mass. Further preferred is 3 to 5% by mass.
  • the content of the oxime ester-based photopolymerization initiator (A1) in the photopolymerization initiator (A) is not particularly limited, but is usually 20% by mass or more. Is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, still more preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 70% by mass or more. . Further, it is usually at most 90 mass%, preferably at most 85 mass%, more preferably at most 80 mass%.
  • the content of the oxime ester-based photopolymerization initiator (A1) in the photopolymerization initiator (A) is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and still more preferably 60 to 85% by mass. , 70 to 80% by mass is particularly preferred.
  • the content ratio of the oxime ester-based photopolymerization initiator (A2) in the photopolymerization initiator is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. , 20% by mass or more is more preferable. Further, it is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the content is not less than the lower limit, the tapered shape tends to be good, and when the content is not more than the upper limit, sufficient ink repellency tends to be generated.
  • the content of the oxime ester-based photopolymerization initiator (A2) in the photopolymerization initiator (A) is preferably from 5 to 70% by mass, more preferably from 5 to 60% by mass, and still more preferably from 10 to 50% by mass. , 15 to 40% by mass is more preferable, and 20 to 30% by mass is particularly preferable.
  • the content ratio of the oxime ester-based photopolymerization initiator (A2) is usually 10 parts by mass or more, preferably 20 parts by mass or more, and more preferably 25 parts by mass with respect to 100 parts by mass of the oxime ester-based photopolymerization initiator (A1). More preferably, the amount is 30 parts by mass or more. Further, it is usually 70 parts by mass or less, preferably 60 parts by mass or less, more preferably 55 parts by mass or less, still more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, and particularly preferably 40 parts by mass or less.
  • the content ratio of the oxime ester-based photopolymerization initiator (A2) to 100 parts by mass of the oxime ester-based photopolymerization initiator (A1) is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, and more preferably 20 to 60% by mass.
  • the content is more preferably 55% by mass, further preferably 20 to 50% by mass, particularly preferably 25 to 45% by mass, and particularly preferably 30 to 40% by mass.
  • the content of the oxime ester-based photopolymerization initiator (A3) in the total solid content is not particularly limited, but is usually 0.1% by mass or more. Is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. Further, it is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. When the amount is equal to or more than the lower limit, sufficient ink repellency tends to occur, and when the amount is equal to or less than the upper limit, the taper shape tends to be good.
  • the content of the oxime ester-based photopolymerization initiator (A3) in the total solid content of the photosensitive colored resin composition is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, and 2 to 8% by mass. % By mass is more preferable, and 3 to 5% by mass is particularly preferable.
  • the mixing ratio of the (A) photopolymerization initiator to the (C) photopolymerizable compound in the photosensitive colored resin composition of the present invention is not particularly limited. Is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 12 parts by mass or more, particularly preferably 15 parts by mass or more, and further preferably 200 parts by mass or less, The amount is more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less.
  • the mixing ratio of the photopolymerization initiator (A) to 100 parts by mass of the photopolymerizable compound (C) is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, and still more preferably 10 to 50 parts by mass.
  • the content is more preferably from 12 to 30 parts by mass, particularly preferably from 15 to 20 parts by mass.
  • the content thereof is not particularly limited, but is usually 0.01% by mass or more, preferably 0% by mass, in the total solid content of the photosensitive colored resin composition. 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, furthermore It is preferably at most 2% by mass.
  • the ratio is equal to or higher than the lower limit, the sensitivity tends to increase, and when the ratio is equal to or lower than the upper limit, a desired pattern tends to be easily formed.
  • the content ratio of the chain transfer agent in the total solid content of the photosensitive colored resin composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass. , 0.5 to 3% by mass, and particularly preferably 0.8 to 2% by mass.
  • the content ratio of the chain transfer agent to the photopolymerization initiator (A) in the photosensitive colored resin composition is not particularly limited, but is preferably 5 parts by mass or more based on 100 parts by mass of the photopolymerization initiator (A). 10 parts by mass or more, more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, even more preferably 100 parts by mass or less, Particularly preferred is 50 parts by mass or less.
  • the ratio is equal to or higher than the lower limit, the sensitivity tends to be high, and when the ratio is lower than the upper limit, a desired pattern tends to be easily formed.
  • the content ratio of the chain transfer agent to 100 parts by mass of the photopolymerization initiator (A) is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, and 15 to 100 parts by mass. Part by mass is more preferable, and 20 to 50 parts by mass is particularly preferable.
  • the photosensitive colored resin composition of the present invention contains (B) an alkali-soluble resin.
  • the alkali-soluble resin (B) is not particularly limited as long as it can be developed with an alkali developer.
  • the alkali-soluble resin include various resins having a carboxyl group or a hydroxyl group, and those having a carboxyl group are preferable from the viewpoint of excellent developability.
  • the alkali-soluble resin having an ethylenically unsaturated group is preferable because the verticality of the side wall of the partition wall is improved, and the outflow of the liquid repellent agent due to the thermal melting of the partition wall is suppressed and the ink repellency is easily maintained. .
  • the (B) alkali-soluble resin of the photosensitive colored resin composition of the present invention is preferably an acrylic copolymer resin (B11) having an ethylenically unsaturated group in a side chain (hereinafter referred to as an “acryl copolymer resin”) from the viewpoint of ink repellency. (B11) ").
  • an epoxy (meth) acrylate resin (B12) it is preferable to include an epoxy (meth) acrylate resin (B12).
  • the alkali-soluble resin (B) contains both an acrylic copolymer resin (B11) and an epoxy (meth) acrylate resin (B12).
  • the acrylic copolymer resin (B11) has an ethylenically unsaturated group in a side chain. It is considered that by having an ethylenically unsaturated group, photo-curing by exposure occurs to form a stronger film, and the liquid-repellent agent hardly flows out during development.
  • the partial structure of the acrylic copolymer resin (B11), including the side chain having an ethylenically unsaturated group, is not particularly limited. From the viewpoint of the ease with which radicals are released due to the flexibility of the film, for example, the following general formula: It preferably has a partial structure represented by (I).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group. * Represents a bond
  • the partial structure represented by the following general formula (I ′) is preferable from the viewpoint of sensitivity and alkali developability.
  • R 1 and R 2 are each independently, .R X represents a hydrogen atom or a methyl group represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endmethylenetetrahydrophthalic acid One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Is tetrahydrophthalic acid or biphenyltetracarboxylic acid.
  • the content ratio is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). 10 mol% or more is preferable, 20 mol% or more is more preferable, 30 mol% or more is further preferable, 40 mol% or more is still more preferable, 50 mol% or more is particularly preferable, and 90 mol% or less is preferable, and 85 mol% or less is preferable. Mol% or less, more preferably 80 mol% or less, even more preferably 75 mol% or less, and particularly preferably 70 mol% or less.
  • the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (I), for example, the content ratio of the partial structure represented by the general formula (I) is preferably 10 to 90 mol%, It is more preferably from 20 to 85 mol%, further preferably from 30 to 80 mol%, further preferably from 40 to 75 mol%, particularly preferably from 50 to 70 mol%.
  • the content thereof is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). Is preferably at least 10 mol%, more preferably at least 20 mol%, still more preferably at least 25 mol%, even more preferably at least 30 mol%, particularly preferably at least 35 mol%, and preferably at most 80 mol%, It is more preferably at most 75 mol%, further preferably at most 70 mol%, particularly preferably at most 65 mol%.
  • the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (I ′), for example, the content ratio of the partial structure represented by the general formula (I ′) is 10 to 80 mol%. Preferably, it is 20 to 80 mol%, more preferably 25 to 75 mol%, still more preferably 30 to 70 mol%, and particularly preferably 35 to 65 mol%.
  • the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (I)
  • the other partial structure is not particularly limited, but from the viewpoint of development adhesion, for example, the following general formula (II) ) Is also preferable.
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent.
  • R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.
  • alkyl group for R 4 include a linear, branched or cyclic alkyl group.
  • the carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, It is more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 3 to 18, more preferably 5 to 16, still more preferably 8 to 14, and particularly preferably 8 to 12.
  • the alkyl group examples include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group.
  • a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
  • the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group.
  • an acryloyl group and a methacryloyl group From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • Examples of the aromatic ring group for R 4 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the number of carbon atoms is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less.
  • the aromatic ring group preferably has 6 to 24 carbon atoms, more preferably has 6 to 22 carbon atoms, further preferably has 6 to 20 carbon atoms, and particularly preferably has 6 to 18 carbon atoms.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene Ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroleimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, flopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benziso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, tri
  • a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable.
  • the substituent which the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, and an epoxy group.
  • an oligoethylene glycol group, a phenyl group, a carboxyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • Examples of the alkenyl group for R 4 include a linear, branched or cyclic alkenyl group.
  • the number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less, and 14 or less Is particularly preferred.
  • the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, and particularly preferably 2 to 14.
  • Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • R 4 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. From the viewpoints of developability and film strength, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.
  • the content thereof is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). 1 mol% or more is preferable, 5 mol% or more is more preferable, 10 mol% or more is more preferable, 20 mol% or more is particularly preferable, and 70 mol% or less is preferable, 60 mol% or less is more preferable, and 50 mol% or less is used. % Or less, more preferably 40 mol% or less.
  • the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced.
  • the content ratio of the partial structure represented by the general formula (II) is preferably 1 to 70 mol%, 5 to 60 mol% is more preferable, 10 to 50 mol% is further preferable, and 20 to 40 mol% is particularly preferable.
  • the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (I)
  • the other partial structure is represented by the following general formula (III) from the viewpoint of heat resistance and film strength.
  • a partial structure is included.
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent.
  • t represents an integer of 0 to 5.
  • R 6 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, and a carboxyl group.
  • Examples of the alkyl group for R 6 include a linear, branched or cyclic alkyl group.
  • the carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, It is still more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
  • the carbon number of the alkyl group is preferably 1 to 20, more preferably 3 to 18, still more preferably 5 to 16, still more preferably 5 to 14, and particularly preferably 5 to 12.
  • alkyl group examples include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group.
  • a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
  • Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And an acryloyl group and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • Examples of the alkenyl group for R 6 include a linear, branched or cyclic alkenyl group.
  • the number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less, and 14 or less Is particularly preferred.
  • the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, and particularly preferably 2 to 14.
  • Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • Examples of the alkynyl group for R 6 include a linear, branched or cyclic alkynyl group.
  • the number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less, and 14 or less Is particularly preferred.
  • the carbon number of the alkynyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, and particularly preferably 2 to 14.
  • Examples of the substituent which the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • halogen atom for R 6 examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom is preferred from the viewpoint of ink repellency.
  • Examples of the alkoxy group for R 6 include a linear, branched or cyclic alkoxy group.
  • the carbon number is 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less, and 12 or less. Is particularly preferred.
  • the carbon number of the alkoxy group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, and particularly preferably 1 to 12.
  • Examples of the substituent which the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And an acryloyl group and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • Examples of the alkyl sulfide group for R 6 include a linear, branched or cyclic alkyl sulfide group.
  • the carbon number is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and even more preferably 14 or less. , 12 or less is particularly preferable.
  • the carbon number of the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, and particularly preferably 1 to 12.
  • Examples of the substituent which the alkyl group in the alkyl sulfide group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, and a phenyl group.
  • Groups, a carboxyl group, an acryloyl group, a methacryloyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • R 6 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, and a halogen atom.
  • t represents an integer of 0 to 5, but from the viewpoint of ease of production, it is preferable that t is 0.
  • the content ratio is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). It is preferably at least 0.5 mol%, more preferably at least 1 mol%, even more preferably at least 2 mol%. Further, it is preferably at most 50 mol%, more preferably at most 30 mol%, further preferably at most 20 mol%, still more preferably at most 10 mol%, particularly preferably at most 5 mol%.
  • the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced.
  • the content ratio of the partial structure represented by the general formula (III) is 0.5 to 50 mol%.
  • it is 0.5 to 30 mol%, more preferably 1 to 20 mol%, still more preferably 1 to 10 mol%, and particularly preferably 2 to 5 mol%.
  • R 7 represents a hydrogen atom or a methyl group.
  • the content ratio is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). 5 mol% or more is preferable, 10 mol% or more is more preferable, 20 mol% or more is more preferable, and 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60 mol% or less is further preferable.
  • the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the development adhesion tends to be improved.
  • the content ratio of the partial structure represented by the general formula (IV) is preferably 5 to 80 mol%, The content is more preferably from 10 to 70 mol%, even more preferably from 20 to 60 mol%.
  • the acid value of the acrylic copolymer resin (B11) is not particularly limited, but is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, still more preferably 50 mgKOH / g or more, and still more preferably 60 mgKOH / g or more. Also, it is preferably 150 mgKOH / g or less, more preferably 140 mgKOH / g or less, still more preferably 130 mgKOH / g or less, and still more preferably 120 mgKOH / g or less. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the development adhesion tends to be improved.
  • the acid value of the acrylic copolymer resin (B11) is preferably 30 to 150 mgKOH / g, more preferably 40 to 140 mgKOH / g, further preferably 50 to 130 mgKOH / g, and particularly preferably 60 to 120 mgKOH / g.
  • the weight average molecular weight (Mw) of the acrylic copolymer resin (B11) is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 4,000 or more, further preferably 6,000 or more, more preferably 7000 or more, and particularly preferably. Is 8000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and further preferably 10,000 or less. When the amount is not less than the lower limit, the adhesiveness for development tends to be improved, and when the amount is not more than the upper limit, the residue tends to be reduced.
  • the weight average molecular weight (Mw) of the acrylic copolymer resin (B11) is preferably from 1,000 to 30,000, more preferably from 2,000 to 20,000, still more preferably from 4,000 to 15,000, still more preferably from 6,000 to 15,000, particularly preferably from 7000 to 10,000.
  • Mw weight average molecular weight
  • 8,000 to 10,000 are particularly preferred.
  • the content ratio of the acrylic copolymer resin (B11) contained in the alkali-soluble resin is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and 70% by mass. %, Particularly preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less.
  • the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced.
  • the content of the acrylic copolymer resin (B11) in the alkali-soluble resin (B) is preferably from 10 to 95% by mass, more preferably from 30 to 95% by mass, still more preferably from 50 to 90% by mass, and preferably from 70 to 90% by mass. 85% by weight is particularly preferred.
  • the alkali-soluble resin contains both the acrylic copolymer resin (B11) and the epoxy (meth) acrylate resin (B12), the content of the acrylic copolymer resin (B11) is ) and the total content of the epoxy (meth) acrylate resin (B12) is preferably at least 10% by mass, more preferably at least 30% by mass, further preferably at least 50% by mass, particularly preferably at least 70% by mass. It is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less.
  • the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced.
  • the alkali-soluble resin contains both the acrylic copolymer resin (B11) and the epoxy (meth) acrylate resin (B12), the acrylic copolymer resin (B11) and the epoxy (meth) acrylate resin (B12) are contained.
  • the content of the acrylic copolymer resin (B11) with respect to the total of the proportions is preferably from 10 to 95% by mass, more preferably from 30 to 95% by mass, further preferably from 50 to 90% by mass, and particularly preferably from 70 to 85% by mass. .
  • acrylic copolymer resin (B11) examples include, for example, the resins described in Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.
  • Epoxy (meth) acrylate resin (B12) The epoxy (meth) acrylate resin (B12) is obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin, optionally reacting an isocyanate group-containing compound, and further reacting with a polybasic acid or an anhydride thereof. It is the resin which was made to be. For example, a carboxyl group of an unsaturated monocarboxylic acid is ring-opened to an epoxy group of an epoxy resin, whereby an ethylenically unsaturated bond is added to an epoxy compound via an ester bond (—COO—).
  • —COO— ester bond
  • the epoxy (meth) acrylate resin (B12) also includes a resin obtained by reacting a compound having a functional group that can be further reacted with a carboxyl group of the resin obtained by the above reaction.
  • the epoxy (meth) acrylate resin has substantially no epoxy group due to its chemical structure and is not limited to “(meth) acrylate”, but the epoxy compound (epoxy resin) is used as a raw material.
  • “(meth) acrylate” is a representative example, and is so named according to common usage.
  • the epoxy resin includes a raw material compound before a resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used.
  • the epoxy resin a compound obtained by reacting a phenolic compound with epihalohydrin can be used.
  • the phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
  • bisphenol A epoxy resin bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, biphenyl novolak epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane Epoxy resin, dihydroxylfluorene type epoxy resin, dihydroxylalkyleneoxylfluorene type epoxy resin, diglycidyl etherified product of 9,9-bis (4′-hydroxyphenyl) fluorene, 1,1-bis (4′-hydroxy And diglycidyl etherified products of phenyl) adamantane.
  • Those having an aromatic ring in the main chain can be suitably used.
  • bisphenol A epoxy resin bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, and 9,9-bis (4′-hydroxyphenyl) fluorene are preferred from the viewpoint of high cured film strength.
  • Diglycidyl ether compounds are preferred, and bisphenol A epoxy resin is particularly preferred.
  • Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin (for example, “jER (registered trademark, the same applies hereinafter) 828”, “jER1001”, “jER1002”, “jER1004”, manufactured by Mitsubishi Chemical Corporation).
  • Epoxy resins and the like represented can be suitably used. Specifically, "XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (i-11), and Nippon Kayaku as an epoxy resin represented by the following general formula (i-12) "NC-3000” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (i-14).
  • n is an average value and represents a number from 0 to 10.
  • R 111 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • a plurality of R 111 present in one molecule may be the same or different.
  • n is an average value and represents a number from 0 to 10.
  • R 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • the plurality of R 121 present in one molecule may be the same or different.
  • X represents a linking group represented by the following general formula (i-13-1) or (i-13-2). However, one or more adamantane structures are included in the molecular structure.
  • c represents 2 or 3.
  • R 131 to R 134 and R 135 to R 137 each independently represent an adamantyl group which may have a substituent, hydrogen Represents an atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. * Represents a bond.
  • p and q each independently represent an integer of 0 to 4
  • R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom
  • R 143 and R 144 each independently represent an alkylene group having 1 to 4 carbon atoms
  • x and y each independently represent an integer of 0 or more.
  • Examples of the ethylenically unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, and pentaerythritol tri (meth) acrylate succinic anhydride adduct, Erythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydro
  • Examples include phthalic anhydride adducts and reaction products of (meth) acrylic acid and ⁇ -caprolactone. Among them, (meth) acrylic acid is preferred from the viewpoint of sensitivity.
  • polybasic acids examples include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid Benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • succinic anhydride succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride is preferable, and succinic anhydride or tetrahydrophthalic anhydride is more preferable.
  • the molecular weight of the epoxy (meth) acrylate resin (B12) can be increased, a branch can be introduced into the molecule, and the molecular weight and the viscosity tend to be balanced.
  • the rate of introduction of acid groups into the molecule can be increased, and there is a tendency that sensitivity, adhesion and the like are easily balanced.
  • the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably, there is.
  • the acid value of the epoxy (meth) acrylate resin (B12) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, still more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more. 80 mgKOH / g or more is particularly preferable, and 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 150 mgKOH / g or less is further preferable, 120 mgKOH / g or less is further preferable, and 110 mgKOH / g or less is particularly preferable.
  • the acid value of the epoxy (meth) acrylate resin (B12) is preferably from 10 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g, still more preferably from 50 to 150 mgKOH / g, even more preferably from 70 to 120 mgKOH / g. Particularly preferred is 110110 mgKOH / g.
  • the weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (B12) is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, further preferably 3500 or more, and usually 30,000 or less. , Preferably 15,000 or less, more preferably 10,000 or less, further preferably 8,000 or less, particularly preferably 5,000 or less.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (B12) is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, further preferably 3500 or more, and usually 30,000 or less. , Preferably 15,000 or less, more preferably 10,000 or less, further preferably 8,000 or less, particularly preferably 5,000 or less.
  • the weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (B12) is preferably from 1,000 to 30,000, more preferably from 2,000 to 15,000, still more preferably from 3,000 to 10,000, still more preferably from 3,500 to 8,000, particularly preferably from 3,500 to 5,000. preferable.
  • the alkali-soluble resin (B) contains the epoxy (meth) acrylate resin (B12), its content is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more in the (B) alkali-soluble resin. Preferably, it is more preferably 30% by mass or more, particularly preferably 35% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less.
  • the content is not less than the lower limit, the residue tends to be reduced, and when the content is not more than the upper limit, the ink repellency tends to be improved.
  • the content in the alkali-soluble resin (B) is preferably from 10 to 90% by mass, more preferably from 20 to 70% by mass, and from 30 to 70% by mass. It is more preferably 50% by mass, particularly preferably 35 to 50% by mass.
  • Epoxy (meth) acrylate resin (B12) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having an ethylenically unsaturated bond is added to cause an addition reaction, and further, a polybasic acid or a polybasic acid or the like is added. A method in which an anhydride is added to continue the reaction can be used. For example, the methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422 are exemplified.
  • examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, and secondary catalysts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride and trimethylbenzylammonium chloride.
  • thermal polymerization inhibitor examples include one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, and the like.
  • the acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, per 1 equivalent of the epoxy group of the epoxy resin. Can be obtained.
  • the temperature at the time of the addition reaction can be usually from 60 to 150 ° C, preferably from 80 to 120 ° C.
  • the amount of the polybasic acid (anhydride) to be used is generally 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents to 1 chemical equivalent of the hydroxyl group generated in the above addition reaction. The amount can be a chemical equivalent.
  • an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (i), represented by the following general formula (ii) It is preferable to include at least one selected from the group consisting of an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (iii) and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (iii).
  • Ra represents a hydrogen atom or a methyl group
  • Rb represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in the formula (i) may be further substituted with any substituent. * Represents a bond.
  • R c each independently represents a hydrogen atom or a methyl group.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond.
  • R e represents a hydrogen atom or a methyl group, gamma is a single bond, -CO-, may have a substituent group alkylene group, or a divalent which may have a substituent Represents a cyclic hydrocarbon group.
  • the benzene ring in the formula (iii) may be further substituted with any substituent. * Represents a bond.
  • epoxy (meth) acrylate resin having a partial structure represented by the following general formula (i) (hereinafter sometimes referred to as “epoxy (meth) acrylate resin (B12-1)”) is described in detail. Will be described.
  • Ra represents a hydrogen atom or a methyl group
  • Rb represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in the formula (i) may be further substituted with any substituent. * Represents a bond.
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups.
  • the divalent aliphatic group includes a linear, branched and cyclic divalent aliphatic group. Among these, a linear one is preferred from the viewpoint of development solubility, and a cyclic one is preferred from the viewpoint of reducing the penetration of the developer into the exposed part.
  • the carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
  • the carbon number of the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, and the like.
  • a methylene group is preferable from the viewpoint of ink repellency and production cost.
  • divalent branched aliphatic group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group as side chains in addition to the aforementioned divalent linear aliphatic group.
  • the number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, and preferably 5 or less.
  • the number of rings in the divalent cyclic aliphatic group is preferably 1 to 10, more preferably 1 to 5.
  • divalent cyclic aliphatic group examples include two hydrogen atoms removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a cyclododecane ring.
  • the following groups are mentioned. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of film strength and developability.
  • Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.
  • examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the carbon number of the divalent aromatic ring group is preferably from 4 to 20, more preferably from 5 to 15, and even more preferably from 6 to 10.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, a chrysene ring having two free valences.
  • Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring and an indole having two free valences.
  • Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. Among these, non-substitution is preferable from the viewpoint of curability.
  • Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include one or more of the above-described divalent aliphatic groups and the above-described divalent aromatic group. Examples thereof include groups in which one or more ring groups are linked.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the film strength tends to be improved.
  • the number of divalent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of divalent aromatic ring groups is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • a group represented by the following formula (iA) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.
  • the benzene ring in the formula (i) may be further substituted with any substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. Among them, unsubstituted is preferred from the viewpoint of curability.
  • the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1) from the viewpoint of development solubility.
  • R a and R b have the same meanings as in the formula (i).
  • RY represents a hydrogen atom or a polybasic acid residue. * Represents a bond.
  • the benzene ring in the formula (i-1) may be further substituted with any substituent.
  • the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endmethylenetetrahydrophthalic acid One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Is tetrahydrophthalic acid or biphenyltetracarboxylic acid.
  • the repeating unit structure represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) may be one type or two or more types.
  • the number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable.
  • the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the film strength tends to be improved.
  • the number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 to 8 Is more preferred.
  • the number of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. It is preferably 3 or more, more preferably 10 or less, and even more preferably 8 or less.
  • the number of the partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 to 3. -8 is more preferable.
  • epoxy (meth) acrylate resin (B12-2) an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (ii) (hereinafter sometimes referred to as “epoxy (meth) acrylate resin (B12-2)”) will be described in detail. .
  • R c each independently represents a hydrogen atom or a methyl group.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of rings in the aliphatic cyclic group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • the number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable.
  • the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of carbon atoms in the aliphatic ring group is preferably from 4 to 40, more preferably from 4 to 30, still more preferably from 6 to 20, and particularly preferably from 8 to 15.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring and the like.
  • an adamantane ring is preferable from the viewpoint of film strength and developability.
  • the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, 5 or less, preferably 4 or less. Is more preferred.
  • the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 4, and particularly preferably 2 to 4.
  • the aromatic ring group examples include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, and more preferably 30 or less. More preferably, it is more preferably 20 or less, particularly preferably 15 or less.
  • the aromatic ring group preferably has 4 to 40 carbon atoms, more preferably has 6 to 30 carbon atoms, further preferably has 8 to 20 carbon atoms, further preferably has 10 to 15 carbon atoms, and particularly preferably has 12 to 15 carbon atoms.
  • aromatic ring in the aromatic ring group benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, And a fluorene ring.
  • a fluorene ring is preferable from the viewpoint of patterning characteristics.
  • the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited.
  • a divalent aliphatic group, a divalent aromatic ring group, and one or more And a group obtained by linking a divalent aliphatic group with one or more divalent aromatic ring groups is not particularly limited.
  • the divalent aliphatic group includes a linear, branched and cyclic divalent aliphatic group.
  • a linear one is preferred from the viewpoint of improvement in developability
  • a cyclic one is preferred from the viewpoint of film strength.
  • the carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the carbon number of the divalent aliphatic group is preferably 1 to 25, more preferably 3 to 20, and still more preferably 6 to 15.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, and the like.
  • a methylene group is preferable from the viewpoint of ink repellency.
  • divalent branched aliphatic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group as side chains in addition to the aforementioned divalent linear aliphatic group.
  • the number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, 5 or less, and more preferably 3 or less.
  • the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of rings in the divalent cyclic aliphatic group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2 to 5.
  • divalent cyclic aliphatic group examples include two hydrogen atoms removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a cyclododecane ring.
  • the following groups may be mentioned. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of film strength.
  • Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.
  • examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the carbon number of the divalent aromatic ring group is preferably from 4 to 30, more preferably from 5 to 20, and even more preferably from 6 to 15.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, a chrysene ring having two free valences.
  • Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
  • Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. Among these, non-substitution is preferable from the viewpoint of curability.
  • Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include one or more of the above-described divalent aliphatic groups and the above-described divalent aromatic group. Examples thereof include groups in which one or more ring groups are linked.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the film strength tends to be improved.
  • the number of divalent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of divalent aromatic ring groups is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (iA) to (iF). Is mentioned. Among these, a group represented by the formula (iC) is preferable from the viewpoint of achieving both film strength and ink repellency.
  • the bonding mode of the cyclic hydrocarbon group which is a side chain to these divalent hydrocarbon groups is not particularly limited.
  • one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain.
  • a cyclic hydrocarbon group which is a side chain including one of the carbon atoms of the aliphatic group is constituted.
  • partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of ink repellency.
  • R c has the same meaning as in the above formula (ii).
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • n is an integer of 1 or more.
  • the benzene ring in the formula (ii-1) may be further substituted with any substituent.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less, and more preferably 3 or less.
  • the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of rings in the aliphatic cyclic group is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 2 to 3.
  • the number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable.
  • the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of carbon atoms in the aliphatic ring group is preferably from 4 to 40, more preferably from 4 to 30, still more preferably from 6 to 20, and particularly preferably from 8 to 15.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring and the like.
  • an adamantane ring is preferred from the viewpoint of achieving both film strength and developability.
  • the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, and preferably 5 or less.
  • the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the number of carbon atoms in the aromatic ring group is preferably from 4 to 30, more preferably from 5 to 20, and even more preferably from 6 to 15.
  • aromatic ring in the aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • a fluorene ring is preferred from the viewpoint of achieving both film strength and developability.
  • Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; Of these, non-substitution is preferred from the viewpoint of ease of synthesis.
  • N represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less.
  • n is preferably an integer of 1 or more and 3 or less, and more preferably an integer of 2 or more and 3 or less.
  • R ⁇ is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group, from the viewpoint of achieving both film strength and developability.
  • the benzene ring in the formula (ii-1) may be further substituted with any substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. Among them, unsubstituted is preferred from the viewpoint of curability.
  • the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of development adhesion.
  • R c has the same meaning as in the above formula (ii).
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the benzene ring in the formula (ii-2) may be further substituted with any substituent.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, and preferably 5 or less.
  • the number of rings in the aliphatic cyclic group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5.
  • the number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • the carbon number of the aliphatic ring group is preferably from 4 to 40, more preferably from 6 to 35, even more preferably from 8 to 30.
  • Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Of these, an adamantane ring is preferred from the viewpoint of achieving both film strength and developability.
  • the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, and preferably 5 or less.
  • the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, still more preferably 2 to 5, and particularly preferably 3 to 5.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Preferably, it is particularly preferably 15 or less.
  • the number of carbon atoms of the aromatic ring group is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15.
  • aromatic ring in the aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • a fluorene ring is preferable from the viewpoint of film strength and developability.
  • Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; Among these, non-substitution is preferred from the viewpoint of simplicity of synthesis.
  • R ⁇ is preferably a divalent aliphatic ring group, more preferably a divalent adamantane ring group, from the viewpoint of achieving both film strength and developability.
  • R ⁇ is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
  • the benzene ring in the formula (ii-2) may be further substituted with any substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like.
  • the number of substituents is not particularly limited either, and may be one or two or more. Among them, unsubstituted is preferred from the viewpoint of curability.
  • the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of developability.
  • R c and R d have the same meanings as in formula (ii).
  • R Z represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endmethylenetetrahydrophthalic acid One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Is tetrahydrophthalic acid or biphenyltetracarboxylic acid.
  • the partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) may be one type or two or more types.
  • the number of the partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Also, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
  • the number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and more preferably 3 to 10 Is more preferred.
  • the number of partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. Preferably, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
  • the number of the partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
  • the number of partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. Preferably, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
  • the number of partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. Preferably, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
  • epoxy (meth) acrylate resin having a partial structure represented by the following general formula (iii) (hereinafter sometimes referred to as “epoxy (meth) acrylate resin (B12-3)”) will be described in detail. .
  • R e represents a hydrogen atom or a methyl group, gamma is a single bond, -CO-, may have a substituent group alkylene group, or a divalent which may have a substituent Represents a cyclic hydrocarbon group.
  • the benzene ring in the formula (iii) may be further substituted with any substituent. * Represents a bond.
  • ⁇ represents a single bond, —CO—, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.
  • the alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility, and is preferably branched from the viewpoint of development adhesion.
  • the number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less.
  • the carbon number of the alkylene group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 2 to 4.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and a heptylene group.From the viewpoint of achieving both film strength and developability, an ethylene group or a propylene group is preferable. Groups are more preferred.
  • Examples of the substituent which the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.
  • divalent cyclic hydrocarbon group examples include a divalent aliphatic ring group and a divalent aromatic ring group.
  • the number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, and preferably 5 or less.
  • the number of rings in the aliphatic cyclic group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5.
  • the number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • the carbon number of the aliphatic ring group is preferably from 4 to 40, more preferably from 6 to 35, even more preferably from 8 to 30.
  • Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Of these, an adamantane ring is preferred from the viewpoint of achieving both film strength and developability.
  • the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, and preferably 5 or less.
  • the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, still more preferably 2 to 5, and particularly preferably 3 to 5.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Preferably, it is particularly preferably 15 or less.
  • the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • the number of carbon atoms of the aromatic ring group is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15.
  • Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among these, non-substitution is preferred from the viewpoint of simplicity of synthesis.
  • ⁇ is preferably an alkylene group which may have a substituent, and more preferably a dimethylmethylene group.
  • the benzene ring in the formula (iii) may be further substituted with any substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like.
  • the number of substituents is not particularly limited either, and may be one or two or more. Among them, unsubstituted is preferred from the viewpoint of curability.
  • the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1) from the viewpoint of development solubility.
  • R W represents a hydrogen atom or a polybasic acid residue. * Represents a bond.
  • the benzene ring in the formula (iii-1) may be further substituted with any substituent.
  • the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endmethylenetetrahydrophthalic acid One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Is tetrahydrophthalic acid or biphenyltetracarboxylic acid.
  • the number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth) acrylate resin (B12-3) is not particularly limited, but is preferably 1 or more, and more preferably 5 or more. , Preferably 10 or more, more preferably 18 or less, even more preferably 15 or less.
  • the number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth) acrylate resin (B12-3) is preferably 1 to 18, more preferably 5 to 15, and more preferably 10 to 15 is more preferred.
  • the number of repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-3) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. More preferably, 5 or more is more preferable, 18 or less is preferable, and 15 or less is further preferable.
  • the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the number of the repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-3) is preferably 1 to 18, more preferably 3 to 15, 5 to 15 are more preferred.
  • the alkali-soluble resin (B) in the present invention may include other alkali-soluble resins in addition to the acrylic copolymer resin (B11) and the epoxy (meth) acrylate resin (B12).
  • the acid value of the alkali-soluble resin as the component (B) is not particularly limited, but is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, further preferably 70 mgKOH / g or more, and further preferably 200 mgKOH / g or less. , 150 mgKOH / g or less, more preferably 100 mgKOH / g or less.
  • the acid value means a weighted average value according to the content ratio.
  • the acid value of the alkali-soluble resin of the component (B) is preferably from 30 to 200 mgKOH / g, more preferably from 50 to 150 mgKOH / g, even more preferably from 70 to 100 mgKOH / g.
  • the content of the alkali-soluble resin (B) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass, based on the total solid content. % By mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass. It is as follows. When the ratio is not less than the lower limit, the shape of the partition tends to be good, and when the ratio is not more than the upper limit, the ink repellency tends to be improved.
  • the content of the alkali-soluble resin (B) in the total solid content of the photosensitive colored resin composition is preferably from 5 to 90% by mass, more preferably from 10 to 90% by mass, even more preferably from 20 to 80% by mass. It is more preferably from 30 to 80% by mass, particularly preferably from 40 to 70% by mass, particularly preferably from 50 to 70% by mass.
  • the total content of the photopolymerizable compound (C) and the content of the alkali-soluble resin (B) in the total solid content is not particularly limited, but is preferably 10% by mass or more, and more preferably 30% by mass or more. , 60% by mass or more, still more preferably 80% by mass or more, preferably 95% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less.
  • the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the shape of the partition wall tends to be good.
  • the total of the content of the photopolymerizable compound (C) and the content of the alkali-soluble resin (B) in the total solid content of the photosensitive colored resin composition is preferably 10 to 95% by mass, and 30 to 92% by mass. Is more preferably 60 to 90% by mass, and particularly preferably 80 to 90% by mass.
  • photopolymerizable Compound The photosensitive colored resin composition of the present invention contains (C) a photopolymerizable compound. It is considered that by containing the photopolymerizable compound (C), the curability of the coating film is increased and the ink repellency is improved.
  • the photopolymerizable compound means a compound having at least one ethylenically unsaturated bond in a molecule, and is polymerizable, crosslinkable, and dissolved in a developing solution in an exposed portion and a non-exposed portion.
  • the compound has two or more ethylenically unsaturated bonds in the molecule from the viewpoint that the difference in sex can be expanded, and the unsaturated bond is derived from a (meth) acryloyloxy group, that is, And (meth) acrylate compounds.
  • a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule is particularly desirable.
  • the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15 or more.
  • the number is preferably 10 or less, more preferably 8 or less, and particularly preferably 7 or less.
  • the content is not less than the lower limit, the polymerizability tends to be improved and the ink repellency tends to be high.
  • the developability tends to be better.
  • the number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is preferably 2 to 15, more preferably 2 to 10, still more preferably 2 to 8, and still more preferably 3 to 7. And 5 to 7 are particularly preferred.
  • Specific examples of the photopolymerizable compound include: an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic polyhydroxy compound, and the like. And an ester obtained by an esterification reaction of the polyvalent hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.
  • ester of the aliphatic polyhydroxy compound and an unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and methacrylic esters in which the acrylate of these exemplified compounds is replaced with methacrylate And itaconic acid esters, chronone Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to bets and the like.
  • ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid examples include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. And the like.
  • ester obtained by an esterification reaction of a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid
  • the ester is not necessarily a single ester, but is typically used.
  • acrylic acid, phthalic acid, and condensates of ethylene glycol acrylic acid, maleic acid, and condensates of diethylene glycol, methacrylic acid, condensates of terephthalic acid and pentaerythritol, acrylic acid, adipic acid, And condensates of butanediol and glycerin.
  • polyfunctional ethylenic monomer used in the present invention examples include a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate.
  • urethane (meth) acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (Nippon Kayaku), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.
  • urethane (meth) acrylates are preferably used as the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid as the photopolymerizable compound (C) from the viewpoint of the perpendicularity of the partition wall side and the ink repellency.
  • the molecular weight of the photopolymerizable compound (C) is not particularly limited, but is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, from the viewpoints of ink repellency and verticality of the side wall of the partition. It is even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1,000 or less, more preferably 700 or less.
  • the molecular weight of the photopolymerizable compound (C) is preferably from 100 to 1,000, more preferably from 150 to 1,000, still more preferably from 200 to 1,000, still more preferably from 300 to 700, still more preferably from 400 to 700, and more preferably from 500 to 700. Is particularly preferred.
  • the number of carbon atoms of the photopolymerizable compound (C) is not particularly limited, but is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, from the viewpoint of ink repellency and verticality of the side wall of the partition. It is preferably at least 20, more preferably at least 25, preferably at most 50, more preferably at most 40, further preferably at most 35, particularly preferably at most 30.
  • the carbon number of the photopolymerizable compound (C) is preferably from 7 to 50, more preferably from 10 to 40, still more preferably from 15 to 35, still more preferably from 20 to 30, and particularly preferably from 25 to 30.
  • ester (meth) acrylates is preferable, and among them, pentaerythritol tetra (meth) acrylate, pentane Trifunctional or higher functional ester (meth) acrylates such as erythritol tri (meth) acrylate dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, 2,2,2-tris (meth) acryloyloxymethylethyl
  • An acid anhydride adduct to tri- or higher functional ester (meth) acrylates such as phthalic acid, dipentaerythritol penta (meth) acrylate dibasic acid anhydride adduct, provides ink repellency and verticality of the side wall
  • the content ratio of the photopolymerizable compound (C) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass in the total solid content. It is at least 15% by mass, more preferably at least 15% by mass, usually at most 80% by mass, preferably at most 60% by mass, more preferably at most 40% by mass, even more preferably at most 30% by mass.
  • the ratio is not less than the lower limit, the perpendicularity of the side wall of the partition during exposure tends to be good, and when the ratio is not more than the upper limit, the developability tends to be good.
  • the content of the photopolymerizable compound (C) in the total solid content of the photosensitive colored resin composition is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 40% by mass. , 15 to 30% by mass is particularly preferred.
  • the content ratio of the photopolymerizable compound (C) to 100 parts by mass of the alkali-soluble resin (B) is not particularly limited, but is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and furthermore It is preferably at least 15 parts by mass, particularly preferably at least 20 parts by mass, usually at most 150 parts by mass, preferably at most 100 parts by mass, more preferably at most 70 parts by mass, still more preferably at most 50 parts by mass, particularly preferably at most 40 parts by mass. It is preferable that the amount is not more than part by mass. When the content is not less than the lower limit, the ink repellency tends to be good, and the verticality of the side wall of the partition tends to be good.
  • the content ratio of the photopolymerizable compound (C) to 100 parts by mass of the alkali-soluble resin (B) is preferably from 1 to 150 parts by mass, more preferably from 5 to 100 parts by mass, still more preferably from 10 to 70 parts by mass, and preferably from 15 to 70 parts by mass.
  • the amount is more preferably from 50 to 50 parts by mass, and particularly preferably from 20 to 40 parts by mass.
  • the photosensitive colored resin composition of the present invention contains (D) a colorant.
  • a coloring agent By containing a coloring agent, it is possible to obtain a suitable light-absorbing property, especially when used for forming a light-blocking member such as a colored partition wall.
  • the type of the colorant (D) used in the present invention is not particularly limited, and a pigment or a dye may be used. Among these, it is preferable to use a pigment from the viewpoint of durability.
  • the pigment contained in the colorant may be used alone or in combination of two or more. In particular, from the viewpoint of uniformly blocking light in the visible region, it is preferable to use two or more types.
  • the type of pigment that can be used as a colorant is not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, it is preferable to use an organic pigment from the viewpoint of controlling the transmission wavelength of the photosensitive colored resin composition and curing efficiently.
  • the organic pigment include an organic coloring pigment and an organic black pigment.
  • the organic coloring pigment means an organic pigment exhibiting a color other than black, and includes a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment, a yellow pigment, and the like.
  • organic coloring pigments it is preferable to use an organic coloring pigment from the viewpoint of light shielding properties and ultraviolet absorbing properties.
  • One type of organic color pigment may be used alone, or two or more types may be used in combination.
  • organic pigments are not particularly limited, but examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based.
  • pigment numbers specific examples of pigments that can be used are shown by pigment numbers. Terms such as "CI Pigment Red 2" below refer to the color index (CI).
  • Red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 185, 187, 188, 190, 193, 194, 200,
  • C.I. is preferable from the viewpoint of light-shielding properties and dispersibility.
  • I. Pigment Red 48 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, and 254.
  • C.I. I. Pigment Red 177, 254, and 272 are preferred.
  • a red pigment having a low ultraviolet absorptivity is preferably used.
  • I. Pigment Red 254, 272 is more preferably used.
  • C.I. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
  • C.I. I. Pigment Orange 13, 43, 64, and 72 are preferably used.
  • an orange pigment having a low ultraviolet absorptivity from this viewpoint.
  • Is C. I. Pigment Orange 64 and 72 are more preferably used.
  • Blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.
  • C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60 and more preferably C.I. I. Pigment Blue 15: 6.
  • C.I. I. Pigment Blue 15: 6, 16, or 60 is preferably used.
  • a blue pigment having a low ultraviolet absorptivity Is C. I. Pigment Blue 60 is more preferably used.
  • purple pigments examples include C.I. I. Pigment Violet 1, 1: 1, 2: 2: 2, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.
  • C.I. I. Pigment Violet 23 or 29 is preferably used.
  • the photosensitive colored resin composition is cured with ultraviolet light, it is preferable to use a purple pigment having a low ultraviolet absorptivity.
  • I. Pigment Violet 29 is more preferably used.
  • Organic pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include, for example, green pigments and yellow pigments.
  • Green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among them, C.I. I. Pigment Green 7 and 36.
  • yellow pigment C.I. I.
  • ⁇ ⁇ ⁇ Among these, it is preferable to use at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments from the viewpoint of light-shielding properties and control of the shape.
  • Red pigment C.I. I. Pigment Red 177, 254, 272
  • Orange pigment C.I. I. Pigment Orange 43, 64, 72
  • Blue pigment C.I. I. Pigment Blue 15: 6, 60 Purple pigment: C.I. I. Pigment Violet 23, 29
  • the combination of the organic coloring pigments is not particularly limited, but from the viewpoint of light shielding properties, at least one selected from the group consisting of red pigments and orange pigments, and blue pigments And at least one member selected from the group consisting of violet pigments.
  • the combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment, an orange pigment, and a violet pigment are exemplified. .
  • black pigments may be used.
  • a black pigment may be used in addition to the organic coloring pigment.
  • the black pigment include an inorganic black pigment and an organic black pigment. From the viewpoint of light-shielding properties, it is preferable to contain one or both of carbon black and an organic black pigment.
  • an organic black pigment from the viewpoint of suppressing absorption of ultraviolet rays to facilitate control of the shape, and particularly from the viewpoint of light-shielding properties, represented by the following general formula (1).
  • At least one selected from the group consisting of a compound hereinafter, also referred to as “compound (1)”
  • a geometric isomer of compound (1) a salt of compound (1)
  • a salt of a geometric isomer of compound (1) It is preferable to use an organic black pigment containing a seed (hereinafter, may be referred to as “organic black pigment represented by the general formula (1)”).
  • R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • compound (1) When compound (1) is anionic, its charge is transferred to any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium It is preferably a salt compensated by a tertiary ammonium such as secondary ammonium, trialkylammonium and the like, a quaternary ammonium such as tetraalkylammonium or an organometallic complex. Further, when the geometric isomer of the compound (1) is anionic, it is preferably a similar salt.
  • suitable cation such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium It is preferably a salt compensated by a tertiary ammonium such as secondary ammonium, trialkylammonium and the like, a quaternary ammonium such as tetraalkylammonium or an
  • R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom.
  • R 13 and R 18 are preferably each independently a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3) (C 2 H 5) , N (C 2 H 5) 2, ⁇ - naphthyl, beta-naphthyl, SO 3 H or SO 3 - and, still more preferably a hydrogen atom or SO 3 H, and particularly preferably Is a hydrogen atom.
  • R 11 and R 16 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
  • at least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, more preferably R 11 is the same as R 16 , R 12 is the same as R 17 , R 13 is the same as R 18 , R 14 is the same as R 19 , and R 15 is the same as R 20 Are identical.
  • the alkyl group having 1 to 12 carbon atoms includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, An ethylhexyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tudyl group, a norbornyl group, a bornyl group, and a norcalyl group.
  • Alkenyl groups having 2 to 12 carbon atoms include, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, A 3-methyl-2-buten-1-yl group, a 1,4-pentadien-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group or a dodecenyl group.
  • Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, and 2-cyclohexen-1-yl.
  • the alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl Group, 1,4-pentadiin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl Group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadin-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, It is a 1-decin-10-yl group or a 1-dodecin-12-yl group.
  • a halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the organic black pigment represented by the general formula (1) is preferably a compound represented by the following general formula (2) (hereinafter, also referred to as “compound (2)”), and geometric isomerism of the compound (2).
  • organic black pigment examples include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
  • This organic black pigment is preferably used after being dispersed by a dispersant, a solvent, and a method described below. Further, when the sulfonic acid derivative of the compound (1), particularly the sulfonic acid derivative of the compound (2) is present at the time of dispersion, the dispersibility and the storage stability may be improved. It is preferable to include
  • Examples of the organic black pigment other than the organic black pigment represented by the general formula (1) include aniline black and perylene black.
  • examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.
  • carbon black can be preferably used from the viewpoint of light-shielding properties and image characteristics.
  • examples of the carbon black include the following carbon blacks.
  • RAVEN registered trademark, the same applies hereinafter
  • RAVEN14 RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVE40, RAVE410, RAVE420, RAVE450, RAVE500, RAVE780, RAVE850, RAVE890V, EN10VAVE10, RAVEN10V, RAVEN10VEN10VAVE10VENVAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVE
  • Carbon black coated with a resin may be used.
  • the use of resin-coated carbon black has the effect of improving adhesion to a glass substrate and volume resistance.
  • carbon black coated with a resin for example, carbon black described in JP-A-09-71733 can be suitably used.
  • Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
  • the carbon black to be subjected to the resin coating treatment preferably has a total content of Na and Ca of 100 ppm or less.
  • Carbon black is usually a raw material oil or a combustion oil (or gas) at the time of production, reaction stop water or granulation water, or Na, Ca, K, Mg, Al, Fe, or the like mixed from a furnace material of a reaction furnace.
  • An ash component having the following composition is contained.
  • Na and Ca are each generally contained in the amount of several hundred ppm or more, but by reducing these, the penetration into the transparent electrode (ITO) and other electrodes is suppressed, and Tends to prevent a short circuit.
  • a material having a minimum of these contents is carefully selected as a raw material oil, a fuel oil (or a gas) and a reaction stop water in producing carbon black. This is possible by minimizing the amount of addition of an alkali substance for adjusting the structure.
  • a method in which carbon black produced from a furnace is washed with water, hydrochloric acid or the like to dissolve and remove Na and Ca.
  • the resin-coated carbon black is preferably a so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is small, it is possible to coat even fine units, which is preferable. Further, the average particle size is preferably 40 nm or less, and the dibutyl phthalate (DBP) absorption amount is preferably 140 mL / 100 g or less. When the content is within the above range, a coating film having good light-shielding properties tends to be obtained.
  • the average particle diameter means a number average particle diameter. A particle image analysis that photographs several tens of thousands of photographs taken at tens of thousands of times by observation with an electron microscope, and measures about 2,000 to 3,000 particles of these photographs by an image processing device. Means the equivalent circle diameter determined by
  • the method for preparing the resin-coated carbon black is not particularly limited. For example, after appropriately adjusting the blending amounts of the carbon black and the resin, Resin and cyclohexanone, toluene, mixed with a solvent such as xylene and heated and dissolved, and a mixture of carbon black and water are mixed and stirred to separate carbon black and water, 1. A method in which a composition obtained by removing water, heating and kneading is formed into a sheet, pulverized, and then dried; A method of mixing and stirring the resin solution and the suspension prepared in the same manner as above to granulate the carbon black and the resin, and then separating and heating the obtained granules to remove the remaining solvent and water; 3.
  • a carboxylic acid such as maleic acid or fumaric acid is dissolved in the solvent exemplified above, carbon black is added, mixed and dried, and after removing the solvent to obtain a carboxylic acid-impregnated carbon black, a resin is added thereto.
  • dry blending method A reactive group-containing monomer component and water constituting the resin to be coated are stirred at high speed to prepare a suspension, and after the polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension.
  • a method in which carbon black is added and kneaded to react the carbon black with a reactive group (graft the carbon black), cool and pulverize, or the like can be employed.
  • the type of the resin to be subjected to the coating treatment is not particularly limited, but a synthetic resin is generally used, and a resin having a benzene ring in the structure has a stronger function as an amphoteric surfactant. It is preferable from the viewpoint of dispersibility and dispersion stability.
  • Specific synthetic resins include thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallyl phthalate resins, glyptal resins, epoxy resins, alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene.
  • Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylene sulfone, polyarylate, and polyetheretherketone can be used.
  • the amount of the coating resin is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin. When the content is not less than the lower limit, the coating tends to be sufficient. On the other hand, when the content is equal to or less than the upper limit value, there is a tendency that adhesion between the resins can be prevented and the dispersibility can be improved.
  • the carbon black thus coated with the resin can be used as a coloring agent for the colored partition walls according to a conventional method.
  • a coloring agent for the colored partition walls According to a conventional method, there is a tendency that a colored partition wall having a high light blocking ratio and a low surface reflectance can be formed at low cost.
  • coating the surface of the carbon black with a resin has a function of sealing ash containing Na and Ca into the carbon black.
  • the average particle diameter of the pigment is usually 1 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.25 ⁇ m or less.
  • the standard of the average particle diameter is the number of pigment particles.
  • the average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS).
  • a sufficiently diluted photosensitive coloring resin composition usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. And the concentration is determined according to the concentration).
  • a dye may be used in addition to the above-mentioned organic color pigment and black pigment.
  • the dye that can be used as the coloring agent include an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone imine dye, a quinoline dye, a nitro dye, a carbonyl dye, and a methine dye.
  • azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I.
  • Direct Orange 26 C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordant Red 7, C.I. I. Mordant Yellow 5, C.I. I. Mordant Black 7 and the like.
  • anthraquinone dye examples include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse Red 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like.
  • Other phthalocyanine dyes include, for example, C.I. I. Pad Blue 5 and the like include quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like include quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like include, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
  • the content of the (D) colorant in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more in the total solid content. It is more preferably at least 4% by mass. Further, it is usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, particularly preferably 10% by mass or less, and 6% by mass or less. Most preferably, it is not more than mass%.
  • the content of the colorant (D) in the total solid content of the photosensitive colored resin composition is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, still more preferably 2 to 25% by mass.
  • the content is more preferably from 20 to 20% by mass, still more preferably from 3 to 15% by mass, particularly preferably from 4 to 10% by mass.
  • Component (E); Liquid Repellent contains, as the liquid repellent (E), a fluorine atom-containing resin having a crosslinking group. It is considered that since the surface of the partition wall obtained by containing the fluorine atom-containing resin having a cross-linking group can be provided with ink repellency, the obtained partition wall can prevent color mixing of each light emitting portion (pixel) of the organic layer. Can be
  • crosslinking group examples include an epoxy group and an ethylenically unsaturated group, and an ethylenically unsaturated group is preferable from the viewpoint of suppressing the outflow of the liquid-repellent component of the developer.
  • a liquid repellent having a cross-linking group By using a liquid repellent having a cross-linking group, a cross-linking reaction on the surface of the formed coating film can be accelerated when the formed coating film is exposed, and the liquid repellent is less likely to flow out in a development process, and as a result, the obtained partition wall Is considered to exhibit high ink repellency.
  • the resin is a fluorine atom-containing resin
  • the fluorine atom-containing resin tends to orient on the surface of the partition wall and work to prevent ink bleeding and color mixing. More specifically, a group having a fluorine atom tends to repel the ink and to prevent the ink from bleeding and color mixing due to the ink entering an adjacent region beyond the partition wall.
  • the fluorine atom-containing resin having a cross-linking group has one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain.
  • the fluorine atom-containing resin is more easily oriented on the surface of the partition wall, exhibits higher ink repellency, and causes ink bleeding and color mixing. There is also a tendency to prevent.
  • Examples of the perfluoroalkyl group include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, and the like.
  • Examples of the perfluoroalkylene ether chain include —CF 2 —O—, — (CF 2 ) 2 —O—, — (CF 2 ) 3 —O—, —CF 2 —C (CF 3 ) O—, and —C ( CF 3 ) —CF 2 —O— and a divalent group having these repeating units.
  • fluorine atom-containing resin having a crosslinking group examples include, for example, an acrylic copolymer resin having an epoxy group and a perfluoroalkyl group, an acrylic copolymer resin having an epoxy group and a perfluoroalkylene ether chain, an ethylenically unsaturated group and Acrylic copolymer resin having a perfluoroalkyl group, acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, epoxya (meth) acrylate resin having an epoxy group and a perfluoroalkyl group, epoxy group and perfluoro Epoxy (meth) acrylate resin having alkylene ether chain, epoxy (meth) acrylate resin having ethylenically unsaturated group and perfluoroalkyl group, ethylenically unsaturated group and perfluoroalkyl Epokishia with ether chain (meth) acrylate resins
  • an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group and an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferable.
  • Acrylic copolymer resins having a saturated group and a perfluoroalkylene ether chain are more preferred.
  • acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene group “Megafax RS-72-K”, “Megafax RS-78” and the like can be suitably used.
  • the fluorine atom content in the fluorine atom-containing resin having a crosslinking group is not particularly limited, but is preferably 5% by weight or more, more preferably 10% by weight or more, and more preferably 20% by weight or more in the fluorine atom-containing resin having a crosslinking group. It is more preferably at least 25% by mass. Further, the content is preferably 50% by mass or less, more preferably 35% by mass or less. When the value is equal to or larger than the lower limit, the outflow to the pixel region tends to be suppressed, and when the value is equal to or smaller than the upper limit, a high contact angle tends to be exhibited.
  • the content of fluorine atoms in the fluorine-containing resin having a cross-linking group is preferably 5 to 50% by mass, more preferably 10 to 35% by mass, and more preferably 20 to 35% by mass in the fluorine-containing resin having a cross-linking group. More preferably, it is particularly preferably from 25 to 35% by mass.
  • the molecular weight of the fluorine-containing resin having a crosslinking group is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound. Higher molecular weight is preferred because the fluidity due to post-baking is suppressed and the outflow from the partition walls can be suppressed, and from this viewpoint, the number average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 100 or more. , 500 or more, more preferably 100,000 or less, and even more preferably 10,000 or less.
  • the molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably from 100 to 100,000, and more preferably from 500 to 10,000.
  • the content of the liquid repellent (E) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.1% by mass or more based on the total solid content. It is 0.5% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less.
  • the amount is equal to or more than the lower limit, high ink repellency tends to be exhibited.
  • the amount is equal to or less than the upper limit, outflow to the pixel region tends to be suppressed.
  • the content of the liquid repellent (E) is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and more preferably 0.5 to 2% by mass based on the total solid content of the photosensitive colored resin composition. % Is more preferred.
  • the content of the fluorine-containing resin having a crosslinking group is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the total solid content. And usually at most 5% by mass, preferably at most 3% by mass, more preferably at most 2% by mass.
  • the amount is equal to or more than the lower limit, high ink repellency tends to be exhibited.
  • the amount is equal to or less than the upper limit, outflow to the pixel region tends to be suppressed.
  • the content of the fluorine atom-containing resin having a crosslinking group is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and more preferably 0.5 to 3% by mass based on the total solid content of the photosensitive colored resin composition. ⁇ 2% by weight is more preferred.
  • a surfactant may be used together with the liquid repellent (E).
  • Surfactants can be used for the purpose of improving the coating properties of the photosensitive coloring resin composition as a coating solution, and the developability of the coating film, among which silicone surfactants and crosslinking groups are not present Fluorinated surfactants are preferred.
  • a silicone surfactant is preferable, and polyether-modified silicone is preferred.
  • a system surfactant is more preferred.
  • a compound having a fluoroalkyl or fluoroalkylene group at at least one of terminal, main chain and side chain is preferable.
  • these commercially available products include "BM-1000" and “BM-1100” manufactured by BM Chemie, "MegaFac F142D”, “MegaFac F172", “MegaFac F173”, and “MegaFac F183" manufactured by DIC. "MegaFac F470”, “MegaFac F475", “MegaFac F554", “MegaFac F559", “FC430” manufactured by 3M Japan, “DFX-18” manufactured by Neos, and the like.
  • silicone surfactant examples include, for example, “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400” manufactured by Dow Corning Toray.
  • Commercial products such as “BYK (registered trademark, hereinafter the same) 323" and "BYK330" manufactured by BYK-Chemie can be mentioned.
  • the surfactant may include other than a fluorine-based surfactant and a silicone-based surfactant, and other surfactants include nonionic, anionic, cationic, and amphoteric surfactants.
  • nonionic surfactant examples include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrit fatty acid esters, polyoxyethylene pentaerythrit fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbite fatty acid esters, polyoxy And ethylene sorbite fatty acid esters.
  • examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen (registered trademark, the same applies hereinafter) 104P" and "Emulgen A60" manufactured by Kao Corporation.
  • anionic surfactant examples include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfates, and higher alcohol sulfates. Ester salts, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, specialty Polymeric surfactants and the like can be mentioned.
  • special polymer surfactants are preferable, and special polycarboxylic acid polymer surfactants are more preferable.
  • Commercially available products can be used as such anionic surfactants.
  • "Emal (registered trademark, the same applies hereinafter) 10" manufactured by Kao Corporation for alkyl sulfate salts, and Kao Corporation for alkyl naphthalene sulfonates.
  • special polymer surfactants such as “Perex (registered trademark) NB-L” manufactured by Kao Corporation include “Homogenol (registered trademark, the same applies hereinafter) L-18" and “Homogenol L-100". .
  • Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.
  • Examples of the amphoteric surfactant include betaine-type compounds, imidazolium salts, imidazolines, and amino acids. And the like. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred.
  • Examples of commercially available products include, for example, “Acetamine (registered trademark) 24” manufactured by Kao Corporation for alkylamine salts, and “Coatamine (registered trademark, same hereafter) 24P” and “Coatamine” manufactured by Kao Corporation for quaternary ammonium salts. 86W ".
  • two or more surfactants may be used in combination.
  • silicone surfactants / fluorine surfactants silicone surfactants / special polymer surfactants, fluorine surfactants / Combinations of special polymer surfactants.
  • a combination of a silicone-based surfactant / a fluorine-based surfactant is preferable.
  • silicone surfactant / fluorine surfactant for example, "DFX-18” manufactured by Neos Co., Ltd., "BYK-300” or “BYK-330” manufactured by BYK-Chemie, or "S- manufactured by AGC Seimi Chemical Co., Ltd.” 393 ”, Shin-Etsu Silicone“ KP340 ”/ DIC“ F-554 ”or“ F-559 ”, Toray Dow Corning“ SH7PA ”/ Daikin“ DS-401 ”, NUC“ L ” -77 “/” FC4430 "manufactured by 3M Japan.
  • the photosensitive colored resin composition of the present invention contains (D) a dispersant in order to finely disperse the (D) colorant and stabilize the dispersion state. It is preferred to include.
  • a dispersant a polymer dispersant having a functional group is preferable, and further from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary, or tertiary.
  • Polymer dispersants having a functional group such as an amino group, a quaternary ammonium base, a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, and pyrazine are preferred.
  • a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine disperses the pigment. It is particularly preferable from the viewpoint that it can be dispersed with a small amount of a dispersant.
  • polymer dispersant examples include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, and a polyoxyethylene alkyl ether.
  • Dispersants polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • dispersants are EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Big Chemie), Dispalon (registered trademark, manufactured by Kusumoto Kasei), SOLSPERSE under trade names.
  • EFKA registered trademark, manufactured by BASF
  • DISPERBYK registered trademark, manufactured by Big Chemie
  • Dispalon registered trademark, manufactured by Kusumoto Kasei
  • SOLSPERSE SOLSPERSE under trade names.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • Azispar registered trademark, manufactured by Ajinomoto Co., Inc.
  • One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.
  • the weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less.
  • the weight average molecular weight (Mw) of the polymer dispersant is preferably from 700 to 100,000, more preferably from 1,000 to 50,000.
  • the dispersant (F) preferably contains one or both of a urethane polymer dispersant and an acrylic polymer dispersant having a functional group. It is particularly preferred to include a molecular dispersant. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having one or both of a polyester bond and a polyether bond is preferable.
  • urethane-based and acrylic-based polymer dispersants examples include DISPERBYK-160 to 167 and 182 series (all are urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 and the like (all are acrylic-based). ).
  • Specific examples of preferable chemical structures for the urethane polymer dispersant include, for example, a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000, and And a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting an active hydrogen with a compound having a tertiary amino group. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.
  • a quaternizing agent such as benzyl chloride
  • polyisocyanate compounds examples include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
  • Aliphatic diisocyanate such as aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ⁇ , ⁇ Alicyclic diisocyanate such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl Aliphatic diisocyanate having an aromatic ring such as silylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, Examples include triisocyanates such as
  • the polyisocyanate is partially reacted with an appropriate trimerization catalyst such as a tertiary amine, a phosphine, an alkoxide, a metal oxide, a carboxylate, or the like.
  • an appropriate trimerization catalyst such as a tertiary amine, a phosphine, an alkoxide, a metal oxide, a carboxylate, or the like.
  • Examples of the compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether glycols, polyester glycols, polycarbonate glycols, polyolefin glycols, and the like. Examples thereof include those alkoxylated with 25 alkyl groups and mixtures of two or more thereof.
  • Examples of the polyether glycol include polyether diol, polyether ester diol, and a mixture of two or more thereof.
  • polyether diol examples include those obtained by homo- or copolymerizing an alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. And mixtures of two or more of the above.
  • polyetherester diol examples include those obtained by reacting a mixture with an ether group-containing diol or another glycol with a dicarboxylic acid or an anhydride thereof, or reacting a polyester glycol with an alkylene oxide, such as poly (poly (Oxytetramethylene) adipate and the like.
  • the most preferred polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which a hydroxyl group at one end of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4 Pentanedio
  • Polycarbonate glycols include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, etc.
  • Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. Is mentioned. These may be used alone or in combination of two or more.
  • the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
  • Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Is preferably a hydrogen atom of the amino group.
  • the tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
  • Examples of such a compound having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-Dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.
  • examples of the nitrogen-containing heterocycle include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzoidyl ring.
  • 5-membered nitrogen-containing hetero ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, etc. Rings.
  • Preferred among these nitrogen-containing hetero rings are an imidazole ring and a triazole ring.
  • these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like.
  • Specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole and 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1.
  • the preferred compounding ratio of the raw materials for producing the urethane-based polymer dispersant is 10 to 200 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule per 100 parts by mass of the polyisocyanate compound. Parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass, of a compound having active hydrogen and a tertiary amino group in the same molecule. Parts by weight.
  • the production of the urethane polymer dispersant is performed according to a known method for producing a polyurethane resin.
  • the solvent for the production usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, secondary butanol, tertiary butanol, some alcohols such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl An aprotic polar solvent such as pyrrolidone and dimethyl sulfoxide is used. These may be used alone or in combination of two or
  • a urethanation reaction catalyst is used.
  • the catalyst include tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannas octoate, iron compounds such as iron acetylacetonate and ferric chloride, and triethylamine and triethylenediamine. Secondary amines and the like. These may be used alone or in combination of two or more.
  • the amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g.
  • the amine value is a value obtained by neutralizing and titrating a basic amino group with an acid and expressing the KOH in mg corresponding to the acid value. When the content is not less than the lower limit, the dispersing ability tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
  • the weight average molecular weight (Mw) of the urethane polymer dispersant is generally in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000.
  • Mw weight average molecular weight
  • the dispersibility and dispersion stability tend to be improved by setting the lower limit or more, and the solubility and dispersibility tend to be improved by setting the lower limit or less.
  • an unsaturated group-containing monomer having a functional group (here, the functional group is a functional group described above as a functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, and a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.
  • Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and 2- (meth) acrylic acid.
  • Unsaturated monomers having a carboxyl group such as loyloxyethyl hexahydrophthalic acid and acrylic acid dimer; tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof;
  • Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.
  • Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivative
  • the acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block having no functional group.
  • the block may include a partial structure derived from the unsaturated group-containing monomer containing no functional group. May be contained in the A block in any mode of random copolymerization or block copolymerization.
  • the content of the partial structure containing no functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
  • the B block is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more types of monomers. These may be contained in the B block in any mode of random copolymerization or block copolymerization.
  • the AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
  • the living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method.
  • the acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer may be used.
  • the / B block ratio is preferably from 1/99 to 80/20, particularly preferably from 5/95 to 60/40 (mass ratio). By keeping the ratio within this range, a balance between dispersibility and storage stability can be ensured. Tend. Further, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer which can be used in the present invention is usually preferably from 0.1 to 10 mmol. When the content is within the range, good dispersibility tends to be ensured.
  • such a block copolymer usually contains an amino group generated during the production process in some cases.
  • the amine value is about 1 to 100 mgKOH / g, and from the viewpoint of dispersibility, It is preferably at least 10 mgKOH / g, more preferably at least 30 mgKOH / g, still more preferably at least 50 mgKOH / g, preferably at most 90 mgKOH / g, more preferably at most 80 mgKOH / g, even more preferably at most 75 mgKOH / g.
  • the amine value of the block copolymer is preferably from 10 to 90 mgKOH / g, more preferably from 30 to 80 mgKOH / g, even more preferably from 50 to 75 mgKOH / g.
  • the amine value of the dispersant such as these block copolymers is represented by the mass of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method. 0.5-1.5 g of the dispersant sample is precisely weighed in a 100 mL beaker, and dissolved with 50 mL of acetic acid.
  • This solution is subjected to neutralization titration with a 0.1 mol / L HClO 4 acetic acid solution using an automatic titrator equipped with a pH electrode.
  • the amine value is determined by the following equation using the inflection point of the titration pH curve as the end point of the titration.
  • Amine value [mgKOH / g] (561 ⁇ V) / (W ⁇ S) [Where, W: weighed amount of dispersant sample [g], V: titer at the end of titration [mL], S: dispersant Indicates the solid content concentration [% by mass] of the sample. ]
  • the acid value of this block copolymer depends on the presence or absence and the type of the acidic group from which the acid value is derived, but is generally preferably lower, usually 10 mgKOH / g or less, and its weight average molecular weight (Mw ) Is preferably in the range of 1,000 to 100,000. When the content is in the above range, good dispersibility tends to be ensured.
  • the specific structure of the polymer dispersant is not particularly limited. However, from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter referred to as “repeating unit”) Unit (i) ”).
  • R 31 to R 33 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an optionally substituted aralkyl group; Two or more of R 31 to R 33 may combine with each other to form a cyclic structure; R 34 is a hydrogen atom or a methyl group; X is a divalent linking group; Y - is a counter anion.
  • the carbon number of the optionally substituted alkyl group in R 31 to R 33 in the above formula (i) is not particularly limited, but is preferably 1 or more, and more preferably 10 or less. It is more preferred that:
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
  • Group, pentyl group or hexyl group more preferably methyl group, ethyl group, propyl group or butyl group. Further, it may be linear or branched. Further, it may include a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.
  • the carbon number of the optionally substituted aryl group in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 12 It is more preferred that:
  • the aryl group preferably has 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
  • a phenyl group a methylphenyl group, an ethylphenyl group , A dimethylphenyl group or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
  • the carbon number of the optionally substituted aralkyl group in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, and 12 It is more preferred that:
  • the aralkyl group preferably has 7 to 16 carbon atoms, and more preferably 7 to 12 carbon atoms.
  • Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group.
  • R 31 to R 33 are each independently an alkyl group or an aralkyl group. Specifically, R 31 and R 33 are each independently a methyl group, Or an ethyl group, and R 32 is preferably a phenylmethyl group or a phenylethyl group, and more preferably, R 31 and R 33 are a methyl group, and R 32 is a phenylmethyl group. .
  • a repeating unit represented by the following formula (ii) (hereinafter, referred to as a “repeating unit (ii)” may be used. ) Is preferable.
  • R 35 and R 36 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
  • R 35 and R 36 may combine with each other to form a cyclic structure;
  • R 37 is a hydrogen atom or a methyl group;
  • Z is a divalent linking group.
  • alkyl group which may have a substituent in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.
  • optionally substituted aryl group in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.
  • aralkyl group which may have a substituent in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.
  • R 35 and R 36 are each independently preferably an alkyl group which may have a substituent, more preferably a methyl group or an ethyl group.
  • Examples of the substituent which the alkyl group, aralkyl group or aryl group of R 31 to R 33 of the above formula (i) and R 35 and R 36 of the above formula (ii) may have include a halogen atom, an alkoxy group, Examples include a benzoyl group and a hydroxyl group.
  • the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 43 — group, A —COOR 44 — group (where R 43 and R 44 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), and the like; Represents a —COO—R 44 — group.
  • examples of the counter anion Y ⁇ include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , and PF 6 ⁇ .
  • the content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (i) is represented by the formula (ii). It is preferably at most 60 mol%, more preferably at most 50 mol%, further preferably at most 40 mol%, particularly preferably at most 35 mol%, based on the total content of the repeating units. Further, it is preferably at least 5 mol%, more preferably at least 10 mol%, further preferably at least 20 mol%, particularly preferably at least 30 mol%.
  • the content ratio of the repeating unit represented by the formula (i) 5 with respect to the sum of the content ratio of the repeating unit represented by the formula (i) and the content ratio of the repeating unit represented by the formula (ii) 5 ⁇ 60 mol% is preferable, 10-50 mol% is more preferable, 20-40 mol% is further preferable, and 30-35 mol% is particularly preferable.
  • the content of the repeating unit represented by the formula (i) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and preferably 5 mol%, from the viewpoint of dispersibility. %, More preferably 10 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. Is more preferable, and it is particularly preferable that it is 15 mol% or less.
  • the content of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, and more preferably 10 to 20 mol%. More preferably, 10 to 15 mol% is particularly preferable.
  • the proportion of the repeating unit represented by the formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, and preferably 10 mol%, from the viewpoint of dispersibility. %, More preferably at least 15 mol%, particularly preferably at least 20 mol%, and preferably at most 60 mol%, and at most 40 mol%. Is more preferably 30 mol% or less, and particularly preferably 25 mol% or less.
  • the content of the repeating unit represented by the formula (ii) in all the repeating units of the polymer dispersant is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and more preferably 15 to 30 mol%. More preferably, it is particularly preferably 20 to 25 mol%.
  • the polymer dispersant enhances the compatibility with a binder component such as a solvent and improves the dispersion stability, so that the repeating unit represented by the following formula (iii) (hereinafter referred to as “the repeating unit (iii)”) is used. Is sometimes referred to as ").”
  • R 40 is an ethylene group or a propylene group;
  • R 41 is an optionally substituted alkyl group;
  • R 42 is a hydrogen atom or a methyl group;
  • n is an integer of 1 to 20.
  • the carbon number of the alkyl group which may have a substituent in R 41 of the formula (iii) is not particularly limited, but is preferably 1 or more, preferably 2 or more, and 10 or less. And more preferably 6 or less.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • the alkyl group may include a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
  • n is 1 or more, preferably 2 or more, more preferably 10 or less, and 5 or less from the viewpoint of compatibility and dispersibility with a binder component such as a solvent. Is more preferable.
  • n is preferably 1 to 10, more preferably 2 to 5.
  • the content of the repeating unit represented by the formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and more preferably 2 mol% or more. More preferably, it is 4 mol% or more, further preferably, 30 mol% or less, more preferably, 20 mol% or less, further preferably, 10 mol% or less.
  • compatibility with a binder component such as a solvent and dispersion stability tend to be compatible.
  • the content of the repeating unit represented by the formula (iii) in the total repeating units of the polymer dispersant is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and more preferably 4 to 10 mol%. More preferred.
  • the polymer dispersant has a repeating unit represented by the following formula (iv) (hereinafter referred to as a “repeating unit (iv) ) ").)).
  • R 38 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent;
  • R 39 is a hydrogen atom or a methyl group.
  • the carbon number of the optionally substituted alkyl group in R 38 in the formula (iv) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 4 or more. More preferably, it is preferably 10 or less, more preferably 8 or less.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably has 2 to 8 carbon atoms, and still more preferably has 4 to 8 carbon atoms.
  • the carbon number of the aryl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. More preferably, it is even more preferably 8 or less.
  • Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
  • a phenyl group a methylphenyl group, an ethylphenyl group , A dimethylphenyl group or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
  • the aryl group preferably has 6 to 16 carbon atoms, more preferably has 6 to 12 carbon atoms, and still more preferably has 8 to 12 carbon atoms.
  • the carbon number of the aralkyl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. More preferably, it is even more preferably 10 or less.
  • Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group.
  • the carbon number of the aralkyl group is preferably 7 to 16, more preferably 7 to 12, and even more preferably 7 to 10.
  • R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethyl group, from the viewpoint of solvent compatibility and dispersion stability.
  • substituent which the alkyl group may have in R 38 include a halogen atom and an alkoxy group.
  • the substituent which the aryl group or the aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.
  • the chain of the alkyl group represented by R 38 include any of linear and branched.
  • the content of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, and more preferably 40 mol% or more. Is more preferably 50 mol% or more, further preferably 80 mol% or less, more preferably 70 mol% or less.
  • the content of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and more preferably 50 to 70 mol%. More preferred.
  • the polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii), and the repeating unit (iv).
  • repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide; (Meth) acrylamide monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl ether crotonic acid; and repeating units derived from monomers such as N-methacryloylmorpholine.
  • the polymer dispersant has an A block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and a repeating unit (ii).
  • the block copolymer is preferably an AB block copolymer or a BAB block copolymer.
  • the repeating unit (i) and the repeating unit (ii) may be contained in any mode of random copolymerization and block copolymerization. Further, the repeating unit (i) and the repeating unit (ii) may each be contained in the A block in two or more types. In this case, each of the repeating units may be randomly copolymerized in the A block. It may be contained in any form of block copolymerization.
  • a repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block.
  • Examples of such a repeating unit include the above-mentioned (meth) acrylate ester-based unit. And repeating units derived from monomers.
  • the content of the repeating unit other than the repeating unit (i) and the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, it is not contained in the block.
  • a repeating unit other than the repeating units (iii) and (iv) may be contained in the B block, and examples of such a repeating unit include styrene monomers such as styrene and ⁇ -methylstyrene; (Meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; glycidyl crotonate Ether; a repeating unit derived from a monomer such as N-methacryloylmorpholine.
  • styrene monomers such as styrene and ⁇ -methylstyrene
  • (Meth) acrylate monomers such as (meth) acrylic acid chloride
  • (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide
  • the content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, it is not contained in the block.
  • the content thereof is not particularly limited, but is preferably 0.1% by mass or more in the total solid content of the photosensitive colored resin composition. , 0.5% by mass or more, more preferably 8% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, particularly preferably 2% by mass or less.
  • the content is not less than the lower limit, the generation of residues due to aggregates tends to be suppressed, and when the content is not more than the upper limit, ink repellency and developability tend to be improved.
  • the content of the (F) dispersant in the total solid content of the photosensitive colored resin composition is preferably 0.1 to 8% by mass, 0.1 to 5% by mass is more preferable, 0.5 to 3% by mass is more preferable, and 0.5 to 2% by mass is particularly preferable.
  • the photosensitive colored resin composition of the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber is added for the purpose of controlling the photo-curing distribution by absorbing a specific wavelength of a light source used for exposure with the ultraviolet absorber.
  • the ultraviolet absorber effects such as improving the perpendicularity of the side wall of the partition wall after development and eliminating residues remaining in the non-exposed area after development are obtained.
  • the ultraviolet absorber for example, a compound having an absorption maximum between a wavelength of 250 nm and 400 nm can be used from the viewpoint of inhibiting the light absorption of the photopolymerization initiator (A).
  • the ultraviolet absorber desirably contains one or both of a benzotriazole-based compound and a triazine-based compound.
  • a benzotriazole-based compound By including one or both of the benzotriazole-based compound and the triazine-based compound, the light absorption at the bottom of the film of the initiator is reduced, and the line width at the bottom of the coating film is reduced, so that the vertical effect on the side wall of the partition is reduced. It is thought that it can be obtained.
  • Benzotriazole compounds include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and 3- [3-tert-butyl- Octyl 5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) ) -4-Hydroxyphenyl] ethylhexyl propionate, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-tbutyl-5-methyl -2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxy) (Ciphenyl) benzotriazole, 2- (2'-
  • benzotriazole-based compounds examples include, for example, Sumisorb (registered trademark, the same applies hereinafter) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 ( JINHOKU INDUSTRIES), TINUVIN (registered trademark, the same applies hereinafter) @PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN @ 326, TINUVIN900, "TINUVIN @ 928", TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSOVER70BVER, 72VERVER , EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVE SORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured
  • triazine compounds examples include 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol and 2- [4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) -4 Reaction product of 2,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2-ethylhexyl glycidyl ether; 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- ( 2,4-dibutoxyphenyl) -1,3-5-triazine and the like.
  • a hydroxyphenyltriazine compound is preferable from the viewpoint of the verticality of the partition wall side surface and the ink repellency.
  • examples of commercially available triazine-based compounds include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (manufactured by BASF).
  • ultraviolet absorbers include benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, dyes and the like.
  • Sumisorb 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eiko Chemical Co., Ltd.), Tomissorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB103, SESEORB103, SESEORB103, SESEORB103 Benzophenone compounds such as SEESORB106, SEESORB107 and SEESORB151 (manufactured by Cipro Kasei); benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical) and phenyl salicylate; 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate and methoxy methoxycinnamate Cinnamic acid derivatives such as isoamyl
  • Anthracene and its derivatives azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, etc. Dyes; and the like.
  • cinnamic acid derivatives and naphthalene derivatives from the viewpoint of ink repellency, it is preferable to use cinnamic acid derivatives and naphthalene derivatives, and it is particularly preferable to use cinnamic acid derivatives.
  • These light absorbers can be used alone or in combination of two or more.
  • a benzotriazole compound and a hydroxyphenyltriazine compound are preferable, and a benzotriazole compound is particularly preferable.
  • one compound may be used alone, or two or more compounds may be used in combination.
  • the content ratio is not particularly limited, but is usually 0.01% by mass or more, preferably 0.01% by mass or more in the total solid content of the photosensitive colored resin composition. 0.05 mass% or more, more preferably 0.1 mass% or more, further preferably 0.5 mass% or more, particularly preferably 1 mass% or more, and usually 15 mass% or less, preferably 10 mass%. Or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.
  • the ratio is equal to or more than the lower limit, the verticality of the side wall of the partition tends to be good, and when the ratio is equal to or less than the upper limit, the ink repellency tends to increase.
  • the content ratio of the ultraviolet absorbent in the total solid content of the photosensitive colored resin composition is preferably 0.01 to 15% by mass, and 0.05 to 15% by mass. 10% by mass is more preferable, 0.1 to 5% by mass is more preferable, 0.5 to 3% by mass is further preferable, and 1 to 3% by mass is particularly preferable.
  • the compounding ratio of (A) the photopolymerization initiator is as follows: (A) the compounding amount of the ultraviolet absorber to 100 parts by mass of the photopolymerization initiator. Is usually at least 1 part by mass, preferably at least 10 parts by mass, more preferably at least 30 parts by mass, even more preferably at least 50 parts by mass, particularly preferably at least 80 parts by mass, usually at most 500 parts by mass, preferably at most 300 parts by mass. It is at most 200 parts by mass, more preferably at most 100 parts by mass, even more preferably at most 100 parts by mass.
  • the ratio When the ratio is equal to or more than the lower limit, the verticality of the side wall of the partition tends to be good, and when the ratio is equal to or less than the upper limit, the ink repellency tends to increase.
  • the amount of the ultraviolet absorber is preferably from 1 to 500 parts by mass, more preferably from 10 to 300 parts by mass, per 100 parts by mass of the photopolymerization initiator (A). It is more preferably 30 to 200 parts by mass, further preferably 50 to 100 parts by mass, and particularly preferably 80 to 100 parts by mass.
  • the photosensitive colored resin composition of the present invention preferably contains a polymerization inhibitor.
  • a polymerization inhibitor By containing a polymerization inhibitor, it inhibits radical polymerization, so that the taper angle of the obtained partition tends to be able to be increased.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT).
  • hydroquinone or methoxyphenol is preferred from the viewpoint of polymerization inhibition ability, and methylhydroquinone is more preferred.
  • the polymerization inhibitor preferably contains one or more kinds.
  • the polymerization inhibitor may be contained in the resin, and may be used as it is, or may be the same as the polymerization inhibitor contained in the resin. Alternatively, a different polymerization inhibitor may be added during the production of the photosensitive colored resin composition.
  • the photosensitive colored resin composition contains a polymerization inhibitor
  • its content is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass, in the total solid content of the photosensitive colored resin composition. It is at least 0.01% by mass, more preferably at least 0.01% by mass, and usually at most 0.1% by mass, preferably at most 0.08% by mass, more preferably at most 0.05% by mass.
  • the taper angle tends to be increased
  • the ink repellency tends to be high.
  • the content ratio of the polymerization inhibitor in the total solid content of the photosensitive colored resin composition is preferably 0.0005% by mass to 0.1%, more preferably 0.1% by mass. 001 to 0.08% by mass is more preferable, and 0.01 to 0.05% by mass is more preferable.
  • the photosensitive colored resin composition of the present invention may contain a thermal polymerization initiator.
  • a thermal polymerization initiator By containing a thermal polymerization initiator, the degree of crosslinking of the film tends to be increased.
  • Specific examples of such a thermal polymerization initiator include, for example, an azo compound, an organic peroxide, and hydrogen peroxide. These may be used alone or in combination of two or more.
  • the sum of the content ratios of the photopolymerization initiators in the photosensitive colored resin composition is preferably set to be the same as the content ratio of the photopolymerization initiator, and the combined use ratio of the photopolymerization initiator and the thermal polymerization initiator is determined based on 100 parts by mass of the photopolymerization initiator from the viewpoint of ink repellency.
  • the polymerization initiator is preferably used in an amount of 5 to 300 parts by mass.
  • the photosensitive colored resin composition of the present invention may contain an amino compound for accelerating thermosetting.
  • the content ratio of the amino compound is usually 40% by mass or less, preferably 30% by mass or less in the total solid content of the photosensitive colored resin composition. Further, it is usually 0.5% by mass or more, preferably 1% by mass or more.
  • the content is equal to or less than the upper limit, storage stability tends to be maintained, and when the content is equal to or more than the lower limit, sufficient thermosetting property tends to be secured.
  • the content of the photosensitive colored resin composition in the total solid content is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass. .
  • amino compound examples include, for example, an amino compound having a methylol group as a functional group and at least two alkoxymethyl groups obtained by subjecting it to alcohol condensation with 1 to 8 carbon atoms.
  • melamine resin obtained by polycondensation of melamine and formaldehyde
  • benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde
  • glycoluril resin obtained by polycondensation of glycoluril and formaldehyde
  • urea and formaldehyde Polycondensed urea resins
  • modified resins obtained by subjecting the above-mentioned resin to alcohol condensation modification of a methylol group.
  • a melamine resin and a modified resin thereof are preferable, a modified resin having a methylol group modification ratio of 70% or more is more preferable, and a modified resin of 80% or more is particularly preferable.
  • melamine resins and modified resins thereof include, for example, “Symel” (registered trademark, the same applies hereinafter) 300, 301, 303, 350, 736, 738, 370, 771, manufactured by Cytec Corporation. 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "Nikarac” (registered trademark, the same hereinafter) manufactured by Sanwa Chemical Co., Ltd. ) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302 and the like.
  • Examples of the benzoguanamine resin and its modified resin include “CYMEL” 1123, 1125, and 1128 manufactured by Cytec Corporation.
  • Examples of the glycoluril resin and its modified resin include “Symel” 1170, 1171, 1174, and 1172 manufactured by Cytec, and “Nikalac” MX-270 manufactured by Sanwa Chemical Co., Ltd.
  • Examples of the urea resin and its modified resin include “UFR” (registered trademark) 65, 300 manufactured by Scitech, and “Nikalac” MX-290 manufactured by Sanwa Chemical Co., Ltd.
  • silane Coupling Agent It is also preferable to add a silane coupling agent to the photosensitive colored resin composition of the present invention in order to improve adhesion to a substrate.
  • a silane coupling agent various types such as an epoxy type, a methacrylic type, an amino type, and an imidazole type can be used. From the viewpoint of improving the adhesion, an epoxy type or imidazole type silane coupling agent is particularly preferable. The content thereof is usually 20% by mass or less, preferably 15% by mass or less in the total solid content of the photosensitive colored resin composition from the viewpoint of adhesion.
  • the photosensitive colored resin composition of the present invention is further improved in strength as a cured product, and has an appropriate interaction with an alkali-soluble resin (formation of a matrix structure).
  • an inorganic filler may be contained. Examples of such an inorganic filler include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, and those obtained by treating these with various silane coupling agents.
  • the average particle size of these inorganic fillers is usually 0.005 to 2 ⁇ m, preferably 0.01 to 1 ⁇ m.
  • the average particle size referred to in the present embodiment is a value measured by a laser diffraction scattering particle size distribution measuring device such as manufactured by Beckman Coulter.
  • silica sol and silica sol-modified products are particularly preferred because they tend to have an excellent effect of improving the taper angle together with the dispersion stability.
  • the content thereof is usually 5% by mass or more, preferably 10% by mass or more in the total solid content from the viewpoint of ink repellency. And is usually 80% by mass or less, preferably 70% by mass or less.
  • the content of the photosensitive colored resin composition in the total solid content is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass.
  • the photosensitive colored resin composition of the present invention may contain a phosphoric acid-based ethylenic monomer for the purpose of imparting adhesion to a substrate.
  • a phosphoric acid-based ethylenic monomer (meth) acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2), and (g3) are preferable.
  • R 51 represents a hydrogen atom or a methyl group
  • l and l ′ are integers of 1 to 10
  • m is 1, 2 or 3.
  • the content ratio is usually preferably 0.02% by mass or more, more preferably 0.05% by mass or more, based on the total solid content of the photosensitive colored resin composition. 1% by mass or more is more preferable, and 0.2% by mass or more is particularly preferable. Further, it is preferably 4% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, particularly preferably 1% by mass or less.
  • the content of the photosensitive colored resin composition in the total solid content is preferably 0.02 to 4% by mass, and 0.05 to 4% by mass.
  • the content is more preferably 3% by mass, further preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass.
  • the photosensitive colored resin composition of the present invention usually contains a solvent, and is used in a state where the above-mentioned components are dissolved or dispersed in the solvent.
  • the solvent is not particularly limited, and examples thereof include the organic solvents described below.
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, Triethylene glycol mono Chirueteru, glycol monoalkyl ethers such as tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, di
  • the solvent which can dissolve or disperse each component in the photosensitive colored resin composition, is selected according to the method of using the photosensitive colored resin composition of the present invention, from the viewpoint of applicability It is preferable to select one having a boiling point in the range of 60 to 280 ° C. under atmospheric pressure. More preferably, it has a boiling point of 70 ° C. or more and 260 ° C. or less, for example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate.
  • the proportion of the total solid content in the photosensitive colored resin composition is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more. It is preferably used so as to be usually 90% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less.
  • the amount is equal to or more than the lower limit, the occurrence of coating unevenness tends to be suppressed, and when the amount is equal to or less than the upper limit, the occurrence of foreign matter, repelling, or the like tends to be suppressed.
  • the proportion of the solvent in the photosensitive colored resin composition is preferably from 10 to 90% by mass, more preferably from 15 to 50% by mass, still more preferably from 20 to 40% by mass, particularly preferably from 25 to 40% by mass. Preferably, it is used in an amount of up to 35% by mass.
  • the photosensitive colored resin composition of the present invention is prepared by mixing the above components with a stirrer.
  • a solvent or a solvent-insoluble component such as a pigment
  • the dispersion treatment is preferably performed in a system in which (D) a colorant, a solvent, and (F) a dispersant, and (B) a part or all of an alkali-soluble resin are used in combination (hereinafter referred to as dispersion treatment).
  • the mixture and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”).
  • the step of producing the photosensitive colored resin composition it is preferable to produce a pigment dispersion containing at least (D) a colorant, a solvent, and (F) a dispersant.
  • a colorant organic solvent, and (F) dispersant that can be used in the pigment dispersion
  • those described as being usable in the photosensitive coloring resin composition can be preferably used.
  • the content ratio of each colorant in the colorant (D) in the pigment dispersion those described as the content ratio in the photosensitive colored resin composition can be preferably employed.
  • the colorant (D) is dispersed by a sand grinder
  • glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used.
  • the dispersing conditions are generally such that the temperature is from 0 ° C to 100 ° C, preferably from room temperature to 80 ° C.
  • the dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, and the like. Controlling the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the photosensitive colored resin composition falls within the range of 50 to 300 is a measure of dispersion.
  • the dispersed particle size of the pigment dispersed in the ink is usually from 0.03 to 0.3 ⁇ m, and is measured by a dynamic light scattering method or the like.
  • the ink obtained by the dispersion treatment and the other components contained in the photosensitive colored resin composition are mixed to form a uniform solution.
  • fine dust may be mixed in the liquid. Therefore, it is desirable that the obtained photosensitive colored resin composition is subjected to a filtration treatment with a filter or the like.
  • Partition wall and method for forming the same By curing the photosensitive colored resin composition of the present invention, the cured product of the present invention can be obtained.
  • the photosensitive colored resin composition of the present invention can be used for forming a partition, and can be particularly suitably used for forming a partition for partitioning an organic layer of an organic electroluminescent element.
  • the method for forming the partition wall using the photosensitive colored resin composition described above is not particularly limited, and a conventionally known method can be employed.
  • a photosensitive colored resin composition is applied on a substrate, a coating step of forming a photosensitive colored resin composition layer, and an exposure step of exposing the photosensitive colored resin composition layer
  • a photosensitive colored resin composition whose viscosity is adjusted by dilution with a solvent or the like is used as an ink, and ink droplets are ejected onto a substrate by an ink-jet method along a predetermined partition pattern to form a photosensitive colored resin.
  • the composition is applied on a substrate to form an uncured partition pattern.
  • the pattern of the uncured partition is exposed to form a cured partition on the substrate.
  • the exposure of the uncured partition wall pattern is performed in the same manner as the exposure step in the photolithography method described below, except that a mask is not used.
  • the photosensitive colored resin composition is applied to the entire surface of the substrate where the partition is to be formed to form a photosensitive colored resin composition layer. After the formed photosensitive colored resin composition layer is exposed according to a predetermined partition pattern, the exposed photosensitive colored resin composition layer is developed to form a partition on the substrate.
  • a contact transfer type application device such as a roll coater, a reverse coater, a bar coater, or a spinner (rotating) is applied on the substrate on which the partition is to be formed.
  • Type coating apparatus applying the photosensitive colored resin composition using a non-contact type coating apparatus such as a curtain flow coater, and, if necessary, removing the solvent by drying to form a photosensitive colored resin composition layer. I do.
  • the photosensitive colored resin composition is irradiated with active energy rays such as ultraviolet rays and excimer laser light using a negative type mask, and the photosensitive colored resin composition layer is formed in accordance with the pattern of the bank. Expose partially.
  • a light source that emits ultraviolet light such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used.
  • the exposure amount varies depending on the composition of the photosensitive colored resin composition, but is preferably, for example, about 10 to 400 mJ / cm 2 .
  • the photosensitive colored resin composition layer exposed according to the pattern of the partition is developed with a developer to form the partition.
  • the developing method is not particularly limited, and an immersion method, a spray method, or the like can be used.
  • Specific examples of the developing solution include organic ones such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. No. Further, an antifoaming agent or a surfactant can be added to the developer.
  • post-baking is applied to the partition walls after development, and heat curing is performed.
  • Post-baking is preferably performed at 150 to 250 ° C. for 15 to 60 minutes.
  • the substrate used for forming the partition is not particularly limited, and is appropriately selected according to the type of the organic electroluminescent device manufactured using the substrate on which the partition is formed.
  • Suitable substrate materials include glass and various resin materials.
  • Specific examples of the resin material include polyester such as polyethylene terephthalate; polyolefin such as polyethylene and polypropylene; polycarbonate; poly (meth) methacrylic resin; polysulfone; and polyimide.
  • these materials for the substrate glass and polyimide are preferable because of their excellent heat resistance.
  • a transparent electrode layer of ITO, ZnO, or the like may be provided in advance on the surface of the substrate on which the partition wall is formed, depending on the type of the organic electroluminescent device to be manufactured.
  • Organic electroluminescent device of the present invention includes a partition wall composed of the above-described photosensitive colored resin composition.
  • Various organic electroluminescent devices are manufactured using the substrate provided with the partition pattern manufactured by the method described above.
  • the method of forming the organic electroluminescent element is not particularly limited, but preferably, after forming a pattern of the partition on the substrate by the above-described method, injecting ink into a region surrounded by the partition on the substrate to form a pixel or the like. By forming an organic layer, an organic electroluminescent device is manufactured.
  • the partition has a skirt shape
  • the ink for forming the organic layer is repelled at the skirt portion of the partition, so that the region surrounded by the partition may not be sufficiently covered with the ink for forming the organic layer.
  • the area surrounded by the partition can be sufficiently covered with the ink for forming an organic layer.
  • Water, an organic solvent, and a mixed solvent thereof can be used as a solvent used when forming an ink for forming an organic layer.
  • the organic solvent is not particularly limited as long as it can be removed from the film formed after the injection of the ink.
  • Specific examples of the organic solvent include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, and butyl acetate, 3-phenoxytoluene, And the like.
  • a surfactant, an antioxidant, a viscosity modifier, an ultraviolet absorber, and the like can be added to the ink.
  • an ink jet method is preferable because a small amount of ink can be easily injected into a predetermined place.
  • the ink used to form the organic layer is appropriately selected according to the type of the organic electroluminescent device to be manufactured.
  • the viscosity of the ink is not particularly limited as long as the ink can be discharged well from the ink-jet head, but is preferably 4 to 20 mPa ⁇ s, more preferably 5 to 10 mPa ⁇ s.
  • the viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, and the like.
  • Examples of the type of the organic electroluminescent device include a bottom emission type and a top emission type.
  • a partition is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer are laminated on an opening surrounded by the partition.
  • the top emission type for example, a partition is formed on a glass substrate on which a metal electrode layer is stacked, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the partition. Created.
  • an organic electroluminescent layer as described in Japanese Patent Application Laid-Open No. 2009-146691 or Japanese Patent No. 5734681 can be used. Further, quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
  • the image display device of the present invention includes the cured product of the present invention, and particularly includes the organic display device of the present invention.
  • the image display device can be assembled in a usual manner using, for example, an active driving type organic electroluminescent device.
  • the image display device of the present invention is formed by a method as described in “Organic EL Display” (Ohm Co., published on August 20, 2004, Shizuki Tokito, Chihaya Adachi, Hideyuki Murata). can do.
  • an image may be displayed by combining an organic electroluminescent element that emits white light and a color filter, or may be displayed by combining organic electroluminescent elements that emit light of different colors such as RGB.
  • the illumination of the present invention includes the cured product of the present invention, and particularly includes the organic electroluminescent device of the present invention.
  • the type and structure are not particularly limited, and can be assembled according to a conventional method using the organic electroluminescent device of the present invention.
  • the organic electroluminescent element may be of a simple matrix drive type or of an active matrix drive type. In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. Further, organic electroluminescent elements having different emission colors may be combined to be configured so that the respective colors are mixed to form white, or a configuration in which the mixture ratio can be adjusted to provide a toning function.
  • the photosensitive colored resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples unless it exceeds the gist.
  • Alkali-soluble resin-I> An equal amount of acrylic acid and glycidyl methacrylate are added to a copolymer resin containing dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.3 / 0.1 / 0.6) as a constituent monomer.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 9000, and the acid value was 80 mgKOH / g.
  • PGMEA propylene glycol monomethyl ether acetate
  • Dispersant-I> "BYK-LPN21116" manufactured by BYK-Chemie (acrylic AB comprising an A block having a quaternary ammonium base and a tertiary amino group in a side chain and a B block having no quaternary ammonium base and a tertiary amino group) (Block copolymer, amine value 70 mgKOH / g, acid value 1 mgKOH / g or less.)
  • the A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains a repeating unit of the following formula (3a).
  • the content of the repeating units of the following formulas (1a), (2a) and (3a) in the total repeating units of Dispersant-I was 11.1 mol%, 22.2 mol% and 6.7 mol%, respectively. It is.
  • ⁇ Photopolymerization initiator-1> A compound having the following chemical structure was used. When this compound was dissolved in PGMEA to a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm was 34 times the absorbance at 368 nm, which is the maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm. %Met. This corresponds to the oxime ester-based photopolymerization initiator (A1).
  • ⁇ Photopolymerization initiator-4> A compound having the following chemical structure, obtained by the method described in Synthesis Example 2 of JP-A-2018-002962, was used. The absorbance at a wavelength of 400 nm was 33% of the absorbance at 368 nm, which is the maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm. This corresponds to the oxime ester-based photopolymerization initiator (A1).
  • ⁇ Photopolymerization initiator-5> A compound having the following chemical structure was used. When this compound was dissolved in PGMEA at a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm was 1% of the absorbance at 328 nm, which is the maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm. 0.1%. This corresponds to the oxime ester-based photopolymerization initiator (A2).
  • ⁇ Photopolymerization initiator-6> An IRGACURE OXE-02 manufactured by BASF was used. When this compound is dissolved in PGMEA at a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm is 0% relative to the absorbance at 336 nm, which is the maximum absorption wavelength ( ⁇ max ) between 300 and 400 nm. 0.1%. This corresponds to the oxime ester-based photopolymerization initiator (A2).
  • ⁇ Preparation of pigment dispersion liquid 1> The pigment, the dispersant, the alkali-soluble resin, and the solvent shown in Table 1 were mixed so as to have the mass ratio shown in Table 1.
  • the amounts of the dispersant and the alkali-soluble resin in Table 1 are solid contents, and the amount of the solvent includes the amount of the dispersant and the solvent derived from the alkali-soluble resin.
  • This solution was subjected to a dispersion treatment at 25 to 45 ° C. for 3 hours using a paint shaker.
  • zirconia beads having a diameter of 0.5 mm were used, and a mass 2.5 times that of the dispersion was added. After the completion of the dispersion treatment, the beads and the dispersion were separated by a filter to prepare a pigment dispersion 1.
  • the weighted average value (%) of the absorbance at 400 nm indicates the value (%) of the absorbance at a wavelength of 400 nm of the oxime ester-based photopolymerization initiator (A3) in the second embodiment of the present invention.
  • Example 5 22.34 parts by mass of the photopolymerizable compound-I of Example 1 was changed to 11.17 parts by mass of the photopolymerizable compound-I and 11.17 parts by mass of the photopolymerizable compound-II.
  • a photosensitive colored resin composition having the same composition as in Example 5 was prepared as Example 5.
  • a photosensitive colored resin composition was applied on a glass substrate so as to have a thickness of 6.0 ⁇ m after heat curing. Then, it was dried by heating on a hot plate at 100 ° C. for 90 seconds to obtain a coated substrate. Next, an aqueous solution in which 0.04% by mass of KOH and 0.07% by mass of Emulgen A-60 (a surfactant manufactured by Kao Corporation) were dissolved was developed without exposing the obtained coated substrate to ultraviolet light. The solution was spray-developed at 24 ° C., and the time required for complete development and removal of the coating film was read and defined as the break time.
  • Emulgen A-60 a surfactant manufactured by Kao Corporation
  • the coating substrate separately prepared under the same conditions as above was exposed to ultraviolet light at an exposure amount of 50 mJ / cm 2 using a high-pressure mercury lamp without using a mask.
  • the intensity at a wavelength of 365 nm was 45 mW / cm 2 .
  • This substrate was subjected to a developing process for 1.6 times the break time under the same developing solution and developing conditions as described above, and then washed with pure water for 10 seconds.
  • This substrate was cured by heating at 230 ° C. for 30 minutes in an oven to obtain a substrate for measuring a contact angle.
  • the photosensitive colored resin composition was applied on a glass substrate using a spinner so as to have a thickness of 6.0 ⁇ m after heat curing. Then, it was dried by heating on a hot plate at 100 ° C. for 90 seconds to obtain a coated substrate. Next, the obtained coated substrate was exposed to ultraviolet light with a high-pressure mercury lamp using a photomask. The exposure amount was 50 mJ / cm 2 and the exposure gap was 130 ⁇ m. At this time, the intensity at a wavelength of 365 nm was 45 mW / cm 2 .
  • the photomask used was an exposure mask having line-shaped openings of various widths with an opening width of 5 to 50 ⁇ m (5 to 20 ⁇ m: every 1 ⁇ m, 25 to 50 ⁇ m: every 5 ⁇ m).
  • a development process is performed for a development time 1.6 times the break time, followed by washing with pure water for 10 seconds and heating in an oven at 230 ° C. for 30 minutes. After curing, a linear pattern substrate assuming partition walls was prepared.
  • oxime ester-based photopolymerization initiators having an absorption band at i-line those that can also use h-line, that is, the absorbance at a wavelength of 400 nm is sufficiently high
  • a method using an oxime ester-based photopolymerization initiator (A1) is exemplified.
  • the oxime ester-based photopolymerization initiator (A1) and the oxime ester-based photopolymerization initiator (A2) as in Examples 1 to 4 the oxime ester-based photopolymerization initiator (A1) alone is used.
  • the absorption rate of h-rays in the upper part of the coating film can be made relatively lower than that in the case of (i), that is, the h-rays can be transmitted to the lower part of the coating film, and the coating film can be formed It is considered that the curing using the h-line at the lower portion is promoted, and the perpendicularity of the taper of the partition wall is improved.
  • oxime ester-based photopolymerization initiator (A1) and the oxime ester-based photopolymerization initiator (A2) in combination, curing using i-line and h-line is performed near the film surface, and the ink repellency is improved. Is also considered to be sufficient.

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Abstract

A photosensitive colored resin composition is provided that has high ink repellency, and with which it is possible to form a partition wall having a good taper shape. This photosensitive colored resin composition contains a photopolymerization initiator (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a coloring agent (D), and a liquid-repelling agent (E), wherein the photopolymerization initiator (A) contains: an oxime ester-based photopolymerization initiator (A1) having absorbance at a wavelength of 400 nm of 20% or more in relation to the absorbance at a maximum absorbance wavelength (λmax) within the range of 300-400 nm; and an oxime ester-based photopolymerization initiator (A2) having absorbance at a wavelength of 400 nm of 10% or less in relation to the absorbance at a maximum absorbance wavelength (λmax) within the range of 300-400 nm, and the liquid-repelling agent (E) contains a fluorine-atom-containing resin having a crosslinking group.

Description

感光性着色樹脂組成物、硬化物、画像表示装置及び照明Photosensitive colored resin composition, cured product, image display device, and illumination
　本発明は、感光性着色樹脂組成物に関し、さらに感光性着色樹脂組成物を硬化させた硬化物や、該硬化物を含む画像表示装置及び照明に関する。
　２０１８年７月２０日に日本国特許庁に出願された日本国特願２０１８－１３６４９１の明細書、特許請求の範囲、図面及び要約書の全内容、並びに、本明細書で引用された文献等に開示された内容の一部又は全部をここに引用し、本明細書の開示内容として取り入れる。 The present invention relates to a photosensitive colored resin composition, and more particularly, to a cured product obtained by curing the photosensitive colored resin composition, and an image display device and an illumination including the cured product.
Description of Japanese Patent Application No. 2018-136491, filed with the Japan Patent Office on July 20, 2018, the entire contents of the claims, drawings, and abstract, and references cited in this specification Some or all of the contents disclosed in the above are cited here, and are incorporated as the disclosure contents of the present specification.
　従来から、有機電界ディスプレイや有機電界照明などに含まれる有機電界発光素子は、基板上に、隔壁（バンク）を形成した後に、隔壁に囲まれた領域内に、種々の機能層を積層して製造されている。このような隔壁を容易に形成する方法として、感光性樹脂組成物を用いたフォトリソグラフィー法により形成する方法が知られている。 2. Description of the Related Art Conventionally, an organic electroluminescent element included in an organic electric field display or an organic electric field lighting is formed by forming a partition (bank) on a substrate and then laminating various functional layers in a region surrounded by the partition. Being manufactured. As a method for easily forming such a partition, a method for forming the partition by a photolithography method using a photosensitive resin composition is known.
　また、隔壁に囲まれた領域内に種々の機能層を積層する方法としては、まず機能層を構成する材料を含むインクを調製し、次いで、調製したインクを隔壁に囲まれた領域（画素領域）内に注入する方法が知られている。この方法の中でも、所定量のインクを所定の箇所に正確に注入しやすいことから、インクジェット法が採用されることが多い。 In addition, as a method of laminating various functional layers in a region surrounded by the partition, first, an ink containing a material constituting the functional layer is prepared, and then the prepared ink is placed in a region surrounded by the partition (pixel region). A method for injecting into) is known. Among these methods, an ink-jet method is often employed because a predetermined amount of ink can be accurately injected into a predetermined location.
　さらに、インクを用いて機能層を形成する場合、隔壁へのインクの付着の予防や、隣接する領域間に注入されるインク同士が混合されることを防ぐ目的等で、隔壁に撥インク性を付与することが求められる場合がある。
　また近年、隔壁には撥インク性以外にも種々の特性が要求されており、種々の感光性樹脂組成物が開発されている。例えば、コントラストの向上や反射防止の観点から、着色隔壁の要求がなされている。特許文献１には、２種類の特定のアルカリ可溶性樹脂を含み、固形分酸価が特定範囲のネガ型感光性樹脂組成物を用いることで、微細なラインパターンと微小なコンタクトホールをともに有する隔壁の形成が可能であり、現像に用いるアルカリ現像液に対して、含有する黒色有機顔料の分散性が良好であるとともに、それ自体の貯蔵安定性が良好となることが記載されている。特許文献２には、特定の撥インク剤と特定の光重合開始剤を含むネガ型感光性樹脂組成物を用いることで、ミラープロジェクション（ＭＰＡ）方式においても撥インク性が良好となり、マスクの線幅の再現が良好となることが記載されている。 Further, when the functional layer is formed using ink, the partition walls are provided with ink repellency for the purpose of preventing the adhesion of the ink to the partition walls and preventing the ink injected between the adjacent regions from being mixed with each other. Granting may be required.
Further, in recent years, various characteristics other than ink repellency are required for the partition walls, and various photosensitive resin compositions have been developed. For example, colored barrier ribs have been demanded from the viewpoint of improving contrast and preventing reflection. Patent Document 1 discloses a partition having both a fine line pattern and a fine contact hole by using a negative photosensitive resin composition containing two specific alkali-soluble resins and having a solid content acid value of a specific range. It is described that the black organic pigment contained therein has good dispersibility with respect to an alkali developing solution used for development and also has good storage stability per se. Patent Document 2 discloses that by using a negative photosensitive resin composition containing a specific ink repellent agent and a specific photopolymerization initiator, the ink repellency is improved even in the mirror projection (MPA) method, and the mask line is improved. It describes that the reproduction of the width is good.
国際公開第２０１３／０６９７８９号International Publication No. WO 2013/069789 国際公開第２０１２／１４７６２６号International Publication No. 2012/147626
　近年、着色隔壁の開発が精力的になされており、例えば、溶剤溶解性の低い成分を含有するインクを用いて所定の膜厚の機能層を形成するためには、着色隔壁で囲まれた領域に希薄なインクを多量に注入する必要があり、自ずと厚膜の着色隔壁が求められる。
　そういった厚膜の着色隔壁においても、隣接する領域間におけるインク同士の混合等を防ぐために、より高い撥インク性を示すことが求められる。また、画素領域に均一にインクが広がり、エッジ部に塗布不良やムラのない均一な機能層を形成するためには、隔壁側面が垂直なテーパ形状であることが望ましい。厚膜になるほど現像により隔壁側面が部分的に現像されて凹凸ができやすくなるため、厚膜になるほど凹凸が少なく垂直なテーパ形状にすることが求められている。 In recent years, development of colored partition walls has been energetically performed. For example, in order to form a functional layer having a predetermined thickness using an ink containing a component having low solvent solubility, a region surrounded by the colored partition walls is required. It is necessary to inject a large amount of dilute ink into the ink, and a thick-film colored partition wall is naturally required.
Even such a thick-walled colored partition wall is required to exhibit higher ink repellency in order to prevent mixing of inks between adjacent regions. In addition, in order to uniformly spread the ink in the pixel region and form a uniform functional layer without coating defects and unevenness at the edge portion, it is desirable that the side wall of the partition wall has a vertical tapered shape. As the thickness of the film increases, the side surfaces of the partition walls are partially developed by development, so that irregularities are likely to be formed.
　本発明者らが検討したところ、特許文献１に記載されている感光性着色樹脂組成物では厚膜の隔壁においては、高い撥インク性と良好なテーパ形状の両立が困難であることが見出された。
　一方で、特許文献２に記載の感光性着色樹脂組成物では塗膜下部に比べて塗膜表面が硬化しすぎてしまい、垂直なテーパ形状にならないことが見出された。 The present inventors have studied and found that it is difficult to achieve both high ink repellency and a good tapered shape in a thick-film partition wall in the photosensitive colored resin composition described in Patent Document 1. Was done.
On the other hand, with the photosensitive colored resin composition described in Patent Document 2, it has been found that the surface of the coating film is excessively hardened as compared with the lower portion of the coating film, and does not have a vertical tapered shape.
　そこで本発明は、上記事情に鑑みてなされたものであり、即ち、撥インク性が高く、かつ、テーパ形状が良好な隔壁を形成することが可能である、感光性着色樹脂組成物を提供することを目的とする。
　また、本発明は、前記感光性着色樹脂組成物を硬化させた硬化物、該硬化物を含む画像表示装置及び照明を提供することを目的とする。 Accordingly, the present invention has been made in view of the above circumstances, that is, to provide a photosensitive colored resin composition which has high ink repellency and is capable of forming a partition having a good tapered shape. The purpose is to:
Another object of the present invention is to provide a cured product obtained by curing the photosensitive colored resin composition, an image display device including the cured product, and illumination.
　本発明者らが鋭意検討した結果、着色剤及び撥液剤を含有する感光性着色樹脂組成物において、特定のオキシムエステル系光重合開始剤を組み合わせることで上記課題を解決できることを見出し、本発明を完成するに至った。
　即ち本発明の要旨は以下の通りである。 As a result of intensive studies by the present inventors, in a photosensitive colored resin composition containing a colorant and a liquid repellent, it has been found that the above problem can be solved by combining a specific oxime ester-based photopolymerization initiator, and the present invention It was completed.
That is, the gist of the present invention is as follows.
［１］　（Ａ）光重合開始剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、（Ｄ）着色剤、及び（Ｅ）撥液剤を含有する感光性着色樹脂組成物であって、
　前記（Ａ）光重合開始剤が、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して２０％以上であるオキシムエステル系光重合開始剤（Ａ１）と、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して１０％以下であるオキシムエステル系光重合開始剤（Ａ２）を含有し、
　前記（Ｅ）撥液剤が、架橋基を有するフッ素原子含有樹脂を含有することを特徴とする感光性着色樹脂組成物。 [1] A photosensitive colored resin composition containing (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent. ,
(A) an oxime ester-based photopolymerization initiator (A1), wherein the photopolymerization initiator has an absorbance at a wavelength of 400 nm of 20% or more with respect to the absorbance at a maximum absorption wavelength (λ max ) of 300 to 400 nm. An oxime ester-based photopolymerization initiator (A2) whose absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm,
(E) The photosensitive colored resin composition, wherein the liquid repellent comprises a fluorine atom-containing resin having a crosslinking group.
［２］　前記オキシムエステル系光重合開始剤（Ａ１）が、ニトロ基及びカルバゾール骨格を有するオキシムエステル系光重合開始剤を含む、［１］に記載の感光性着色樹脂組成物。
［３］　前記オキシムエステル系光重合開始剤（Ａ２）が、下記一般式（Ａ２－１）で表される化合物を含む、［１］又は［２］に記載の感光性着色樹脂組成物。 [2] The photosensitive colored resin composition according to [1], wherein the oxime ester-based photopolymerization initiator (A1) includes an oxime ester-based photopolymerization initiator having a nitro group and a carbazole skeleton.
[3] The photosensitive colored resin composition according to [1] or [2], wherein the oxime ester-based photopolymerization initiator (A2) contains a compound represented by the following general formula (A2-1).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
（式（Ａ２－１）中、Ｒ13Aは、置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。
　Ｒ14Aは、アルキル基、又は芳香族環基を表す。
　Ｒ15Aは、１価の置換基を表す。
　ｎは０又は１を表す。
　ｈは０～２の整数を表す。） (In the formula (A2-1), R 13A represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R 14A represents an alkyl group or an aromatic ring group.
R 15A represents a monovalent substituent.
n represents 0 or 1.
h represents an integer of 0 to 2. )
［４］　前記式（Ａ２－１）において、Ｒ14Aが芳香族環基である、［３］に記載の感光性着色樹脂組成物。 [4] The photosensitive colored resin composition according to [3], wherein in the formula (A2-1), R 14A is an aromatic ring group.
［５］　（Ａ）光重合開始剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、（Ｄ）着色剤、及び（Ｅ）撥液剤を含有する感光性着色樹脂組成物であって、
　前記（Ａ）光重合開始剤が、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して８～３０％であるオキシムエステル系光重合開始剤（Ａ３）を含有し、
　前記（Ｅ）撥液剤が、架橋基を有するフッ素原子含有樹脂を含有することを特徴とする感光性着色樹脂組成物。 [5] A photosensitive colored resin composition containing (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent. ,
The oxime ester-based photopolymerization initiator (A3), wherein the photopolymerization initiator (A) has an absorbance at a wavelength of 400 nm of 8 to 30% of an absorbance at a maximum absorption wavelength (λ max ) of 300 to 400 nm. Containing
(E) The photosensitive colored resin composition, wherein the liquid repellent comprises a fluorine atom-containing resin having a crosslinking group.
［６］　前記架橋基を有するフッ素原子含有樹脂が、パーフルオロアルキル基及びパーフルオロアルキレンエーテル鎖のいずれか一方又は両方を有する、［１］～［５］のいずれかに記載の感光性着色樹脂組成物。
［７］　前記（Ｄ）着色剤が、赤色顔料及び橙色顔料からなる群から選ばれる少なくとも１種と、青色顔料及び紫色顔料からなる群から選ばれる少なくとも１種とを含有する、［１］～［６］のいずれかに記載の感光性着色樹脂組成物。 [6] The photosensitive colored resin according to any one of [1] to [5], wherein the fluorine atom-containing resin having a crosslinking group has one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. Composition.
[7] The colorant (D) contains at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and purple pigments, [1] to The photosensitive colored resin composition according to any one of [6].
［８］　前記（Ｄ）着色剤が、下記一般式（１）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含む有機黒色顔料を含有する、［１］～［７］のいずれかに記載の感光性着色樹脂組成物。 [8] The colorant (D) is selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound. The photosensitive colored resin composition according to any one of [1] to [7], comprising an organic black pigment containing at least one kind.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（式（１）中、Ｒ11及びＲ16は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ17、Ｒ18、Ｒ19及びＲ20は各々独立に、水素原子、ハロゲン原子、Ｒ21、ＣＯＯＨ、ＣＯＯＲ21、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲ21、ＣＯＮＲ21Ｒ22、ＣＮ、ＯＨ、ＯＲ21、ＣＯＣＲ21、ＯＯＣＮＨ2、ＯＯＣＮＨＲ21、ＯＯＣＮＲ21Ｒ22、ＮＯ2、ＮＨ2、ＮＨＲ21、ＮＲ21Ｒ22、ＮＨＣＯＲ22、ＮＲ21ＣＯＲ22、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲ21、Ｎ＝ＣＲ21Ｒ22、ＳＨ、ＳＲ21、ＳＯＲ21、ＳＯ2Ｒ21、ＳＯ3Ｒ21、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲ21又はＳＯ2ＮＲ21Ｒ22を表し；
Ｒ12とＲ13、Ｒ13とＲ14、Ｒ14とＲ15、Ｒ17とＲ18、Ｒ18とＲ19、及びＲ19とＲ20からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲ21ブリッジによって互いに結合してもよく；
Ｒ21及びＲ22は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。） (In the formula (1), R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, a halogen atom, R 21 , COOH, COOR 21 , COO − , CONH 2 , CONHR 21 , CONR 21 R 22 , CN, OH, OR 21 , COCR 21 , OOCNH 2 , OOCNHR 21 , OOCNR 21 R 22 , NO 2 , NH 2 , NHR 21 , NR 21 R 22 , NHCOR 22 , NR 21 COR 22 , N = CH 2 , N = CHR 21 , N = CR 21 R 22 , SH, SR 21 , SOR 21 , SO 2 R 21 , SO 3 R 21 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR Represents 21 or SO 2 NR 21 R 22 ;
R 12 and R 13, at least one combination selected from R 13 and R 14, R 14 and R 15, the group consisting of R 17 and R 18, R 18, R 19, and R 19 and R 20 are each other directly May be linked together or may be linked to each other by an oxygen, sulfur, NH or NR 21 bridge;
R 21 and R 22 are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or Represents 2 to 12 alkynyl groups. )
［９］　隔壁形成用である、［１］～［８］のいずれかに記載の感光性着色樹脂組成物。

［１０］　［１］～［９］のいずれかに記載の感光性着色樹脂組成物を硬化させた硬化物。
［１１］　［１０］に記載の硬化物を含む画像表示装置。
［１２］　［１０］に記載の硬化物を含む照明。 [9] The photosensitive colored resin composition according to any one of [1] to [8], for forming a partition.

[10] A cured product obtained by curing the photosensitive colored resin composition according to any one of [1] to [9].
[11] An image display device including the cured product according to [10].
[12] An illumination comprising the cured product according to [10].
　本発明により、撥インク性が高く、かつ、テーパ形状が良好な隔壁を形成することが可能である、感光性着色樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a photosensitive colored resin composition having high ink repellency and capable of forming a partition having a good tapered shape.
図１はライン状パターンのテーパの垂直性評価の説明図である。FIG. 1 is an explanatory diagram of the evaluation of the perpendicularity of the taper of the linear pattern.
　以下、本発明を詳細に説明する。なお、以下の記載は本発明の実施形態の一例であり、本発明はその要旨を超えない限り、これらに特定されない。
　なお、本発明において、「（メタ）アクリル」とは、「アクリル及びメタクリルのいずれか一方又は両方」を意味するものとし、また、「全固形分」とは、感光性着色樹脂組成物における溶剤以外の全成分を意味するものとする。さらに、本発明において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　また、本発明において、「（共）重合体」とは、単一重合体（ホモポリマー）と共重合体（コポリマー）の双方を含むことを意味し、また、「（酸）無水物」、「（無水）…酸」とは、酸とその無水物の双方を含むことを意味する。
　本発明において、隔壁材とはバンク材、壁材、ウォール材をさし、同様に、隔壁とはバンク、壁、ウォールをさす。
　本発明において、重量平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量（Ｍｗ）をさす。
　本発明において、酸価とは、特に断りのない限り有効固形分換算の酸価を表し、中和滴定により算出される。 Hereinafter, the present invention will be described in detail. Note that the following description is an example of an embodiment of the present invention, and the present invention is not limited thereto without departing from the gist thereof.
In the present invention, “(meth) acryl” means “one or both of acryl and methacryl”, and “total solid content” means a solvent in the photosensitive colored resin composition. Means all components other than. Further, in the present invention, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
Further, in the present invention, the “(co) polymer” means including both a homopolymer and a copolymer, and further includes “(acid) anhydride”, “ (Anhydrous) ... acid "means to include both an acid and its anhydride.
In the present invention, the partition material means a bank material, a wall material, and a wall material, and similarly, the partition material means a bank, a wall, and a wall.
In the present invention, the weight average molecular weight means a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
In the present invention, the acid value represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
　本発明において隔壁とは、例えば、アクティブ駆動型有機電界発光素子における機能層（有機層）を区画するためのものであり、区画された領域（画素領域）に機能層を構成するための材料であるインクを吐出、乾燥することで、機能層及び隔壁からなる画素等を形成させていくために使用されるものである。 In the present invention, the partition is, for example, for partitioning a functional layer (organic layer) in an active drive type organic electroluminescent element, and is a material for forming the functional layer in a partitioned region (pixel region). It is used to form pixels comprising a functional layer and partition walls by discharging and drying a certain ink.
［１］感光性着色樹脂組成物
　本発明の感光性着色樹脂組成物は、（Ａ）光重合開始剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、（Ｄ）着色剤、及び（Ｅ）撥液剤を必須成分として含有し、さらに必要に応じてその他の成分を含んでいてもよく、例えば溶剤等を含んでいてもよい。 [1] Photosensitive colored resin composition The photosensitive colored resin composition of the present invention comprises (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) It may contain a liquid repellent as an essential component, and may further contain other components as necessary, for example, may contain a solvent or the like.
　本発明の第１の態様に係る感光性着色樹脂組成物は、（Ａ）光重合開始剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、（Ｄ）着色剤、及び（Ｅ）撥液剤を含有する感光性着色樹脂組成物であって、前記（Ａ）光重合開始剤が、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して２０％以上であるオキシムエステル系光重合開始剤（Ａ１）と、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して１０％以下であるオキシムエステル系光重合開始剤（Ａ２）を含有し、前記（Ｅ）撥液剤が、架橋基を有するフッ素原子含有樹脂を含有する。 The photosensitive colored resin composition according to the first aspect of the present invention comprises (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E). A photosensitive colored resin composition containing a liquid-repellent agent, wherein the (A) photopolymerization initiator has an absorbance at a wavelength of 400 nm of 20 to an absorbance at a maximum absorption wavelength (λ max ) of 300 to 400 nm. % Of an oxime ester-based photopolymerization initiator (A1) and an oxime ester-based photopolymerization wherein the absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm. It contains an initiator (A2), and the liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.
　本発明の第２の態様に係る感光性着色樹脂組成物は、（Ａ）光重合開始剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、（Ｄ）着色剤、及び（Ｅ）撥液剤を含有する感光性着色樹脂組成物であって、前記（Ａ）光重合開始剤が、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して８～３０％であるオキシムエステル系光重合開始剤（Ａ３）を含有し、前記（Ｅ）撥液剤が、架橋基を有するフッ素原子含有樹脂を含有する。 The photosensitive colored resin composition according to the second aspect of the present invention comprises (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E). A photosensitive colored resin composition containing a liquid-repellent agent, wherein the (A) photopolymerization initiator has an absorbance at a wavelength of 400 nm of 8 to an absorbance at a maximum absorption wavelength (λ max ) of 300 to 400 nm. It contains an oxime ester-based photopolymerization initiator (A3) in an amount of up to 30%, and the liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.
　以下、特に断りがない限り、「本発明の感光性着色樹脂組成物」は、前記第１の態様に係る感光性着色樹脂組成物と、第２の態様に係る感光性着色樹脂組成物の両方を指す。 Hereinafter, unless otherwise specified, the “photosensitive colored resin composition of the present invention” includes both the photosensitive colored resin composition according to the first aspect and the photosensitive colored resin composition according to the second aspect. Point to.
［１－１］感光性着色樹脂組成物の成分および組成
　本発明の感光性着色樹脂組成物を構成する成分およびその組成について順に説明する。 [1-1] Components and Composition of Photosensitive Colored Resin Composition Components constituting the photosensitive colored resin composition of the present invention and the composition thereof will be described in order.
［１－１－１］（Ａ）成分；光重合開始剤
　本発明の感光性着色樹脂組成物は、（Ａ）光重合開始剤を含有する。（Ａ）光重合開始剤は、活性光線により（Ｃ）光重合性化合物を重合させる、例えば、（Ｃ）光重合性化合物が有するエチレン性不飽和結合を重合させる化合物であれば特に限定されない。 [1-1-1] (A) Component; Photopolymerization Initiator The photosensitive colored resin composition of the present invention contains (A) a photopolymerization initiator. The photopolymerization initiator (A) is not particularly limited as long as it is a compound that polymerizes the photopolymerizable compound (C) with actinic rays, for example, a compound that polymerizes the ethylenically unsaturated bond of the photopolymerizable compound (C).
　本発明の第１の態様に係る感光性着色樹脂組成物における（Ａ）光重合開始剤は、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して２０％以上であるオキシムエステル系光重合開始剤（Ａ１）（以下、「オキシムエステル系光重合開始剤（Ａ１）」と略記する場合がある。）と、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して１０％以下であるオキシムエステル系光重合開始剤（Ａ２）（以下、「オキシムエステル系光重合開始剤（Ａ２）」と略記する場合がある。）を含有する。 The photopolymerization initiator (A) in the photosensitive colored resin composition according to the first embodiment of the present invention has an absorbance at a wavelength of 400 nm which is 20 times the absorbance at the maximum absorption wavelength (λ max ) between 300 and 400 nm. % Of the oxime ester-based photopolymerization initiator (A1) (hereinafter sometimes abbreviated as “oxime ester-based photopolymerization initiator (A1)”) at a wavelength of 400 nm between 300 and 400 nm. The oxime ester-based photopolymerization initiator (A2) (hereinafter, may be abbreviated as “oxime ester-based photopolymerization initiator (A2)”) having an absorbance of 10% or less with respect to the absorbance at the maximum absorption wavelength (λ max ). ).
　隔壁に撥インク性を付与するためには、隔壁の表面に撥液剤を固定させることが必要になる。しかしながら、紫外線露光後の塗膜の硬化度が不十分だと、現像処理時に膜表面の一部が溶解し、撥液剤が現像液に流れ出てしまう。光重合開始剤として、主にｉ線を利用するオキシムエステル系光重合開始剤（Ａ２）を単独で用いた場合には、紫外線露光後の硬化が不十分なため撥インク性が損なわれる。 た め In order to impart ink repellency to the partition, it is necessary to fix a liquid repellent on the surface of the partition. However, if the degree of curing of the coating film after the exposure to ultraviolet light is insufficient, a part of the film surface is dissolved during the developing treatment, and the lyophobic agent flows out into the developing solution. When the oxime ester-based photopolymerization initiator (A2) mainly using i-ray is used alone as the photopolymerization initiator, the ink repellency is impaired due to insufficient curing after exposure to ultraviolet light.
　紫外線露光による硬化度を上げるためには、ｉ線に吸収帯を有するオキシムエステル系光重合開始剤の中でも、ｈ線も利用可能なもの、つまり、波長４００ｎｍにおける吸光度が十分に高いオキシムエステル系光重合開始剤（Ａ１）を用いる方法が挙げられる。 In order to increase the degree of curing by ultraviolet light exposure, among oxime ester-based photopolymerization initiators having an absorption band at i-line, those which can also use h-line, that is, oxime ester-based light having sufficiently high absorbance at a wavelength of 400 nm A method using a polymerization initiator (A1) is exemplified.
　一方で例えば、厚膜パターンを形成する場合には、紫外線露光時に塗膜表面から侵入した紫外線は、塗膜に含まれる光重合開始剤や着色剤等によって吸収され、塗膜内部まで透過しにくく、塗膜上部に比べて塗膜下部の硬化度が低くなりやすい。そのため、現像処理時に硬化度の低い塗膜下部が過度に現像されてそのパターン幅が細くなるということがある。 On the other hand, for example, in the case of forming a thick film pattern, ultraviolet light that has entered from the surface of the coating film when exposed to ultraviolet light is absorbed by a photopolymerization initiator or a coloring agent contained in the coating film, and is hardly transmitted to the inside of the coating film. The degree of curing of the lower part of the coating film tends to be lower than the upper part of the coating film. For this reason, the lower part of the coating film having a low degree of curing may be excessively developed during the development processing, and the pattern width may be reduced.
　オキシムエステル系光重合開始剤（Ａ１）を単独で使用した場合には、塗膜上部における硬化性向上によって撥インク性は高くなるものの、ｈ線の多くが塗膜上部でオキシムエステル系光重合開始剤（Ａ１）に吸収されてしまい、塗膜下部に到達するｈ線は少なくなり、塗膜上部に比べて塗膜下部のパターン幅が細くなり、隔壁側面のテーパの垂直性がさらに損なわれる。 When the oxime ester-based photopolymerization initiator (A1) is used alone, although the ink repellency increases due to the improvement in the curability at the top of the coating film, most of the h-rays start the oxime ester-based photopolymerization at the top of the coating film. The h-line that is absorbed by the agent (A1) and reaches the lower part of the coating film is reduced, the pattern width of the lower part of the coating film becomes narrower than that of the upper part of the coating film, and the perpendicularity of the taper on the side wall of the partition is further impaired.
　そこで、オキシムエステル系光重合開始剤（Ａ１）とオキシムエステル系光重合開始剤（Ａ２）を組み合わせることで、オキシムエステル系光重合開始剤（Ａ１）単独の場合に比べて、塗膜上部におけるｈ線の吸収率を相対的に低くできる、つまり、塗膜下部までｈ線を透過させることができ、オキシムエステル系光重合開始剤（Ａ１）によってガラス基板近傍でのｈ線を利用した硬化が推進され、隔壁側面のテーパの垂直性が良好になると考えられる。また、オキシムエステル系光重合開始剤（Ａ１）とオキシムエステル系光重合開始剤（Ａ２）とを併用することで、膜表面近傍ではｉ線及びｈ線を利用した硬化が行われ、撥インク性が十分となると考えられる。 Therefore, by combining the oxime ester-based photopolymerization initiator (A1) and the oxime ester-based photopolymerization initiator (A2), the h in the upper part of the coating film is higher than when the oxime ester-based photopolymerization initiator (A1) is used alone. The line absorptivity can be relatively lowered, that is, h-line can be transmitted to the lower part of the coating film, and curing using h-line near the glass substrate is promoted by the oxime ester-based photopolymerization initiator (A1). It is considered that the verticality of the taper on the side wall of the partition is improved. In addition, by using the oxime ester-based photopolymerization initiator (A1) and the oxime ester-based photopolymerization initiator (A2) in combination, curing using i-line and h-line is performed near the film surface, and the ink repellency is improved. Is considered to be sufficient.
［１－１－１－１］オキシムエステル系光重合開始剤（Ａ１）
　オキシムエステル系光重合開始剤（Ａ１）は、波長３００～４００ｎｍ間に吸収極大を有し、かつ、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して２０％以上である。このようにオキシムエステル系光重合開始剤（Ａ１）は、波長４００ｎｍにおいて十分な吸光度を有するものであり、高圧水銀灯の発する紫外線のうち、ｉ線だけでなくｈ線をも十分に利用して硬化反応を促進させることができると考えられる。 [1-1-1-1] Oxime ester photopolymerization initiator (A1)
The oxime ester-based photopolymerization initiator (A1) has an absorption maximum at a wavelength of 300 to 400 nm, and the absorbance at a wavelength of 400 nm is higher than the absorbance at a maximum absorption wavelength (λ max ) of 300 to 400 nm. 20% or more. As described above, the oxime ester-based photopolymerization initiator (A1) has a sufficient absorbance at a wavelength of 400 nm, and is cured by sufficiently utilizing not only the i-line but also the h-line among the ultraviolet rays emitted from the high-pressure mercury lamp. It is believed that the reaction can be accelerated.
　オキシムエステル系光重合開始剤（Ａ１）の波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して２０％以上であれば特に限定されないが、２５％以上が好ましく、３０％以上がより好ましく、３２％以上がさらに好ましく、３５％以上がよりさらに好ましく、４０％以上が特に好ましく、また、８０％以下が好ましく、７０％以下がより好ましく、６０％以下がさらに好ましく、５０％以下がよりさらに好ましく、４０％以下が特に好ましい。前記下限値以上とすることで撥インク性が高くなる傾向があり、また、前記上限値以下とすることで隔壁側面のテーパ形状が良好となる傾向がある。例えば、オキシムエステル系光重合開始剤（Ａ１）の波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して２０～８０％が好ましく、２５～７０％がより好ましく、３０～６０％がさらに好ましく、３０～５０％がよりさらに好ましく、３２～４０％が特に好ましい。 The absorbance of the oxime ester-based photopolymerization initiator (A1) at a wavelength of 400 nm is not particularly limited as long as it is 20% or more with respect to the absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm, but 25% or more. It is preferably at least 30%, more preferably at least 32%, still more preferably at least 35%, particularly preferably at least 40%, preferably at most 80%, more preferably at most 70%, and at most 60%. More preferably, it is still more preferably 50% or less, particularly preferably 40% or less. When the amount is not less than the lower limit, the ink repellency tends to be high, and when the amount is not more than the upper limit, the tapered shape of the side wall of the partition tends to be good. For example, the absorbance of the oxime ester-based photopolymerization initiator (A1) at a wavelength of 400 nm is preferably from 20 to 80%, more preferably from 25 to 70%, with respect to the absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm. Preferably, it is more preferably from 30 to 60%, still more preferably from 30 to 50%, particularly preferably from 32 to 40%.
　また、オキシムエステル系光重合開始剤（Ａ１）の波長３００～４００ｎｍ間の極大吸収波長（λmax）は特に限定されないが、３２０ｎｍ以上が好ましく、３４０ｎｍ以上がより好ましく、３６０ｎｍ以上がさらに好ましく、また、３９０ｎｍ以下が好ましく、３８０ｎｍ以下がより好ましく、３７０ｎｍ以下が特に好ましい。前記下限値以上とすることで撥インク性が高くなる傾向があり、また、前記上限値以下とすることで隔壁側面のテーパ形状が良好となる傾向がある。例えば、オキシムエステル系光重合開始剤（Ａ１）の波長３００～４００ｎｍ間の極大吸収波長（λmax）は３２０～３９０ｎｍが好ましく、３４０～３８０ｎｍがより好ましく、３６０～３７０ｎｍがさらに好ましい。 The maximum absorption wavelength (λ max ) of the oxime ester-based photopolymerization initiator (A1) between 300 and 400 nm is not particularly limited, but is preferably 320 nm or more, more preferably 340 nm or more, still more preferably 360 nm or more. 390 nm or less, more preferably 380 nm or less, and particularly preferably 370 nm or less. When the amount is not less than the lower limit, the ink repellency tends to be high, and when the amount is not more than the upper limit, the tapered shape of the side wall of the partition tends to be good. For example, the maximum absorption wavelength (λ max ) of the oxime ester-based photopolymerization initiator (A1) between 300 and 400 nm is preferably from 320 to 390 nm, more preferably from 340 to 380 nm, and still more preferably from 360 to 370 nm.
　オキシムエステル系光重合開始剤（Ａ１）の吸光度及び極大吸収波長の測定は、まずオキシムエステル系光重合開始剤（Ａ１）の０．０１質量％のＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）溶液を作成し、それに分光光度計で波長３００～４００ｎｍの光を照射して１ｎｍおきに測定して得ることができる。分光光度計としては、例えばＵＶ－３０００シリーズ（島津製作所社製）、Ｖ－７００シリーズ（日本分光社製）などが挙げられるが、これに限定されるものではない。測定セルとしては、１ｃｍ角の石英セルを使用することができる。 The measurement of the absorbance and the maximum absorption wavelength of the oxime ester-based photopolymerization initiator (A1) was performed by first preparing a 0.01% by mass PGMEA (propylene glycol monomethyl ether acetate) solution of the oxime ester-based photopolymerization initiator (A1). It can be obtained by irradiating it with light having a wavelength of 300 to 400 nm with a spectrophotometer, and measuring the light every 1 nm. Examples of the spectrophotometer include, but are not limited to, UV-3000 series (manufactured by Shimadzu Corporation) and V-700 series (manufactured by JASCO Corporation). As the measurement cell, a 1 cm square quartz cell can be used.
　オキシムエステル系光重合開始剤（Ａ１）は波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して２０％以上のものであるが、波長４００ｎｍにおける吸光度が高いものとしては、例えば、フルオレン骨格やカルバゾール骨格にニトロ基等の電子吸引性基が結合したものを有するものが挙げられ、ニトロ基及びカルバゾール骨格を有するオキシムエステル系光重合開始剤が好ましい。 The oxime ester-based photopolymerization initiator (A1) has an absorbance at a wavelength of 400 nm of at least 20% of the absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm, but has a high absorbance at a wavelength of 400 nm. Examples thereof include those having an electron-withdrawing group such as a nitro group bonded to a fluorene skeleton or a carbazole skeleton, and an oxime ester-based photopolymerization initiator having a nitro group and a carbazole skeleton is preferable.
　オキシムエステル系光重合開始剤（Ａ１）の化学構造は特に限定されないが、撥インク性やテーパ形状の観点から、下記一般式（Ａ１－１）で表される化学構造を有する化合物であることが好ましい。 The chemical structure of the oxime ester-based photopolymerization initiator (A1) is not particularly limited, but may be a compound having a chemical structure represented by the following general formula (A1-1) from the viewpoint of ink repellency and tapered shape. preferable.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（式（Ａ１－１）中、Ｒ1A、Ｒ3A、Ｒ4A、Ｒ5A、Ｒ6A及びＲ8Aは各々独立に、水素原子、ニトロ基、アルキル基、又は芳香族環基を表す。
　Ｒ2A及びＲ7Aは各々独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族環基、ニトロ基、又は下記一般式（Ａ１－２）で表される１価の基を表す。ただし、Ｒ2A及びＲ7Aのいずれか一方又は両方が、下記一般式（Ａ１－２）で表される１価の基である。
　Ｒ1A～Ｒ8Aのうち、少なくとも１つ以上はニトロ基である。
　Ｒ9Aは、水素原子、又はアルキル基を表す。
　ｍ及びｎは各々独立に、０又は１を表す。） (In the formula (A1-1), R 1A , R 3A , R 4A , R 5A , R 6A and R 8A each independently represent a hydrogen atom, a nitro group, an alkyl group, or an aromatic ring group.
R 2A and R 7A are each independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, a nitro group, or a compound represented by the following general formula (A1-2) ) Represents a monovalent group. However, one or both of R 2A and R 7A are a monovalent group represented by the following general formula (A1-2).
At least one of R 1A to R 8A is a nitro group.
R 9A represents a hydrogen atom or an alkyl group.
m and n each independently represent 0 or 1. )
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（式（Ａ１－２）中、Ｒ11Aは、アルキル基、又は芳香族環基を表す。
　Ｒ12Aは、置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。） (In the formula (A1-2), R 11A represents an alkyl group or an aromatic ring group.
R 12A represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. )
（Ｒ1A、Ｒ3A、Ｒ4A、Ｒ5A、Ｒ6A及びＲ8A）
　上記式（Ａ１－１）中のＲ1A、Ｒ3A、Ｒ4A、Ｒ5A、Ｒ6A及びＲ8Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、通常１以上であり、また、８以下が好ましく、６以下がより好ましい。前記下限値以上とすることで溶剤への溶解性が高くなる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。例えば、アルキル基の炭素数は１～８が好ましく、１～６がより好ましい。 (R 1A , R 3A , R 4A , R 5A , R 6A and R 8A )
The alkyl group represented by R 1A , R 3A , R 4A , R 5A , R 6A and R 8A in the above formula (A1-1) may be a straight-chain, branched-chain, or cyclic-alkyl group. There may be. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 8 or less, more preferably 6 or less. When the content is not less than the lower limit, the solubility in the solvent tends to be high, and when the content is not more than the upper limit, the ink repellency tends to be high. For example, the alkyl group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、撥インク性の観点から、メチル基、エチル基、プロピル基であることが好ましく、メチル基であることがより好ましい。 Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, from the viewpoint of ink repellency, a methyl group, It is preferably an ethyl group or a propyl group, and more preferably a methyl group.
　上記式（Ａ１－１）のＲ1A、Ｒ3A、Ｒ4A、Ｒ5A、Ｒ6A及びＲ8Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。その炭素数は特に限定されないが、通常４以上であり、６以上が好ましく、また、２０以下が好ましく、１２以下がより好ましい。前記下限値以上とすることで溶剤への溶解性が高くなる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。例えば、芳香族環基の炭素数は４～２０が好ましく、４～１２がより好ましい。
　芳香族環基の具体例としては、フェニル基、ナフチル基、アントラセニル基、チエニル基、フリル基、ベンゾチエニル基、ベンゾフリル基などが挙げられ、これらの中でも、撥インク性の観点からフェニル基であることがより好ましい。 Examples of the aromatic ring group represented by R 1A , R 3A , R 4A , R 5A , R 6A and R 8A in the formula (A1-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Although the carbon number is not particularly limited, it is usually 4 or more, preferably 6 or more, more preferably 20 or less, and more preferably 12 or less. When the content is not less than the lower limit, the solubility in the solvent tends to be high, and when the content is not more than the upper limit, the ink repellency tends to be high. For example, the aromatic ring group preferably has 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms.
Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, an anthracenyl group, a thienyl group, a furyl group, a benzothienyl group, and a benzofuryl group. Among these, a phenyl group is preferred from the viewpoint of ink repellency. Is more preferable.
　これらの中でも、撥インク性の観点から、Ｒ1A、Ｒ3A、Ｒ4A、Ｒ5A、Ｒ6A及びＲ8Aは各々独立に水素原子又はニトロ基であることが好ましく、水素原子であることがより好ましい。 Among these, from the viewpoint of ink repellency, R 1A , R 3A , R 4A , R 5A , R 6A and R 8A are each independently preferably a hydrogen atom or a nitro group, and more preferably a hydrogen atom. preferable.
（Ｒ2A及びＲ7A）
　上記式（Ａ１－１）のＲ2A及びＲ7Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、通常１以上であり、また、８以下が好ましく、６以下がより好ましい。前記下限値以上とすることで溶剤への溶解性が高くなる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。例えば、アルキル基の炭素数は１～８が好ましく、１～６がより好ましい。 (R 2A and R 7A )
The alkyl group for R 2A and R 7A in the above formula (A1-1) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 8 or less, more preferably 6 or less. When the content is not less than the lower limit, the solubility in the solvent tends to be high, and when the content is not more than the upper limit, the ink repellency tends to be high. For example, the alkyl group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、撥インク性の観点から、メチル基、エチル基、プロピル基であることが好ましく、メチル基であることがより好ましい。
　アルキル基が有していてもよい置換基としては、水酸基、カルボキシル基などが挙げられ、現像性の観点から水酸基が好ましい。 Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, from the viewpoint of ink repellency, a methyl group, It is preferably an ethyl group or a propyl group, and more preferably a methyl group.
Examples of the substituent which the alkyl group may have include a hydroxyl group and a carboxyl group, and a hydroxyl group is preferable from the viewpoint of developability.
　上記式（Ａ１－１）のＲ2A及びＲ7Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。その炭素数は特に限定されないが、通常４以上であり、６以上が好ましく、１０以上がより好ましく、また、２０以下が好ましく、１２以下がより好ましい。前記下限値以上とすることで溶剤への溶解性が高くなる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。例えば、芳香族環基の炭素数は４～２０が好ましく、４～１２がより好ましい。 Examples of the aromatic ring group for R 2A and R 7A in the formula (A1-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is not particularly limited, but is usually 4 or more, preferably 6 or more, more preferably 10 or more, and preferably 20 or less, more preferably 12 or less. When the content is not less than the lower limit, the solubility in the solvent tends to be high, and when the content is not more than the upper limit, the ink repellency tends to be high. For example, the aromatic ring group preferably has 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms.
　芳香族環基の具体例としては、フェニル基、ナフチル基、アントラセニル基、チエニル基、フリル基、ベンゾチエニル基、ベンゾフリル基などが挙げられる。これらの中でも、撥インク性の観点からフェニル基、ナフチル基であることがより好ましい。
　芳香族環基が有していてもよい置換基としては、水酸基、アルキル基などが挙げられ、現像性の観点からアルキル基が好ましい。 Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, an anthracenyl group, a thienyl group, a furyl group, a benzothienyl group and a benzofuryl group. Among these, a phenyl group and a naphthyl group are more preferable from the viewpoint of ink repellency.
Examples of the substituent which the aromatic ring group may have include a hydroxyl group and an alkyl group, and an alkyl group is preferable from the viewpoint of developability.
　上記式（Ａ１－１）において、Ｒ2A及びＲ7Aのいずれか又は両方が、前記一般式（Ａ１－２）で表される１価の基である。 In the formula (A1-1), one or both of R 2A and R 7A is a monovalent group represented by the general formula (A1-2).
　上記式（Ａ１－２）のＲ11Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、通常１以上であり、また、５以下が好ましく、３以下がより好ましい。前記上限値以下とすることで感度が良好となる傾向がある。例えば、アルキル基の炭素数は１～５が好ましく、１～３がより好ましい。
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ペンチル基などが挙げられ、これらの中でも撥インク性の観点から、メチル基が好ましい。 The alkyl group for R 11A in the formula (A1-2) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 5 or less, more preferably 3 or less. When the content is not more than the upper limit, the sensitivity tends to be good. For example, the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a pentyl group. Among them, a methyl group is preferable from the viewpoint of ink repellency.
　Ｒ11Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、通常４以上であり、５以上が好ましく、また、３０以下が好ましく、２０以下がより好ましく、１２以下がさらに好ましい。前記下限値以上とすることで溶剤への溶解性が良好となる傾向があり、また、前記上限値以下とすることでテーパ形状が良好となる傾向がある。例えば、芳香族環基の炭素数は４～３０が好ましく、４～２０がより好ましく、５～１２がさらに好ましい。 Examples of the aromatic ring group for R 11A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. When the content is not less than the lower limit, the solubility in a solvent tends to be good, and when the content is not more than the upper limit, the tapered shape tends to be good. For example, the number of carbon atoms in the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, and even more preferably 5 to 12.
　芳香族環基の具体例としては、フェニル基、ナフチル基、チエニル基、フリル基などが挙げられ、これらの中でもテーパ形状の観点から、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。 具体 Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a thienyl group, a furyl group, and the like. Among them, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of a tapered shape.
　これらの中でもＲ11Aは撥インク性の観点から、アルキル基が好ましく、メチル基がより好ましい。 Among them, R 11A is preferably an alkyl group, more preferably a methyl group, from the viewpoint of ink repellency.
　Ｒ12Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、通常１以上であり、３以上が好ましく、５以上がより好ましく、６以上がさらに好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましく、８以下がよりさらに好ましく、７以下が特に好ましい。前記下限値以上とすることで溶剤への溶解性が良好となる傾向があり、前記上限値以下とすることで現像性が良好となる傾向がある。例えば、アルキル基の炭素数は１～２０が好ましく、３～１５がより好ましく、５～１０がさらに好ましく、５～８がよりさらに好ましく、５～７が特に好ましい。
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、シクロペンチル基、シクロヘキシル基などが挙げられ、これらの中でも現像性の観点から、イソペンチル基、へキシル基、ヘプチル基が好ましく、ヘプチル基がより好ましい。
　アルキル基が有していてもよい置換基としては、芳香族環基、水酸基、カルボキシル基などが挙げられ、合成容易性の観点からは、無置換であることが好ましい。 The alkyl group for R 12A may be linear, branched, cyclic, or a combination thereof. The carbon number of the alkyl group is not particularly limited, but is usually 1 or more, preferably 3 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and more preferably 10 or less. It is still more preferably 8 or less, further preferably 7 or less. When the content is not less than the lower limit, the solubility in the solvent tends to be good, and when the content is not more than the upper limit, the developability tends to be good. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 3 to 15, more preferably 5 to 10, still more preferably 5 to 8, and particularly preferably 5 to 7.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, a cyclopentyl group, and a cyclohexyl group. , An isopentyl group, a hexyl group, and a heptyl group are preferable, and a heptyl group is more preferable.
Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, and the like. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
　Ｒ12Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、通常４以上であり、５以上が好ましい。また、３０以下が好ましく、２０以下がより好ましく、１２以下がさらに好ましい。前記下限値以上とすることで溶剤への溶解性が良好となる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。芳香族環基の炭素数は４～３０が好ましく、４～２０がより好ましく、４～１２がさらに好ましく、５～１２がよりさらに好ましい。 Examples of the aromatic ring group for R 12A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more. Further, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less. When the content is not less than the lower limit, solubility in a solvent tends to be good, and when the content is not more than the upper limit, developability tends to be good. The number of carbon atoms in the aromatic ring group is preferably from 4 to 30, more preferably from 4 to 20, still more preferably from 4 to 12, and even more preferably from 5 to 12.
　芳香族環基の具体例としては、フェニル基、ナフチル基、チエニル基、フリル基などが挙げられ、これらの中でも現像性の観点から、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。
　芳香族環基が有していてもよい置換基としては、水酸基、アルキル基、アルコキシ基、アルコキシ基で置換されたアルコキシ基、水酸基で置換されたアルコキシ基などが挙げられる。これらの中でも現像性の観点からアルキル基、アルコキシ基で置換されたアルコキシ基、又は水酸基で置換されたアルコキシ基が好ましい。芳香族環基が有していてもよい置換基におけるアルキル基としては、炭素数１～６のアルキルが挙げられ、炭素数１～４のアルキルが好ましく、炭素数１～３のアルキルがより好ましく、メチルが特に好ましい。芳香族環基が有していてもよい置換基におけるアルコキシ基、及び芳香族環基が有していてもよい置換基におけるアルコキシ基上に置換するアルコキシ基としては、炭素数１～８のアルコキシが挙げられ、炭素数１～６のアルコキシが好ましく、炭素数１～４のアルコキシがより好ましい。 Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a thienyl group, and a furyl group. Of these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of developability.
Examples of the substituent which the aromatic ring group may have include a hydroxyl group, an alkyl group, an alkoxy group, an alkoxy group substituted with an alkoxy group, an alkoxy group substituted with a hydroxyl group, and the like. Among these, an alkoxy group substituted with an alkyl group or an alkoxy group, or an alkoxy group substituted with a hydroxyl group is preferable from the viewpoint of developability. Examples of the alkyl group in the substituent which the aromatic ring group may have include alkyl having 1 to 6 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, and more preferably alkyl having 1 to 3 carbon atoms. And methyl are particularly preferred. The alkoxy group in the substituent which the aromatic ring group optionally has and the alkoxy group which is substituted on the alkoxy group in the substituent which the aromatic ring group may have may be an alkoxy group having 1 to 8 carbon atoms. The alkoxy having 1 to 6 carbon atoms is preferable, and the alkoxy having 1 to 4 carbon atoms is more preferable.
　また、上記式（Ａ１－１）において、ｍ及びｎは各々独立に０又は１を表すが、接触角の観点からは０が好ましく、一方でテーパ形状の観点からは１が好ましい。 In the above formula (A1-1), m and n each independently represent 0 or 1, but 0 is preferable from the viewpoint of the contact angle, and 1 is preferable from the viewpoint of the tapered shape.
　これらの中でも、撥インク性の観点から、Ｒ2A及びＲ7Aが各々独立にニトロ基又は前記一般式（Ａ１－２）で表される１価の基であることが好ましく、Ｒ2Aがニトロ基であり、かつ、Ｒ7Aが前記一般式（Ａ１－２）で表される１価の基であることがより好ましい。 Among these, from the viewpoint of ink repellency, it is preferable that R 2A and R 7A are each independently a nitro group or a monovalent group represented by formula (A1-2), and R 2A is a nitro group. And R 7A is more preferably a monovalent group represented by the general formula (A1-2).
（ニトロ基）
　Ｒ1A～Ｒ8Aのうち、少なくとも１つ以上はニトロ基である。
　Ｒ1A～Ｒ8Aのうち、ニトロ基の数は特に限定されないが、通常１以上であり、４以下が好ましく、３以下がより好ましく、２以下がさらに好ましい。前記上限値以下とすることで現像性が良好となる傾向がある。ニトロ基の数としては１～４が好ましく、１～３がより好ましく、１～２がさらに好ましい。 (Nitro group)
At least one of R 1A to R 8A is a nitro group.
The number of nitro groups among R 1A to R 8A is not particularly limited, but is usually 1 or more, preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less. When the content is not more than the upper limit, the developability tends to be good. The number of nitro groups is preferably from 1 to 4, more preferably from 1 to 3, and even more preferably from 1 to 2.
　これらの中でも、撥インク性の観点から、Ｒ2A又はＲ7Aがニトロ基であることが好ましい。
　一方で、感度の観点から、Ｒ4A及びＲ5Aのいずれか一方又は両方がニトロ基であることが好ましく、Ｒ4A及びＲ5Aがニトロ基であることがより好ましい。 Among these, it is preferable that R 2A or R 7A is a nitro group from the viewpoint of ink repellency.
On the other hand, from the viewpoint of sensitivity, it is preferred that either or both of R 4A and R 5A is a nitro group, more preferably R 4A and R 5A is a nitro group.
（Ｒ9A）
　上記式（Ａ１－１）中のＲ9Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、通常１以上であり、２以上が好ましく、また、１０以下が好ましく、８以下がより好ましく、６以下がさらに好ましい。前記下限値以上とすることで溶剤への溶解性が良化する傾向があり、また、前記上限値以下とすることで撥インク性が良化する傾向がある。例えば、アルキル基の炭素数は１～１０が好ましく、１～８がより好ましく、１～６がさらに好ましく、２～６が特に好ましい。
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、撥インク性の観点から、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましく、エチル基であることがさらに好ましい。 (R 9A )
The alkyl group for R 9A in the above formula (A1-1) may be linear, branched, cyclic, or a combination thereof. Although the carbon number of the alkyl group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less. When the content is not less than the lower limit, the solubility in a solvent tends to be improved, and when the content is not more than the upper limit, the ink repellency tends to be improved. For example, the carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 2 to 6.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, from the viewpoint of ink repellency, a methyl group, It is preferably an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and further preferably an ethyl group.
　オキシムエステル系光重合開始剤（Ａ１）の公知化合物の具体例としては以下のものが挙げられる。 Specific examples of the known compounds of the oxime ester-based photopolymerization initiator (A1) include the following.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　これらオキシムエステル系光重合開始剤（Ａ１）の中でも、テーパ形状の観点から、前記式（Ａ１－１１）で表される化学構造の化合物が好ましい。 中 で も Among these oxime ester-based photopolymerization initiators (A1), compounds having a chemical structure represented by the formula (A1-11) are preferable from the viewpoint of the tapered shape.
［１－１－１－２］オキシムエステル系光重合開始剤（Ａ２）
　オキシムエステル系光重合開始剤（Ａ２）は、波長３００～４００ｎｍ間に吸収極大を有し、かつ、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して１０％以下である。このようにオキシムエステル系光重合開始剤（Ａ２）は、波長４００ｎｍにおける吸光度が十分に低く、高圧水銀灯の発する紫外線のうち、ｈ線をあまり利用することなく、主にｉ線を利用して硬化反応を促進させるため、塗膜上部におけるｈ線の吸収率を低くでき、塗膜下部のガラス基板近傍までｈ線を透過させることができ、オキシムエステル系光重合開始剤（Ａ１）を利用した塗膜下部における硬化を促進することができ、得られるパターンの垂直性が良好になると考えられる。 [1-1-1-2] Oxime ester photopolymerization initiator (A2)
The oxime ester-based photopolymerization initiator (A2) has an absorption maximum at a wavelength of 300 to 400 nm, and the absorbance at a wavelength of 400 nm is higher than the absorbance at a maximum absorption wavelength (λ max ) of 300 to 400 nm. 10% or less. As described above, the oxime ester-based photopolymerization initiator (A2) has a sufficiently low absorbance at a wavelength of 400 nm, and is hardened mainly by using i-line among ultraviolet rays emitted from a high-pressure mercury lamp without using h-line so much. In order to promote the reaction, the absorption rate of h-rays in the upper part of the coating film can be reduced, the h-rays can be transmitted to the vicinity of the glass substrate in the lower part of the coating film, and coating using an oxime ester-based photopolymerization initiator (A1) can be performed. It is considered that the curing at the lower part of the film can be promoted, and the perpendicularity of the obtained pattern is improved.
　オキシムエステル系光重合開始剤（Ａ２）の波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して１０％以下であれば特に限定されないが、５％以下が好ましく、３％以下がより好ましく、１％以下がさらに好ましく、また、０．０１％以上が好ましく、０．０５％以上がより好ましく、０．１％以上がさらに好ましく、０．３％以上がよりさらに好ましく、０．５％以上が特に好ましい。前記上限値以下とすることで隔壁側面のテーパ形状が良好となる傾向があり、また、前記下限値以上とすることでｉ線での硬化性が十分に発現する傾向がある。例えば、オキシムエステル系光重合開始剤（Ａ２）の波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して０．０１～１０％が好ましく、０．０５～５％がより好ましく、０．１～３％がさらに好ましく、０．３～３％がよりさらに好ましく、０．５～１％が特に好ましい。 The absorbance of the oxime ester-based photopolymerization initiator (A2) at a wavelength of 400 nm is not particularly limited as long as it is 10% or less with respect to the absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm, but is preferably 5% or less. It is preferably 3% or less, more preferably 1% or less, further preferably 0.01% or more, more preferably 0.05% or more, still more preferably 0.1% or more, and more preferably 0.3% or more. Even more preferably, it is particularly preferably 0.5% or more. When the content is not more than the upper limit, the tapered shape of the side wall of the partition tends to be good, and when the content is not less than the lower limit, the curability at the i-line tends to be sufficiently exhibited. For example, the absorbance of the oxime ester-based photopolymerization initiator (A2) at a wavelength of 400 nm is preferably 0.01 to 10% with respect to the absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm, and is preferably 0.05 to 10%. 5% is more preferable, 0.1 to 3% is further preferable, 0.3 to 3% is still more preferable, and 0.5 to 1% is particularly preferable.
　また、オキシムエステル系光重合開始剤（Ａ２）の波長３００～４００ｎｍ間の極大吸収波長（λmax）は特に限定されないが、３１０ｎｍ以上が好ましく、３２０ｎｍ以上がより好ましく、３２５ｎｍ以上がさらに好ましく、また、３５０ｎｍ以下が好ましく、３４０ｎｍ以下がより好ましく、３３０ｎｍ以下がさらに好ましい。前記下限値以上とすることでｉ線での硬化性が良好となる傾向があり、また、前記上限値以下とすることで隔壁側面のテーパ形状が良好となる傾向がある。例えば、オキシムエステル系光重合開始剤（Ａ２）の波長３００～４００ｎｍ間の極大吸収波長（λmax）は３１０～３５０ｎｍが好ましく、３２０～３４０ｎｍがより好ましく、３２５～３４０ｎｍがさらに好ましい。 The maximum absorption wavelength (λ max ) of the oxime ester photopolymerization initiator (A2) between 300 and 400 nm is not particularly limited, but is preferably 310 nm or more, more preferably 320 nm or more, still more preferably 325 nm or more. , 350 nm or less, more preferably 340 nm or less, even more preferably 330 nm or less. When the content is not less than the lower limit, the curability at the i-line tends to be good, and when the content is not more than the upper limit, the tapered shape of the side wall of the partition tends to be good. For example, the maximum absorption wavelength (λ max ) of the oxime ester-based photopolymerization initiator (A2) between 300 and 400 nm is preferably 310 to 350 nm, more preferably 320 to 340 nm, and still more preferably 325 to 340 nm.
　オキシムエステル系光重合開始剤（Ａ２）の吸光度及び極大吸収波長の測定は、まずオキシムエステル系光重合開始剤（Ａ２）の０．０１質量％のＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）溶液を作成し、それを分光光度計でオキシムエステル光重合開始剤（Ａ１）と同様の方法にて測定することができる。 For the measurement of the absorbance and the maximum absorption wavelength of the oxime ester-based photopolymerization initiator (A2), a 0.01% by mass PGMEA (propylene glycol monomethyl ether acetate) solution of the oxime ester-based photopolymerization initiator (A2) was prepared. It can be measured with a spectrophotometer in the same manner as for the oxime ester photopolymerization initiator (A1).
　オキシムエステル系光重合開始剤（Ａ２）は波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して１０％以下のものであるが、波長４００ｎｍにおける吸光度が低いものとしては、例えば、ジフェニルスルフィド、カルバゾール、フルオレン等の骨格にニトロ基等の電子吸引基を有さないオキシムエステル系光重合開始剤、例えば、これらの骨格に置換基を有さないオキシムエステル系光重合開始剤や、これらの骨格にアリールカルボニル基、アルコキシ基等の置換基を有するオキシムエステル系光重合開始剤が挙げられる。 The oxime ester-based photopolymerization initiator (A2) has an absorbance at a wavelength of 400 nm of 10% or less of the absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm, but has a low absorbance at a wavelength of 400 nm. Examples thereof include oxime ester-based photopolymerization initiators having no electron withdrawing group such as a nitro group in the skeleton of diphenyl sulfide, carbazole, fluorene, etc., for example, oxime ester-based initiators having no substituent in these skeletons Examples thereof include photopolymerization initiators and oxime ester-based photopolymerization initiators having a substituent such as an arylcarbonyl group or an alkoxy group on their skeleton.
　オキシムエステル系光重合開始剤（Ａ２）の化学構造は特に限定されないが、テーパ形状の観点から、下記一般式（Ａ２－１）で表される化合物を含むことが好ましい。 化学 The chemical structure of the oxime ester-based photopolymerization initiator (A2) is not particularly limited, but preferably contains a compound represented by the following general formula (A2-1) from the viewpoint of a tapered shape.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（式（Ａ２－１）中、Ｒ13Aは、置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。
　Ｒ14Aは、アルキル基、又は芳香族環基を表す。
　Ｒ15Aは、１価の置換基を表す。
　ｎは０又は１を表す。
　ｈは０～２の整数を表す。） (In the formula (A2-1), R 13A represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R 14A represents an alkyl group or an aromatic ring group.
R 15A represents a monovalent substituent.
n represents 0 or 1.
h represents an integer of 0 to 2. )
（Ｒ13A）
　上記式（Ａ２－１）中のＲ13Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、通常１以上であり、４以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１０以下がより好ましく、８以下がさらに好ましく、７以下がよりさらに好ましい。前記上限値以下とすることで溶剤への溶解性が良好となる傾向がある。例えば、アルキル基の炭素数は１～２０が好ましく、１～１０がより好ましく、１～８がさらに好ましく、１～７がよりさらに好ましく、４～７が特に好ましい。 ( R13A )
The alkyl group for R 13A in the above formula (A2-1) may be linear, branched, cyclic, or a combination thereof. Although the carbon number of the alkyl group is not particularly limited, it is usually 1 or more, preferably 4 or more, more preferably 6 or more, also preferably 20 or less, more preferably 10 or less, still more preferably 8 or less, and 7 or less. Even more preferred. When the content is not more than the upper limit, the solubility in the solvent tends to be good. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 7, and particularly preferably 4 to 7.
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、イソペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基、シクロペンチルメチル基、シクロペンチルエチル基、シクロヘキシルメチル基、シクロヘキシルエチル基などが挙げられ、これらの中でも現像性の観点から、メチル基、ヘキシル基、イソペンチル基、へキシル基、シクロペンチルメチル基、シクロヘキシルメチル基が好ましく、ヘキシル基、シクロペンチルメチル基がより好ましい。 Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, isopentyl, hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl Among these, from the viewpoint of developability, a methyl group, a hexyl group, an isopentyl group, a hexyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group are preferable, and a hexyl group and a cyclopentylmethyl group are more preferable.
　アルキル基が有していてもよい置換基としては、芳香族環基、水酸基、カルボキシル基などが挙げられ、合成容易性の観点からは、無置換であることが好ましい。 Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, and the like. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
　上記式（Ａ２－１）中のＲ13Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、通常４以上、５以上が好ましく、また、３０以下が好ましく、２０以下がより好ましく、１２以下がさらに好ましい。前記下限値以上とすることで溶剤への溶解性が良好となる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。例えば、芳香族環基の炭素数は４～３０が好ましく、４～２０がより好ましく、４～１２がさらに好ましく、５～１２が特に好ましい。 Examples of the aromatic ring group for R 13A in the above formula (A2-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually preferably 4 or more, 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. When the content is not less than the lower limit, solubility in a solvent tends to be good, and when the content is not more than the upper limit, developability tends to be good. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 12, and particularly preferably 5 to 12.
　芳香族環基の具体例としては、フェニル基、ナフチル基、ピリジル基、フリル基などが挙げられ、これらの中でも現像性の観点から、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。
　芳香族環基が有していてもよい置換基としては、水酸基、アルキル基などが挙げられ、現像性の観点からアルキル基が好ましい。
　これらの中でも、テーパ形状の観点から、Ｒ13Aが、置換基を有していてもよいアルキル基であることが好ましい。 Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable, from the viewpoint of developability.
Examples of the substituent which the aromatic ring group may have include a hydroxyl group and an alkyl group, and an alkyl group is preferable from the viewpoint of developability.
Among these, from the viewpoint of the tapered shape, R 13A is preferably an alkyl group which may have a substituent.
（Ｒ14A）
　上記式（Ａ２－１）中のＲ14Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、通常１以上であり、また、５以下が好ましく、３以下がより好ましい。前記上限値以下とすることで感度が良好となる傾向がある。例えば、アルキル基の炭素数は１～５が好ましく、１～３がより好ましい。 ( R14A )
The alkyl group for R 14A in the above formula (A2-1) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 5 or less, more preferably 3 or less. When the content is not more than the upper limit, the sensitivity tends to be good. For example, the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3.
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ペンチル基などが挙げられ、これらの中でもテーパ形状の観点から、メチル基が好ましい。 Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a pentyl group. Among them, a methyl group is preferable from the viewpoint of a tapered shape.
　上記式（Ａ２－１）中のＲ14Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、通常４以上であり、５以上が好ましく、また、３０以下が好ましく、２０以下がより好ましく、１２以下がさらに好ましい。前記下限値以上とすることで溶剤への溶解性が良好となる傾向があり、また、前記上限値以下とすることで感度が良好となる傾向がある。例えば、芳香族環基の炭素数は４～３０が好ましく、４～２０がより好ましく、４～１２がさらに好ましく、５～１２が特に好ましい。 Examples of the aromatic ring group for R 14A in the above formula (A2-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. When the content is not less than the lower limit, the solubility in the solvent tends to be good, and when the content is not more than the upper limit, the sensitivity tends to be good. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 12, and particularly preferably 5 to 12.
　芳香族環基の具体例としては、フェニル基、ナフチル基、ピリジル基、フリル基などが挙げられ、これらの中でもテーパ形状の観点から、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。 具体 Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and the like. Among them, from the viewpoint of a tapered shape, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
　これらの中でも上記式（Ａ２－１）中のＲ14Aとしては、接触角の観点から、芳香族環基が好ましく、フェニル基又はナフチル基がより好ましく、フェニル基がさらに好ましい。一方、テーパ形状の観点から、メチル基が好ましい。 Among these, as R 14A in the formula (A2-1), an aromatic ring group is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is more preferable, from the viewpoint of a contact angle. On the other hand, from the viewpoint of the tapered shape, a methyl group is preferable.
（Ｒ15A）
　上記式（Ａ２－１）中のＲ15Aにおける１価の置換基は特に限定されないが、現像性の観点から、Ｒ16A－Ｏ－、又はＲ16A－（Ｃ＝Ｏ）－が好ましい。 ( R15A )
The monovalent substituent for R 15A in the formula (A2-1) is not particularly limited, but R 16A —O— or R 16A — (C ＝ O) — is preferable from the viewpoint of developability.
　Ｒ16Aとしては、置換基を有してもよいアルキル基、置換基を有してもよい芳香族環基が挙げられる。
　Ｒ16Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、通常１以上であり、２以上が好ましく、３以上がより好ましく、また、８以下が好ましく、５以下がより好ましい。前記下限値以上とすることで現像性が良好となる傾向があり、また、前記上限値以下とすることでテーパ形状が良好となる傾向がある。例えば、アルキル基の炭素数は１～８が好ましく、２～５がより好ましい。 Examples of R 16A include an alkyl group which may have a substituent and an aromatic ring group which may have a substituent.
The alkyl group for R 16A may be linear, branched, cyclic, or a combination thereof. Although the carbon number of the alkyl group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 8 or less, more preferably 5 or less. When the content is not less than the lower limit, the developability tends to be good, and when the content is not more than the upper limit, the tapered shape tends to be good. For example, the alkyl group preferably has 1 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms.
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ペンチル基などが挙げられ、これらの中でも溶解性の観点から、メチル基、エチル基が好ましく、エチル基がより好ましい。
　アルキル基が有していてもよい置換基としては、水酸基、カルボキシル基などが挙げられ、現像性の観点から水酸基が好ましい。 Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a pentyl group. Among them, from the viewpoint of solubility, a methyl group and an ethyl group are preferable, and an ethyl group is more preferable.
Examples of the substituent which the alkyl group may have include a hydroxyl group and a carboxyl group, and a hydroxyl group is preferable from the viewpoint of developability.
　Ｒ16Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、通常４以上であり、５以上が好ましく、また、３０以下が好ましく、２０以下がより好ましく、１２以下がさらに好ましい。前記下限値以上とすることで現像性が良好となる傾向があり、また、前記上限値以下とすることでテーパ形状が良好となる傾向がある。例えば、芳香族環基の炭素数は４～３０が好ましく、４～２０がより好ましく、４～１２がさらに好ましく、５～１２が特に好ましい。
　芳香族環基の具体例としては、フェニル基、ナフチル基、チエニル基、フリル基、ベンゾチエニル基、ベンゾフリル基などが挙げられる。これらの中でもテーパ形状の観点から、ベンゾチエニル基又はベンゾフリル基が好ましく、ベンゾフリル基がより好ましい。
　芳香族環基が有していてもよい置換基としては、アルキル基、水酸基、カルボキシル基などが挙げられ、合成性の観点から無置換が好ましい。 Examples of the aromatic ring group for R 16A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. When the content is not less than the lower limit, the developability tends to be good, and when the content is not more than the upper limit, the tapered shape tends to be good. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 12, and particularly preferably 5 to 12.
Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a thienyl group, a furyl group, a benzothienyl group and a benzofuryl group. Among these, from the viewpoint of the tapered shape, a benzothienyl group or a benzofuryl group is preferable, and a benzofuryl group is more preferable.
Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, a carboxyl group, and the like.
　上記式（Ａ２－１）中のＲ15Aにおける１価の置換基としては、テーパ形状の観点から、Ｒ16Aが水酸基置換のエチル基であるＲ16A－Ｏ－、Ｒ16Aがベンゾフリル基であるＲ16A－（Ｃ＝Ｏ）－が好ましく、Ｒ16Aが水酸基置換のエチル基であるＲ16A－Ｏ－がより好ましい。 As the monovalent substituent for R 15A in the above formula (A2-1), from the viewpoint of the tapered shape, R 16A is a hydroxyl-substituted ethyl group, R 16A —O—, and R 16A is a benzofuryl group. Preferred is 16A- (C = O)-, and more preferred is R16A- O-, wherein R16A is a hydroxyl-substituted ethyl group.
（ｎ）
　上記式（Ａ２－１）において、ｎは０又は１を表す。テーパ形状の観点からはｎが１であることが好ましく、一方で、感度の観点からはｎが０であることが好ましい。 (N)
In the above formula (A2-1), n represents 0 or 1. It is preferable that n is 1 from the viewpoint of the tapered shape, while it is preferable that n is 0 from the viewpoint of sensitivity.
（ｈ）
　上記式（Ａ２－１）において、ｈは０～２の整数を表す。テーパ形状の観点からはｈが０又は１であることが好ましく、０であることがより好ましい。
　ｈが１以上の整数の場合、Ｒ15Aの置換位置は特に限定されないが、合成上の観点からｏ位又はｐ位が好ましく、ｐ位がより好ましい。 (H)
In the above formula (A2-1), h represents an integer of 0 to 2. From the viewpoint of the tapered shape, h is preferably 0 or 1, and more preferably 0.
When h is an integer of 1 or more, the substitution position of R 15A is not particularly limited, but the o-position or the p-position is preferable from the viewpoint of synthesis, and the p-position is more preferable.
　オキシムエステル系光重合開始剤（Ａ２）の公知化合物の具体例としては以下のものが挙げられる。 Specific examples of known compounds of the oxime ester-based photopolymerization initiator (A2) include the following.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　これらの中でも、テーパ形状の観点から、前記式（Ａ２－１９）で表される化学構造の化合物が好ましい。一方で接触角の観点から、前記式（Ａ２－１７）又は（Ａ２－１８）で表される化学構造の化合物が好ましい。 中 で も Among these, compounds having the chemical structure represented by the formula (A2-19) are preferable from the viewpoint of the tapered shape. On the other hand, from the viewpoint of the contact angle, a compound having the chemical structure represented by the formula (A2-17) or (A2-18) is preferable.
　本発明の第１の態様に係る感光性着色樹脂組成物における（Ａ）光重合開始剤は、オキシムエステル系光重合開始剤（Ａ１）及びオキシムエステル系光重合開始剤（Ａ２）以外の光重合開始剤（以下、「その他の光重合開始剤」と称する場合がある。）を含有してもよい。その他の光重合開始剤は、オキシムエステル系化合物であってもよいし、オキシムエステル系化合物以外のものであってもよい。 The photopolymerization initiator (A) in the photosensitive colored resin composition according to the first embodiment of the present invention is a photopolymerization initiator other than the oxime ester photopolymerization initiator (A1) and the oxime ester photopolymerization initiator (A2). An initiator (hereinafter, may be referred to as “other photopolymerization initiator”) may be contained. The other photopolymerization initiator may be an oxime ester compound, or may be other than the oxime ester compound.
　その他の光重合開始剤としては、この分野で通常用いられているものを使用することができる。例えば、日本国特開昭５９－１５２３９６号公報、日本国特開昭６１－１５１１９７号公報に記載のチタノセン化合物を含むメタロセン化合物；日本国特開２０００－５６１１８号公報に記載のヘキサアリールビイミダゾール誘導体類；日本国特開平１０－３９５０３号公報記載のハロメチル化オキサジアゾール誘導体類、ハロメチル－ｓ－トリアジン誘導体類、Ｎ－フェニルグリシン等のＮ－アリール－α－アミノ酸類、Ｎ－アリール－α－アミノ酸塩類、Ｎ－アリール－α－アミノ酸エステル類等のラジカル活性剤、α－アミノアルキルフェノン誘導体類等が挙げられる。 As other photopolymerization initiators, those usually used in this field can be used. For example, metallocene compounds containing titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118 N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in Japanese Patent Application Laid-Open No. 10-39503, N-aryl-α- Radical activators such as amino acid salts, N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives.
　具体的には、例えば、メタロセン化合物としては、ジシクロペンタジエニルチタニウムジクロリド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６－ペンタフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６－テトラフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，４，６－トリフルオロフェニル）、ジシクロペンタジエニルチタニウムジ（２，６－ジフルオロフェニル）、ジシクロペンタジエニルチタニウムジ（２，４－ジフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６－ペンタフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６－ジフルオロフェニル）、ジシクロペンタジエニルチタニウム〔２，６－ジ－フルオロ－３－（ピロール－１－イル）フェニル〕等が挙げられる。 Specifically, for example, as the metallocene compound, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl ), Dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium di ( 2,6-difluorophenyl), dicyclopentadienyl titanium di (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), Di (methylcyclopentadienyl) titanium bis (2,6-difluoro Phenyl), dicyclopentadienyl titanium [2,6-di - fluoro-3- (pyrrol-1-yl) phenyl], and the like.
　また、ビイミダゾール誘導体類としては、２－（２’－クロロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－クロロフェニル）－４，５－ビス（３’－メトキシフェニル）イミダゾール２量体、２－（２’－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体、（４’－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体等が挙げられる。 Examples of the biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.
　また、ハロメチル化オキサジアゾール誘導体類としては、２－トリクロロメチル－５－（２’－ベンゾフリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－ベンゾフリル）ビニル〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－（６’’－ベンゾフリル）ビニル）〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－フリル－１，３，４－オキサジアゾール等が挙げられる。 Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5- [β- (2'- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.
　また、ハロメチル－ｓ－トリアジン誘導体類としては、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン等が挙げられる。 Examples of the halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) —S-triazine and the like.
　また、α－アミノアルキルフェノン誘導体類としては、２－メチル－１〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、４－ジメチルアミノエチルベンゾエ－ト、４－ジメチルアミノイソアミルベンゾエ－ト、４－ジエチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン、２－エチルヘキシル－１，４－ジメチルアミノベンゾエート、２，５－ビス（４－ジエチルアミノベンザル）シクロヘキサノン、７－ジエチルアミノ－３－（４－ジエチルアミノベンゾイル）クマリン、４－（ジエチルアミノ）カルコン等が挙げられる。 Examples of the α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo Ethate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- ( 4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. And the like.
　その他の光重合開始剤は、１種類を単独で用いても、２種類以上を組み合わせて使用してもよい。 は Other photopolymerization initiators may be used alone or in combination of two or more.
［１－１－１－３］オキシムエステル系光重合開始剤（Ａ３）
　前述のとおり、本発明の第２の態様に係る感光性着色樹脂組成物における（Ａ）光重合開始剤は、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して８～３０％であるオキシムエステル系光重合開始剤（Ａ３）（以下、「オキシムエステル系光重合開始剤（Ａ３）」と略記する場合がある。）を含有する。このようにオキシムエステル系光重合開始剤（Ａ３）を含有することで、塗膜上部においてｈ線を利用した硬化によって撥液剤の固定ができ、かつ、塗膜下部まで一定量のｈ線を透過させることでガラス基板近傍でのｈ線を利用した硬化が推進されて隔壁側面のテーパの垂直性が良好になると考えられる。 [1-1-1-3] Oxime ester photopolymerization initiator (A3)
As described above, the photopolymerization initiator (A) in the photosensitive colored resin composition according to the second aspect of the present invention has an absorbance at a wavelength of 400 nm, an absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm. Oxime ester-based photopolymerization initiator (A3) (hereinafter sometimes abbreviated as “oxime ester-based photopolymerization initiator (A3)”) in an amount of 8 to 30% based on the total amount of the oxime ester-based photopolymerization initiator (A3). By containing the oxime ester-based photopolymerization initiator (A3) in this manner, the liquid repellent can be fixed by curing using h-rays at the upper part of the coating film, and a certain amount of h-rays can be transmitted to the lower part of the coating film. It is considered that by doing so, the hardening utilizing the h-line near the glass substrate is promoted, and the perpendicularity of the taper on the side wall of the partition is improved.
　オキシムエステル系光重合開始剤（Ａ３）は１種類単独でもよく、２種類以上の混合物であってもよい。
　２種類以上の混合物である場合、例えば、オキシムエステル系光重合開始剤（Ａ３－１）とオキシムエステル系光重合開始剤（Ａ３－２）の混合物である場合には、オキシムエステル系光重合開始剤（Ａ３）の波長４００ｎｍにおける吸光度は、まずオキシムエステル系光重合開始剤（Ａ３－１）の波長４００ｎｍにおける吸光度とオキシムエステル系光重合開始剤（Ａ３－２）の波長４００ｎｍにおける吸光度を各々測定し、それをオキシムエステル系光重合開始剤（Ａ３－１）とオキシムエステル系光重合開始剤（Ａ３－２）の感光性着色樹脂組成物中の含有割合（質量基準）で加重平均することで算出できる。３種類以上の場合も同様である。 The oxime ester-based photopolymerization initiator (A3) may be a single type or a mixture of two or more types.
When the mixture is a mixture of two or more types, for example, when the mixture is an oxime ester-based photopolymerization initiator (A3-1) and an oxime ester-based photopolymerization initiator (A3-2), the oxime ester-based photopolymerization initiator is used. First, the absorbance of the oxime ester-based photopolymerization initiator (A3-1) at a wavelength of 400 nm and the absorbance of the oxime ester-based photopolymerization initiator (A3-2) at a wavelength of 400 nm are measured. Then, the weighted average is calculated based on the content ratio (by mass) of the oxime ester-based photopolymerization initiator (A3-1) and the oxime ester-based photopolymerization initiator (A3-2) in the photosensitive colored resin composition. Can be calculated. The same applies to three or more types.
　オキシムエステル系光重合開始剤（Ａ３）の波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して８～３０％であれば特に限定されないが、１０％以上が好ましく、１５％以上がより好ましく、２０％以上がさらに好ましく、２３％以上がよりさらに好ましく、また、２８％以下が好ましく、２７％以下がより好ましく、２６％以下がさらに好ましい。前記下限値以上とすることで撥インク性が高くなる傾向があり、また、前記上限値以下とすることで隔壁側面のテーパ形状が良好となる傾向がある。例えば、オキシムエステル系光重合開始剤（Ａ３）の波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して８～２８％が好ましく、１０～２８％がより好ましく、１５～２８％がさらに好ましく、２０～２７％がよりさらに好ましく、２３～２６％が特に好ましい。 The absorbance of the oxime ester-based photopolymerization initiator (A3) at a wavelength of 400 nm is not particularly limited as long as it is 8 to 30% of the absorbance at a maximum absorption wavelength (λ max ) of 300 to 400 nm, but is 10% or more. Is preferably 15% or more, more preferably 20% or more, even more preferably 23% or more, and preferably 28% or less, more preferably 27% or less, and even more preferably 26% or less. When the amount is not less than the lower limit, the ink repellency tends to be high, and when the amount is not more than the upper limit, the tapered shape of the side wall of the partition tends to be good. For example, the absorbance of the oxime ester-based photopolymerization initiator (A3) at a wavelength of 400 nm is preferably from 8 to 28%, more preferably from 10 to 28%, relative to the absorbance at the maximum absorption wavelength (λ max ) between 300 and 400 nm. Preferably, it is more preferably from 15 to 28%, further preferably from 20 to 27%, particularly preferably from 23 to 26%.
　本発明の第２の態様に係る感光性着色樹脂組成物における（Ａ）光重合開始剤は、オキシムエステル系光重合開始剤以外の光重合開始剤を含有してもよい。オキシムエステル系光重合開始剤以外の光重合開始剤としては、その他の光重合開始剤として前述したものが挙げられる。 （The photopolymerization initiator (A) in the photosensitive colored resin composition according to the second aspect of the present invention may contain a photopolymerization initiator other than the oxime ester-based photopolymerization initiator. Examples of the photopolymerization initiator other than the oxime ester-based photopolymerization initiator include those described above as other photopolymerization initiators.
　また、本発明の感光性着色樹脂組成物における光重合開始剤には、必要に応じて、感応感度を高める目的で、画像露光光源の波長に応じた増感色素、重合促進剤を配合させることができる。増感色素としては、日本国特開平４－２２１９５８号公報、日本国特開平４－２１９７５６号公報に記載のキサンテン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の複素環を有するクマリン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の３－ケトクマリン化合物、日本国特開平６－１９２４０号公報に記載のピロメテン色素、その他、日本国特開昭４７－２５２８号公報、日本国特開昭５４－１５５２９２号公報、日本国特公昭４５－３７３７７号公報、日本国特開昭４８－８４１８３号公報、日本国特開昭５２－１１２６８１号公報、日本国特開昭５８－１５５０３号公報、日本国特開昭６０－８８００５号公報、日本国特開昭５９－５６４０３号公報、日本国特開平２－６９号公報、日本国特開昭５７－１６８０８８号公報、日本国特開平５－１０７７６１号公報、日本国特開平５－２１０２４０号公報、日本国特開平４－２８８８１８号公報に記載のジアルキルアミノベンゼン骨格を有する色素等を挙げることができる。 Further, the photopolymerization initiator in the photosensitive colored resin composition of the present invention, if necessary, for the purpose of increasing the sensitivity, may be blended with a sensitizing dye according to the wavelength of the image exposure light source, a polymerization accelerator. Can be. Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, and JP-A-5-289335. Coumarin dyes having a heterocyclic ring described in JP-A-3-239703, 3-ketocoumarin compounds described in JP-A-5-289335, and pyromethene described in JP-A-6-19240. Dyes and others, Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Japanese Patent Application Laid-Open No. Sho 52-11681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application No. Sho 59-56403. Gazette, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-1077761, Japanese Patent Application Laid-Open No. 5-210240, Japanese Patent Application Laid-Open No. 4-288818. And a dye having a dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open (JP-A) No. 6-131131.
　これらの増感色素のうち好ましいものは、アミノ基含有増感色素であり、更に好ましいものは、アミノ基及びフェニル基を同一分子内に有する化合物である。特に、好ましいのは、例えば、４，４’－ジメチルアミノベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン、２－アミノベンゾフェノン、４－アミノベンゾフェノン、４，４’－ジアミノベンゾフェノン、３，３’－ジアミノベンゾフェノン、３，４－ジアミノベンゾフェノン等のベンゾフェノン系化合物；２－（ｐ－ジメチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［４，５］ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［６，７］ベンゾオキサゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）－１，３，４－オキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジメチルアミノフェニル）ベンズイミダゾール、２－（ｐ－ジエチルアミノフェニル）ベンズイミダゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）－１，３，４－チアジアゾール、（ｐ－ジメチルアミノフェニル）ピリジン、（ｐ－ジエチルアミノフェニル）ピリジン、（ｐ－ジメチルアミノフェニル）キノリン、（ｐ－ジエチルアミノフェニル）キノリン、（ｐ－ジメチルアミノフェニル）ピリミジン、（ｐ－ジエチルアミノフェニル）ピリミジン等のｐ－ジアルキルアミノフェニル基含有化合物等である。このうち最も好ましいものは、４，４’－ジアルキルアミノベンゾフェノンである。
　増感色素もまた１種を単独で用いてもよく、２種以上を併用してもよい。 Preferred among these sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone , Benzophenone-based compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl ) Benzothiazole, 2- (p-diethyl) L-aminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (P-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine And p-dialkylaminophenyl group-containing compounds. The most preferred of these is 4,4'-dialkylaminobenzophenone.
As the sensitizing dye, one type may be used alone, or two or more types may be used in combination.
　重合促進剤としては、例えば、ｐ－ジメチルアミノ安息香酸エチル、安息香酸２－ジメチルアミノエチル等の芳香族アミン、ｎ－ブチルアミン、Ｎ－メチルジエタノールアミン等の脂肪族アミン等が用いられる。
　重合促進剤は、１種類を単独で用いても、２種以上を組み合わせて使用してもよい。
　また上記光重合開始剤と併用して、連鎖移動剤を用いることが好ましい。連鎖移動剤としてはメルカプト基含有化合物や、四塩化炭素等が挙げられ、連鎖移動効果が高い傾向があることからメルカプト基含有化合物を用いることがより好ましい。Ｓ－Ｈ結合エネルギーが小さいことによって結合開裂が起こりやすく、水素引きぬき反応や連鎖移動反応を起こしやすいためであると考えられる。高感度化のために好適である。 Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, and aliphatic amines such as n-butylamine and N-methyldiethanolamine.
One type of polymerization accelerator may be used alone, or two or more types may be used in combination.
It is preferable to use a chain transfer agent in combination with the above photopolymerization initiator. Examples of the chain transfer agent include a mercapto group-containing compound and carbon tetrachloride. It is more preferable to use a mercapto group-containing compound because the chain transfer effect tends to be high. This is considered to be because bond breaking is likely to occur due to a small SH bond energy, and a hydrogen abstraction reaction and a chain transfer reaction are likely to occur. It is suitable for increasing the sensitivity.
　メルカプト基含有化合物としては、芳香族環を有するメルカプト基含有化合物、脂肪族系のメルカプト基含有化合物が好ましく、脂肪族系のメルカプト基含有化合物がさらに好ましい。
　芳香族環を有するメルカプト基含有化合物としては、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、３－メルカプト－１，２，４－トリアゾール、２－メルカプト－４（３Ｈ）－キナゾリン、β－メルカプトナフタレン、１，４－ジメチルメルカプトベンゼン等が挙げられ、高感度の観点から、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾールが好ましい。
　脂肪族系のメルカプト基含有化合物としては、へキサンジチオール、デカンジチオール、ブタンジオールビス（３－メルカプトプロピオネート）、ブタンジオールビスチオグリコレート、エチレングリコールビス（３－メルカプトプロピオネート）、エチレングリコールビスチオグリコレート、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリメチロールプロパントリスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、ブタンジオールビス（３－メルカプトブチレート）、エチレングリコールビス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン等が挙げられる。 As the mercapto group-containing compound, a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are preferable, and an aliphatic mercapto group-containing compound is more preferable.
Examples of the mercapto group-containing compound having an aromatic ring include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -Quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene and the like, and from the viewpoint of high sensitivity, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred.
Aliphatic mercapto group-containing compounds include hexanedithiol, decanedithiol, butanediol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis (3-mercaptopropionate), ethylene Glycol bisthioglycolate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol Tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane Squirrel (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3 , 5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.
　このうち撥インク性の観点から、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンがより好ましく、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）がさらに好ましい。 Among these, from the viewpoint of ink repellency, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) 3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, more preferably pentane Erythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferred.
　連鎖移動剤は１種を単独で使用してもよいし、２種以上を併用して使用してもよい。 The chain transfer agent may be used alone or in combination of two or more.
　本発明の感光性着色樹脂組成物における（Ａ）光重合開始剤の含有割合は特に限定されないが、感光性着色樹脂組成物の全固形分中に、通常０．１質量％以上、好ましくは１質量％以上、より好ましくは２質量％以上、さらに好ましくは３質量％以上であり、通常１５質量％以下、好ましくは１０質量％以下、より好ましくは８質量％以下、さらに好ましくは５質量％以下である。前記下限値以上とすることで、十分な撥インク性が生じる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。例えば、感光性着色樹脂組成物の全固形分中の（Ａ）光重合開始剤の含有割合は０．１～１５質量％が好ましく、１～１０質量％がより好ましく、２～８質量％がさらに好ましく、３～５質量％が特に好ましい。 The content of the photopolymerization initiator (A) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 0.1% by mass or more, preferably 1% by mass, in the total solid content of the photosensitive colored resin composition. % By mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. It is. When the content is equal to or more than the lower limit, sufficient ink repellency tends to be generated, and when the content is equal to or less than the upper limit, developability tends to be improved. For example, the content of the photopolymerization initiator (A) in the total solid content of the photosensitive colored resin composition is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, and more preferably 2 to 8% by mass. Further preferred is 3 to 5% by mass.
　本発明の第１の態様に係る感光性着色樹脂組成物において、（Ａ）光重合開始剤中におけるオキシムエステル系光重合開始剤（Ａ１）の含有割合も特に限定されないが、通常２０質量％以上であり、３０質量％以上が好ましく、４０質量％以上がより好ましく、４５質量％以上がさらに好ましく、５０質量％以上がよりさらに好ましく、６０質量％以上が特に好ましく、７０質量％以上が最も好ましい。また通常９０質量％以下であり、８５質量％以下が好ましく、８０質量％以下がより好ましい。前記下限値以上とすることで、十分な撥インク性が生じる傾向があり、前記上限値以下とすることでテーパ形状が良好となる傾向がある。例えば、（Ａ）光重合開始剤中におけるオキシムエステル系光重合開始剤（Ａ１）の含有割合は３０～９０質量％が好ましく、５０～９０質量％がより好ましく、６０～８５質量％がさらに好ましく、７０～８０質量％が特に好ましい。 In the photosensitive colored resin composition according to the first aspect of the present invention, the content of the oxime ester-based photopolymerization initiator (A1) in the photopolymerization initiator (A) is not particularly limited, but is usually 20% by mass or more. Is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, still more preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 70% by mass or more. . Further, it is usually at most 90 mass%, preferably at most 85 mass%, more preferably at most 80 mass%. When the amount is equal to or more than the lower limit, sufficient ink repellency tends to occur, and when the amount is equal to or less than the upper limit, the taper shape tends to be good. For example, the content of the oxime ester-based photopolymerization initiator (A1) in the photopolymerization initiator (A) is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and still more preferably 60 to 85% by mass. , 70 to 80% by mass is particularly preferred.
　（Ａ）光重合開始剤中におけるオキシムエステル系光重合開始剤（Ａ２）の含有割合も特に限定されないが、通常５質量％以上であり、１０質量％以上が好ましく、１５質量％以上がより好ましく、２０質量％以上がさらに好ましい。また通常７０質量％以下であり、６０質量％以下が好ましく、５０質量％以下がより好ましく、４０質量％以下がさらに好ましく、３０質量％以下が特に好ましい。前記下限値以上とすることで、テーパ形状が良好となる傾向があり、前記上限値以下とすることで十分な撥インク性が生じる傾向がある。例えば、（Ａ）光重合開始剤中におけるオキシムエステル系光重合開始剤（Ａ２）の含有割合は５～７０質量％が好ましく、５～６０質量％がより好ましく、１０～５０質量％がさらに好ましく、１５～４０質量％がよりさらに好ましく、２０～３０質量％が特に好ましい。 (A) The content ratio of the oxime ester-based photopolymerization initiator (A2) in the photopolymerization initiator is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. , 20% by mass or more is more preferable. Further, it is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the content is not less than the lower limit, the tapered shape tends to be good, and when the content is not more than the upper limit, sufficient ink repellency tends to be generated. For example, the content of the oxime ester-based photopolymerization initiator (A2) in the photopolymerization initiator (A) is preferably from 5 to 70% by mass, more preferably from 5 to 60% by mass, and still more preferably from 10 to 50% by mass. , 15 to 40% by mass is more preferable, and 20 to 30% by mass is particularly preferable.
　オキシムエステル系光重合開始剤（Ａ２）の含有割合は、オキシムエステル系光重合開始剤（Ａ１）１００質量部に対して、通常１０質量部以上であり、２０質量部以上が好ましく、２５質量部以上がより好ましく、３０質量部以上がさらに好ましい。また通常７０質量部以下であり、６０質量部以下が好ましく、５５質量部以下がより好ましく、５０質量部以下がさらに好ましく、４５質量部以下がよりさらに好ましく、４０質量部以下が特に好ましい。前記下限値以上とすることで、テーパ形状が良好となる傾向があり、前記上限値以下とすることで十分な撥インク性が生じる傾向がある。例えば、オキシムエステル系光重合開始剤（Ａ１）１００質量部に対する、オキシムエステル系光重合開始剤（Ａ２）の含有割合は１０～７０質量％が好ましく、１０～６０質量％がより好ましく、２０～５５質量％がさらに好ましく、２０～５０質量％がよりさらに好ましく、２５～４５質量％がとりわけ好ましく、３０～４０質量％が特に好ましい。 The content ratio of the oxime ester-based photopolymerization initiator (A2) is usually 10 parts by mass or more, preferably 20 parts by mass or more, and more preferably 25 parts by mass with respect to 100 parts by mass of the oxime ester-based photopolymerization initiator (A1). More preferably, the amount is 30 parts by mass or more. Further, it is usually 70 parts by mass or less, preferably 60 parts by mass or less, more preferably 55 parts by mass or less, still more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, and particularly preferably 40 parts by mass or less. When the content is not less than the lower limit, the tapered shape tends to be good, and when the content is not more than the upper limit, sufficient ink repellency tends to be generated. For example, the content ratio of the oxime ester-based photopolymerization initiator (A2) to 100 parts by mass of the oxime ester-based photopolymerization initiator (A1) is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, and more preferably 20 to 60% by mass. The content is more preferably 55% by mass, further preferably 20 to 50% by mass, particularly preferably 25 to 45% by mass, and particularly preferably 30 to 40% by mass.
　また、本発明の第２の態様に係る感光性着色樹脂組成物において、全固形分中におけるオキシムエステル系光重合開始剤（Ａ３）の含有割合も特に限定されないが、通常０．１質量％以上であり、１質量％以上が好ましく、２質量％以上がより好ましく、３質量％以上がさらに好ましい。また通常１５質量％以下であり、１０質量％以下が好ましく、８質量％以下がより好ましく、５質量％以下がさらに好ましい。前記下限値以上とすることで、十分な撥インク性が生じる傾向があり、前記上限値以下とすることでテーパ形状が良好となる傾向がある。例えば、感光性着色樹脂組成物の全固形分中におけるオキシムエステル系光重合開始剤（Ａ３）の含有割合は０．１～１５質量％が好ましく、１～１０質量％がより好ましく、２～８質量％がさらに好ましく、３～５質量％が特に好ましい。 In the photosensitive colored resin composition according to the second aspect of the present invention, the content of the oxime ester-based photopolymerization initiator (A3) in the total solid content is not particularly limited, but is usually 0.1% by mass or more. Is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. Further, it is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. When the amount is equal to or more than the lower limit, sufficient ink repellency tends to occur, and when the amount is equal to or less than the upper limit, the taper shape tends to be good. For example, the content of the oxime ester-based photopolymerization initiator (A3) in the total solid content of the photosensitive colored resin composition is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, and 2 to 8% by mass. % By mass is more preferable, and 3 to 5% by mass is particularly preferable.
　また、本発明の感光性着色樹脂組成物中の（Ｃ）光重合性化合物に対する（Ａ）光重合開始剤の配合割合も特に限定されないが、（Ｃ）光重合性化合物１００質量部に対して、１質量部以上が好ましく、５質量部以上がより好ましく、１０質量部以上がさらに好ましく、１２質量部以上がよりさらに好ましく、１５質量部以上が特に好ましく、また、２００質量部以下が好ましく、１００質量部以下がより好ましく、５０質量部以下がさらに好ましく、３０質量部以下がよりさらに好ましく、２０質量部以下が特に好ましい。前記下限値以上とすることで適切な感度となる傾向があり、また、前記上限値以下とすることで所望のパターン形状にしやすくなる傾向がある。例えば、（Ｃ）光重合性化合物１００質量部に対する（Ａ）光重合開始剤の配合割合は１～２００質量部が好ましく、５～１００質量部がより好ましく、１０～５０質量部がさらに好ましく、１２～３０質量部がよりさらに好ましく、１５～２０質量部が特に好ましい。 Further, the mixing ratio of the (A) photopolymerization initiator to the (C) photopolymerizable compound in the photosensitive colored resin composition of the present invention is not particularly limited. Is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 12 parts by mass or more, particularly preferably 15 parts by mass or more, and further preferably 200 parts by mass or less, The amount is more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less. When the value is not less than the lower limit, the sensitivity tends to be appropriate, and when the value is not more than the upper limit, a desired pattern shape tends to be easily obtained. For example, the mixing ratio of the photopolymerization initiator (A) to 100 parts by mass of the photopolymerizable compound (C) is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, and still more preferably 10 to 50 parts by mass. The content is more preferably from 12 to 30 parts by mass, particularly preferably from 15 to 20 parts by mass.
　本発明の感光性着色樹脂組成物が連鎖移動剤を含む場合、その含有割合は特に限定されないが、感光性着色樹脂組成物の全固形分中に、通常０．０１質量％以上、好ましくは０．１質量％以上、より好ましくは０．５質量％以上、さらに好ましくは０．８質量％以上であり、通常５質量％以下、好ましくは４質量％以下、より好ましくは３質量％以下、さらに好ましくは２質量％以下である。前記下限値以上とすることで感度が高くなる傾向があり、また、前記上限値以下とすることで所望のパターンを形成しやすくなる傾向がある。連鎖移動剤を含む場合には、例えば、感光性着色樹脂組成物の全固形分中における連鎖移動剤の含有割合は０．０１～５質量％が好ましく、０．１～４質量％がより好ましく、０．５～３質量％がさらに好ましく、０．８～２質量％が特に好ましい。 When the photosensitive colored resin composition of the present invention contains a chain transfer agent, the content thereof is not particularly limited, but is usually 0.01% by mass or more, preferably 0% by mass, in the total solid content of the photosensitive colored resin composition. 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, furthermore It is preferably at most 2% by mass. When the ratio is equal to or higher than the lower limit, the sensitivity tends to increase, and when the ratio is equal to or lower than the upper limit, a desired pattern tends to be easily formed. When a chain transfer agent is contained, for example, the content ratio of the chain transfer agent in the total solid content of the photosensitive colored resin composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass. , 0.5 to 3% by mass, and particularly preferably 0.8 to 2% by mass.
　また、感光性着色樹脂組成物中の（Ａ）光重合開始剤に対する連鎖移動剤の含有割合も特に限定されないが、（Ａ）光重合開始剤１００質量部に対して、５質量部以上が好ましく、１０質量部以上がより好ましく、１５質量部以上がさらに好ましく、２０質量部以上が特に好ましく、また、５００質量部以下が好ましく、３００質量部以下がより好ましく、１００質量部以下がさらに好ましく、５０質量部以下が特に好ましい。前記下限値以上とすることで高感度となる傾向があり、また、前記上限値以下とすることで所望のパターンを形成しやすくなる傾向がある。連鎖移動剤を含む場合には、例えば、（Ａ）光重合開始剤１００質量部に対する連鎖移動剤の含有割合は５～５００質量部が好ましく、１０～３００質量部がより好ましく、１５～１００質量部がさらに好ましく、２０～５０質量部が特に好ましい。 The content ratio of the chain transfer agent to the photopolymerization initiator (A) in the photosensitive colored resin composition is not particularly limited, but is preferably 5 parts by mass or more based on 100 parts by mass of the photopolymerization initiator (A). 10 parts by mass or more, more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, even more preferably 100 parts by mass or less, Particularly preferred is 50 parts by mass or less. When the ratio is equal to or higher than the lower limit, the sensitivity tends to be high, and when the ratio is lower than the upper limit, a desired pattern tends to be easily formed. When a chain transfer agent is contained, for example, the content ratio of the chain transfer agent to 100 parts by mass of the photopolymerization initiator (A) is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, and 15 to 100 parts by mass. Part by mass is more preferable, and 20 to 50 parts by mass is particularly preferable.
［１－１－２］（Ｂ）成分；アルカリ可溶性樹脂
　本発明の感光性着色樹脂組成物は、（Ｂ）アルカリ可溶性樹脂を含有する。本発明において、（Ｂ）アルカリ可溶性樹脂としてはアルカリ現像液で現像可能なものであれば特に限定されない。
　アルカリ可溶性樹脂としては、カルボキシル基又は水酸基を有する各種樹脂が挙げられるが、現像性に優れるとの観点からはカルボキシル基を有するものが好ましい。
　また、また隔壁側面の垂直性が良好となり、隔壁の熱溶融による撥液剤の流出が抑えられて撥インク性を保持しやすい等の理由からは、エチレン性不飽和基を有するアルカリ可溶性樹脂が好ましい。 [1-1-2] Component (B); Alkali-Soluble Resin The photosensitive colored resin composition of the present invention contains (B) an alkali-soluble resin. In the present invention, the alkali-soluble resin (B) is not particularly limited as long as it can be developed with an alkali developer.
Examples of the alkali-soluble resin include various resins having a carboxyl group or a hydroxyl group, and those having a carboxyl group are preferable from the viewpoint of excellent developability.
In addition, the alkali-soluble resin having an ethylenically unsaturated group is preferable because the verticality of the side wall of the partition wall is improved, and the outflow of the liquid repellent agent due to the thermal melting of the partition wall is suppressed and the ink repellency is easily maintained. .
　本発明の感光性着色樹脂組成物の（Ｂ）アルカリ可溶性樹脂は、撥インク性の観点から、側鎖にエチレン性不飽和基を有するアクリル共重合樹脂（Ｂ１１）（以下、「アクリル共重合樹脂（Ｂ１１）」と略記する場合がある。）を含むことが好ましい。また一方で、パターンの直線性の観点からは、エポキシ（メタ）アクリレート樹脂（Ｂ１２）を含むことが好ましい。 The (B) alkali-soluble resin of the photosensitive colored resin composition of the present invention is preferably an acrylic copolymer resin (B11) having an ethylenically unsaturated group in a side chain (hereinafter referred to as an “acryl copolymer resin”) from the viewpoint of ink repellency. (B11) "). On the other hand, from the viewpoint of the linearity of the pattern, it is preferable to include an epoxy (meth) acrylate resin (B12).
　さらには、撥インク性と直線性の両立の観点からは、（Ｂ）アルカリ可溶性樹脂として、アクリル共重合樹脂（Ｂ１１）と、エポキシ（メタ）アクリレート樹脂（Ｂ１２）の両者を含むことが好ましい。 From the viewpoint of achieving both ink repellency and linearity, it is preferable that the alkali-soluble resin (B) contains both an acrylic copolymer resin (B11) and an epoxy (meth) acrylate resin (B12).
　まずは、アクリル共重合樹脂（Ｂ１１）について詳述する。 First, the acrylic copolymer resin (B11) will be described in detail.
［アクリル共重合樹脂（Ｂ１１）］
　アクリル共重合樹脂（Ｂ１１）は、側鎖にエチレン性不飽和基を有する。エチレン性不飽和基を有するものとすることで、露光による光硬化が起こってより強固な膜となり、現像時にも撥液剤が流出しにくくなると考えられる。 [Acrylic copolymer resin (B11)]
The acrylic copolymer resin (B11) has an ethylenically unsaturated group in a side chain. It is considered that by having an ethylenically unsaturated group, photo-curing by exposure occurs to form a stronger film, and the liquid-repellent agent hardly flows out during development.
（一般式（Ｉ）で表される部分構造）
　アクリル共重合樹脂（Ｂ１１）が有する、エチレン性不飽和基を有する側鎖を含む部分構造は特に限定されないが、膜の柔軟性に伴うラジカルの発散しやすさの観点から、例えば、下記一般式（Ｉ）で表される部分構造を有することが好ましい。 (Partial structure represented by general formula (I))
The partial structure of the acrylic copolymer resin (B11), including the side chain having an ethylenically unsaturated group, is not particularly limited. From the viewpoint of the ease with which radicals are released due to the flexibility of the film, for example, the following general formula: It preferably has a partial structure represented by (I).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
（式（Ｉ）中、Ｒ1及びＲ2は各々独立に、水素原子又はメチル基を表す。＊は結合手を表す。） (In the formula (I), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. * Represents a bond)
　また、前記式（Ｉ）で表される部分構造の中でも、感度やアルカリ現像性の観点から、下記一般式（Ｉ’）で表される部分構造が好ましい。 中 で も Also, among the partial structures represented by the formula (I), the partial structure represented by the following general formula (I ′) is preferable from the viewpoint of sensitivity and alkali developability.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（式（Ｉ’）中、Ｒ1及びＲ2は各々独立に、水素原子又はメチル基を表す。ＲXは水素原
子又は多塩基酸残基を表す。） (In the formula (I '), R 1 and R 2 are each independently, .R X represents a hydrogen atom or a methyl group represents a hydrogen atom or a polybasic acid residue.)
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。多塩基酸としては、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた１種又は２種以上が挙げられる。
　これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。 The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endmethylenetetrahydrophthalic acid One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, preferably, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Is tetrahydrophthalic acid or biphenyltetracarboxylic acid.
　アクリル共重合樹脂（Ｂ１１）が前記一般式（Ｉ）で表される部分構造を含む場合、その含有割合は特に限定されないが、アクリル共重合樹脂（Ｂ１１）の構成単位の総モル数に対して１０モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上がさらに好ましく、４０モル％以上がよりさらに好ましく、５０モル％以上が特に好ましく、また、９０モル％以下が好ましく、８５モル％以下がより好ましく、８０モル％以下がさらに好ましく、７５モル％以下がよりさらに好ましく、７０モル％以下が特に好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。アクリル共重合樹脂（Ｂ１１）が前記一般式（Ｉ）で表される部分構造を含む場合、例えば、前記一般式（Ｉ）で表される部分構造の含有割合は１０～９０モル％が好ましく、２０～８５モル％がより好ましく、３０～８０モル％がさらに好ましく、４０～７５モル％がよりさらに好ましく、５０～７０モル％が特に好ましい。 When the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (I), the content ratio is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). 10 mol% or more is preferable, 20 mol% or more is more preferable, 30 mol% or more is further preferable, 40 mol% or more is still more preferable, 50 mol% or more is particularly preferable, and 90 mol% or less is preferable, and 85 mol% or less is preferable. Mol% or less, more preferably 80 mol% or less, even more preferably 75 mol% or less, and particularly preferably 70 mol% or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. When the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (I), for example, the content ratio of the partial structure represented by the general formula (I) is preferably 10 to 90 mol%, It is more preferably from 20 to 85 mol%, further preferably from 30 to 80 mol%, further preferably from 40 to 75 mol%, particularly preferably from 50 to 70 mol%.
　アクリル共重合樹脂（Ｂ１１）が前記一般式（Ｉ’）で表される部分構造を含む場合、その含有割合は特に限定されないが、アクリル共重合樹脂（Ｂ１１）の構成単位の総モル数に対して１０モル％以上が好ましく、２０モル％以上がより好ましく、２５モル％以上がさらに好ましく、３０モル％以上がよりさらに好ましく、３５モル％以上が特に好ましく、また、８０モル％以下が好ましく、７５モル％以下がより好ましく、７０モル％以下がさらに好ましく、６５モル％以下が特に好ましい。前記下限値以上とすることでアルカリ現像性が良好になりやすい傾向があり、また、前記上限値以下とすることで現像密着性が確保しやすい傾向がある。アクリル共重合樹脂（Ｂ１１）が前記一般式（Ｉ’）で表される部分構造を含む場合、例えば、前記一般式（Ｉ’）で表される部分構造の含有割合は１０～８０モル％が好ましく、２０～８０モル％がより好ましく、２５～７５モル％がさらに好ましく、３０～７０モル％がよりさらに好ましく、３５～６５モル％が特に好ましい。 When the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (I ′), the content thereof is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). Is preferably at least 10 mol%, more preferably at least 20 mol%, still more preferably at least 25 mol%, even more preferably at least 30 mol%, particularly preferably at least 35 mol%, and preferably at most 80 mol%, It is more preferably at most 75 mol%, further preferably at most 70 mol%, particularly preferably at most 65 mol%. When the content is not less than the lower limit, alkali developability tends to be good, and when the content is not more than the upper limit, development adhesion tends to be easily ensured. When the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (I ′), for example, the content ratio of the partial structure represented by the general formula (I ′) is 10 to 80 mol%. Preferably, it is 20 to 80 mol%, more preferably 25 to 75 mol%, still more preferably 30 to 70 mol%, and particularly preferably 35 to 65 mol%.
（一般式（ＩＩ）で表される部分構造）
　アクリル共重合樹脂（Ｂ１１）が前記一般式（Ｉ）で表される部分構造を含む場合、他に含まれる部分構造は特に限定されないが、現像密着性の観点から、例えば、下記一般式（ＩＩ）で表される部分構造を有することも好ましい。 (Partial structure represented by general formula (II))
When the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (I), the other partial structure is not particularly limited, but from the viewpoint of development adhesion, for example, the following general formula (II) ) Is also preferable.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　上記式（ＩＩ）中、Ｒ3は水素原子又はメチル基を表し、Ｒ4は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族環基、又は置換基を有していてもよいアルケニル基を表す。 In the formula (II), R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent. Represents an alkenyl group which may have
（Ｒ4）
　前記式（ＩＩ）において、Ｒ4は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族環基、又は置換基を有していてもよいアルケニル基を表す。
　Ｒ4におけるアルキル基としては直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上であることが好ましく、３以上であることがより好ましく、５以上であることがさらに好ましく、８以上であることが特に好ましく、また、２０以下であることが好ましく、１８以下であることがより好ましく、１６以下であることがさらに好ましく、１４以下であることがよりさらに好ましく、１２以下であることが特に好ましい。前記下限値以上とすることで膜強度が高くなり、現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。例えば、アルキル基の炭素数は１～２０が好ましく、３～１８がより好ましく、５～１６がさらに好ましく、８～１４がよりさらに好ましく、８～１２が特に好ましい。 (R 4 )
In the formula (II), R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. .
Examples of the alkyl group for R 4 include a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, It is more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. When the amount is equal to or more than the lower limit, the film strength tends to increase, and the adhesion to development tends to be improved. When the amount is equal to or less than the upper limit, the residue tends to decrease. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 3 to 18, more preferably 5 to 16, still more preferably 8 to 14, and particularly preferably 8 to 12.
　アルキル基の具体例としては、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基等が挙げられる。これらの中でも現像性の観点から、ジシクロペンタニル基又はドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。
　また、アルキル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoint of developability, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And an acryloyl group and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ4における芳香族環基としては、１価の芳香族炭化水素環基及び１価の芳香族複素環基が挙げられる。その炭素数は６以上であることが好ましく、また、２４以下であることが好ましく、２２以下であることがより好ましく、２０以下であることがさらに好ましく、１８以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。例えば、芳香族環基の炭素数は６～２４が好ましく、６～２２がより好ましく、６～２０がさらに好ましく、６～１８が特に好ましい。
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよく、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などが挙げられる。
　また、芳香族複素環基における芳香族複素環基としては、単環であっても縮合環であってもよく、例えば、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などが挙げられる。これらの中でも現像性の観点から、ベンゼン環、又はナフタレン環が好ましく、ベンゼン環がより好ましい。
　また、芳香族環基が有していてもよい置換基としては、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the aromatic ring group for R 4 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. For example, the aromatic ring group preferably has 6 to 24 carbon atoms, more preferably has 6 to 22 carbon atoms, further preferably has 6 to 20 carbon atoms, and particularly preferably has 6 to 18 carbon atoms.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene Ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
Further, the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroleimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, flopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benziso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolino Ring, and azulene ring. Among these, from the viewpoint of developability, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable.
Examples of the substituent which the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, and an epoxy group. And an oligoethylene glycol group, a phenyl group, a carboxyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ4におけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上であり、また、２２以下であることが好ましく、２０以下であることがより好ましく、１８以下であることがさらに好ましく、１６以下であることがよりさらに好ましく、１４以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。例えば、アルケニル基の炭素数は２～２２が好ましく、２～２０がより好ましく、２～１８がさらに好ましく、２～１６がよりさらに好ましく、２～１４が特に好ましい。 Examples of the alkenyl group for R 4 include a linear, branched or cyclic alkenyl group. The number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less, and 14 or less Is particularly preferred. When the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, and particularly preferably 2 to 14.
　また、アルケニル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　このように、Ｒ4は置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアルケニル基を表すが、これらの中でも現像性と膜強度の観点から、アルキル基又はアルケニル基が好ましく、アルキル基がより好ましい。 As described above, R 4 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. From the viewpoints of developability and film strength, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.
　アクリル共重合樹脂（Ｂ１１）が前記一般式（ＩＩ）で表される部分構造を含む場合、その含有割合は特に限定されないが、アクリル共重合樹脂（Ｂ１１）の構成単位の総モル数に対して１モル％以上が好ましく、５モル％以上がより好ましく、１０モル％以上がさらに好ましく、２０モル％以上が特に好ましく、また、７０モル％以下が好ましく、６０モル％以下がより好ましく、５０モル％以下がさらに好ましく、４０モル％以下が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。アクリル共重合樹脂（Ｂ１１）が前記一般式（ＩＩ）で表される部分構造を含む場合、例えば、前記一般式（ＩＩ）で表される部分構造の含有割合は１～７０モル％が好ましく、５～６０モル％がより好ましく、１０～５０モル％がさらに好ましく、２０～４０モル％が特に好ましい。 When the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (II), the content thereof is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). 1 mol% or more is preferable, 5 mol% or more is more preferable, 10 mol% or more is more preferable, 20 mol% or more is particularly preferable, and 70 mol% or less is preferable, 60 mol% or less is more preferable, and 50 mol% or less is used. % Or less, more preferably 40 mol% or less. When the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. When the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (II), for example, the content ratio of the partial structure represented by the general formula (II) is preferably 1 to 70 mol%, 5 to 60 mol% is more preferable, 10 to 50 mol% is further preferable, and 20 to 40 mol% is particularly preferable.
（一般式（ＩＩＩ）で表される部分構造）
　アクリル共重合樹脂（Ｂ１１）が前記一般式（Ｉ）で表される部分構造を含む場合、他に含まれる部分構造として、耐熱性、膜強度の観点から下記一般式（ＩＩＩ）で表される部分構造が含まれることが好ましい。 (Partial structure represented by general formula (III))
When the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (I), the other partial structure is represented by the following general formula (III) from the viewpoint of heat resistance and film strength. Preferably, a partial structure is included.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記式（ＩＩＩ）中、Ｒ5は水素原子又はメチル基を表し、Ｒ6は置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、ヒドロキシル基、カルボキシル基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。ｔは０～５の整数を表す。 In the formula (III), R 5 represents a hydrogen atom or a methyl group, and R 6 has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Represents an alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group. t represents an integer of 0 to 5.
（Ｒ6）
　前記式（ＩＩＩ）においてＲ6は置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、ヒドロキシル基、カルボキシル基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。
　Ｒ6におけるアルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上であることが好ましく、３以上であることがより好ましく、５以上であることがさらに好ましく、また、２０以下であることが好ましく、１８以下であることがより好ましく、１６以下であることがさらに好ましく、１４以下であることがよりさらに好ましく、１２以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。例えば、アルキル基の炭素数は１～２０が好ましく、３～１８がより好ましく、５～１６がさらに好ましく、５～１４がよりさらに好ましく、５～１２が特に好ましい。 (R 6)
In the formula (III), R 6 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, and a carboxyl group. , A halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
Examples of the alkyl group for R 6 include a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, It is still more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. When the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 3 to 18, still more preferably 5 to 16, still more preferably 5 to 14, and particularly preferably 5 to 12.
　アルキル基の具体例としては、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基等が挙げられる。これらの中でも現像性と膜強度の観点から、ジシクロペンタニル基又はドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。
　また、アルキル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoints of developability and film strength, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And an acryloyl group and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ6におけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上であり、また、２２以下であることが好ましく、２０以下であることがより好ましく、１８以下であることがさらに好ましく、１６以下であることがよりさらに好ましく、１４以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。例えば、アルケニル基の炭素数は２～２２が好ましく、２～２０がより好ましく、２～１８がさらに好ましく、２～１６がよりさらに好ましく、２～１４が特に好ましい。 Examples of the alkenyl group for R 6 include a linear, branched or cyclic alkenyl group. The number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less, and 14 or less Is particularly preferred. When the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, and particularly preferably 2 to 14.
　また、アルケニル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ6におけるアルキニル基としては、直鎖状、分岐鎖状又は環状のアルキニル基が挙げられる。その炭素数は、２以上であり、また、２２以下であることが好ましく、２０以下であることがより好ましく、１８以下であることがさらに好ましく、１６以下であることがよりさらに好ましく、１４以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。例えば、アルキニル基の炭素数は２～２２が好ましく、２～２０がより好ましく、２～１８がさらに好ましく、２～１６がよりさらに好ましく、２～１４が特に好ましい。 Examples of the alkynyl group for R 6 include a linear, branched or cyclic alkynyl group. The number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less, and 14 or less Is particularly preferred. When the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. For example, the carbon number of the alkynyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, and particularly preferably 2 to 14.
　また、アルキニル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent which the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ6におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、これらの中でも撥インク性の観点からはフッ素原子が好ましい。 Examples of the halogen atom for R 6 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom is preferred from the viewpoint of ink repellency.
　Ｒ6におけるアルコキシ基としては、直鎖状、分岐鎖状又は環状のアルコキシ基が挙げられる。その炭素数は、１以上であり、また、２０以下であることが好ましく、１８以下であることがより好ましく、１６以下であることがさらに好ましく、１４以下であることがよりさらに好ましく、１２以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。例えば、アルコキシ基の炭素数は１～２０が好ましく、１～１８がより好ましく、１～１６がさらに好ましく、１～１４がよりさらに好ましく、１～１２が特に好ましい。 Examples of the alkoxy group for R 6 include a linear, branched or cyclic alkoxy group. The carbon number is 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less, and 12 or less. Is particularly preferred. When the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. For example, the carbon number of the alkoxy group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, and particularly preferably 1 to 12.
　また、アルコシ基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent which the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. And an acryloyl group and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ6におけるアルキルスルフィド基としては、直鎖状、分岐鎖状又は環状のアルキルスルフィド基が挙げられる。その炭素数は、１以上であることが好ましく、また、２０以下であることが好ましく、１８以下であることがより好ましく、１６以下であることがさらに好ましく、１４以下であることがよりさらに好ましく、１２以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。例えば、アルキルスルフィド基の炭素数は１～２０が好ましく、１～１８がより好ましく、１～１６がさらに好ましく、１～１４がよりさらに好ましく、１～１２が特に好ましい。 Examples of the alkyl sulfide group for R 6 include a linear, branched or cyclic alkyl sulfide group. The carbon number is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and even more preferably 14 or less. , 12 or less is particularly preferable. When the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. For example, the carbon number of the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, and particularly preferably 1 to 12.
　また、アルキルスルフィド基におけるアルキル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent which the alkyl group in the alkyl sulfide group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, and a phenyl group. Groups, a carboxyl group, an acryloyl group, a methacryloyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　このように、Ｒ6は置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、ヒドロキシル基、カルボキシル基、ハロゲン原子、アルコキシ基、ヒドロキシアルキル基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表すが、これらの中でも現像性の観点から、ヒドロキシル基又はカルボキシル基が好ましく、カルボキシル基がより好ましい。 As described above, R 6 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, and a halogen atom. An atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkyl sulfide group which may have a substituent, and among these, a hydroxyl group or a carboxyl group is preferable from the viewpoint of developability, and a carboxyl group is more preferable. preferable.
　前記式（ＩＩＩ）においてｔは０～５の整数を表すが、製造容易性の観点からはｔが０であることが好ましい。 Ｔ In the above formula (III), t represents an integer of 0 to 5, but from the viewpoint of ease of production, it is preferable that t is 0.
　アクリル共重合樹脂（Ｂ１１）が前記一般式（ＩＩＩ）で表される部分構造を含む場合、その含有割合は特に限定されないが、アクリル共重合樹脂（Ｂ１１）の構成単位の総モル数に対して０．５モル％以上が好ましく、１モル％以上がより好ましく、２モル％以上がさらに好ましい。また、５０モル％以下が好ましく、３０モル％以下がより好ましく、２０モル％以下がさらに好ましく、１０モル％以下がよりさらに好ましく、５モル％以下が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。アクリル共重合樹脂（Ｂ１１）が前記一般式（ＩＩＩ）で表される部分構造を含む場合、例えば、前記一般式（ＩＩＩ）で表される部分構造の含有割合は０．５～５０モル％が好ましく、０．５～３０モル％がより好ましく、１～２０モル％がさらに好ましく、１～１０モル％がよりさらに好ましく、２～５モル％が特に好ましい。 When the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (III), the content ratio is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). It is preferably at least 0.5 mol%, more preferably at least 1 mol%, even more preferably at least 2 mol%. Further, it is preferably at most 50 mol%, more preferably at most 30 mol%, further preferably at most 20 mol%, still more preferably at most 10 mol%, particularly preferably at most 5 mol%. When the content is not less than the lower limit, the adhesiveness for development tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. When the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (III), for example, the content ratio of the partial structure represented by the general formula (III) is 0.5 to 50 mol%. Preferably, it is 0.5 to 30 mol%, more preferably 1 to 20 mol%, still more preferably 1 to 10 mol%, and particularly preferably 2 to 5 mol%.
（一般式（ＩＶ）で表される部分構造）
　アクリル共重合樹脂（Ｂ１１）が前記一般式（Ｉ）で表される部分構造を有する場合、他に含まれる部分構造として、現像性の観点から下記一般式（ＩＶ）で表される部分構造を有することも好ましい。 (Partial structure represented by general formula (IV))
When the acrylic copolymer resin (B11) has a partial structure represented by the general formula (I), a partial structure represented by the following general formula (IV) from the viewpoint of developability is included as another partial structure. It is also preferred to have.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　上記式（ＩＶ）中、Ｒ7は水素原子又はメチル基を表す。 In the above formula (IV), R 7 represents a hydrogen atom or a methyl group.
　アクリル共重合樹脂（Ｂ１１）が前記一般式（ＩＶ）で表される部分構造を含む場合、その含有割合は特に限定されないが、アクリル共重合樹脂（Ｂ１１）の構成単位の総モル数に対して５モル％以上が好ましく、１０モル％以上がより好ましく、２０モル％以上がさらに好ましく、また、８０モル％以下が好ましく７０モル％以下がより好ましく、６０％モル以下がさらに好ましい。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで現像密着性が向上する傾向がある。アクリル共重合樹脂（Ｂ１１）が前記一般式（ＩＶ）で表される部分構造を含む場合、例えば、前記一般式（ＩＶ）で表される部分構造の含有割合は５～８０モル％が好ましく、１０～７０モル％がより好ましく、２０～６０モル％がさらに好ましい。 When the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (IV), the content ratio is not particularly limited, but is based on the total number of moles of the structural units of the acrylic copolymer resin (B11). 5 mol% or more is preferable, 10 mol% or more is more preferable, 20 mol% or more is more preferable, and 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60 mol% or less is further preferable. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the development adhesion tends to be improved. When the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (IV), for example, the content ratio of the partial structure represented by the general formula (IV) is preferably 5 to 80 mol%, The content is more preferably from 10 to 70 mol%, even more preferably from 20 to 60 mol%.
　一方で、アクリル共重合樹脂（Ｂ１１）の酸価は特に限定されないが、３０ｍｇＫＯＨ／ｇ以上が好ましく、４０ｍｇＫＯＨ／ｇ以上がより好ましく、５０ｍｇＫＯＨ／ｇ以上がさらに好ましく、６０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、また、１５０ｍｇＫＯＨ／ｇ以下が好ましく、１４０ｍｇＫＯＨ／ｇ以下がより好ましく、１３０ｍｇＫＯＨ／ｇ以下がさらに好ましく、１２０ｍｇＫＯＨ／ｇ以下がよりさらに好ましい。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで現像密着性が向上する傾向がある。例えば、アクリル共重合樹脂（Ｂ１１）の酸価は３０～１５０ｍｇＫＯＨ／ｇが好ましく、４０～１４０ｍｇＫＯＨ／ｇがより好ましく、５０～１３０ｍｇＫＯＨ／ｇがさらに好ましく、６０～１２０ｍｇＫＯＨ／ｇが特に好ましい。 On the other hand, the acid value of the acrylic copolymer resin (B11) is not particularly limited, but is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, still more preferably 50 mgKOH / g or more, and still more preferably 60 mgKOH / g or more. Also, it is preferably 150 mgKOH / g or less, more preferably 140 mgKOH / g or less, still more preferably 130 mgKOH / g or less, and still more preferably 120 mgKOH / g or less. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the development adhesion tends to be improved. For example, the acid value of the acrylic copolymer resin (B11) is preferably 30 to 150 mgKOH / g, more preferably 40 to 140 mgKOH / g, further preferably 50 to 130 mgKOH / g, and particularly preferably 60 to 120 mgKOH / g.
　アクリル共重合樹脂（Ｂ１１）の重量平均分子量（Ｍｗ）は特に限定されないが、通常１０００以上、好ましくは２０００以上、より好ましくは４０００以上、さらに好ましくは６０００以上、よりさらに好ましくは７０００以上、特に好ましくは８０００以上であり、また、通常３００００以下、好ましくは２００００以下、より好ましくは１５０００以下、さらに好ましくは１００００以下である。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣は低減する傾向がある。例えば、アクリル共重合樹脂（Ｂ１１）の重量平均分子量（Ｍｗ）は１０００～３００００が好ましく、２０００～２００００がより好ましく、４０００～１５０００がさらに好ましく、６０００～１５０００がよりさらに好ましく、７０００～１００００がとりわけ好ましく、８０００～１００００が特に好ましい。 The weight average molecular weight (Mw) of the acrylic copolymer resin (B11) is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 4,000 or more, further preferably 6,000 or more, more preferably 7000 or more, and particularly preferably. Is 8000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and further preferably 10,000 or less. When the amount is not less than the lower limit, the adhesiveness for development tends to be improved, and when the amount is not more than the upper limit, the residue tends to be reduced. For example, the weight average molecular weight (Mw) of the acrylic copolymer resin (B11) is preferably from 1,000 to 30,000, more preferably from 2,000 to 20,000, still more preferably from 4,000 to 15,000, still more preferably from 6,000 to 15,000, particularly preferably from 7000 to 10,000. Preferably, 8,000 to 10,000 are particularly preferred.
　（Ｂ）アルカリ可溶性樹脂に含まれるアクリル共重合樹脂（Ｂ１１）の含有割合は特に限定されないが、１０質量％以上が好ましく、３０質量％以上がより好ましく、５０質量％以上がさらに好ましく、７０質量％以上が特に好ましく、また、９５質量％以下が好ましく、９０質量％以下がより好ましく、８５質量％以下がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。例えば、（Ｂ）アルカリ可溶性樹脂に含まれるアクリル共重合樹脂（Ｂ１１）の含有割合は１０～９５質量％が好ましく、３０～９５質量％がより好ましく、５０～９０質量％がさらに好ましく、７０～８５質量％が特に好ましい。 (B) The content ratio of the acrylic copolymer resin (B11) contained in the alkali-soluble resin is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and 70% by mass. %, Particularly preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. For example, the content of the acrylic copolymer resin (B11) in the alkali-soluble resin (B) is preferably from 10 to 95% by mass, more preferably from 30 to 95% by mass, still more preferably from 50 to 90% by mass, and preferably from 70 to 90% by mass. 85% by weight is particularly preferred.
　また、（Ｂ）アルカリ可溶性樹脂がアクリル共重合樹脂（Ｂ１１）とエポキシ（メタ）アクリレート樹脂（Ｂ１２）の両方を含む場合、アクリル共重合樹脂（Ｂ１１）の含有割合は、アクリル共重合樹脂（Ｂ１１）とエポキシ（メタ）アクリレート樹脂（Ｂ１２）との含有割合の合計に対して、１０質量％以上が好ましく、３０質量％以上がより好ましく、５０質量％以上がさらに好ましく、７０質量％以上が特に好ましく、また９５質量％以下が好ましく、９０質量％以下がより好ましく、８５質量％以下がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。（Ｂ）アルカリ可溶性樹脂がアクリル共重合樹脂（Ｂ１１）とエポキシ（メタ）アクリレート樹脂（Ｂ１２）の両方を含む場合、アクリル共重合樹脂（Ｂ１１）とエポキシ（メタ）アクリレート樹脂（Ｂ１２）との含有割合の合計に対する、アクリル共重合樹脂（Ｂ１１）の含有割合は１０～９５質量％が好ましく、３０～９５質量％がより好ましく、５０～９０質量％がさらに好ましく、７０～８５質量％が特に好ましい。 When (B) the alkali-soluble resin contains both the acrylic copolymer resin (B11) and the epoxy (meth) acrylate resin (B12), the content of the acrylic copolymer resin (B11) is ) And the total content of the epoxy (meth) acrylate resin (B12) is preferably at least 10% by mass, more preferably at least 30% by mass, further preferably at least 50% by mass, particularly preferably at least 70% by mass. It is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. (B) When the alkali-soluble resin contains both the acrylic copolymer resin (B11) and the epoxy (meth) acrylate resin (B12), the acrylic copolymer resin (B11) and the epoxy (meth) acrylate resin (B12) are contained. The content of the acrylic copolymer resin (B11) with respect to the total of the proportions is preferably from 10 to 95% by mass, more preferably from 30 to 95% by mass, further preferably from 50 to 90% by mass, and particularly preferably from 70 to 85% by mass. .
　なお、アクリル共重合樹脂（Ｂ１１）の具体例としては、例えば、日本国特開平８－２９７３６６号公報や日本国特開２００１－８９５３３号公報に記載の樹脂が挙げられる。 Specific examples of the acrylic copolymer resin (B11) include, for example, the resins described in Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.
　次に、エポキシ（メタ）アクリレート樹脂（Ｂ１２）について詳述する。 Next, the epoxy (meth) acrylate resin (B12) will be described in detail.
［エポキシ（メタ）アクリレート樹脂（Ｂ１２）］
　エポキシ（メタ）アクリレート樹脂（Ｂ１２）は、エポキシ樹脂にエチレン性不飽和モノカルボン酸又はエステル化合物を付加し、任意でイソシアネート基含有化合物を反応させた後、更に多塩基酸又はその無水物を反応させた樹脂である。例えば、エポキシ樹脂のエポキシ基に、不飽和モノカルボン酸のカルボキシル基が開環付加されることにより、エポキシ化合物にエステル結合（－ＣＯＯ－）を介してエチレン性不飽和結合が付加されると共に、その際生じた水酸基に、多塩基酸無水物の一方のカルボキシ基が付加されたものが挙げられる。また多塩基酸無水物を付加するときに、多価アルコールを同時に添加して付加されたものも挙げられる。 [Epoxy (meth) acrylate resin (B12)]
The epoxy (meth) acrylate resin (B12) is obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin, optionally reacting an isocyanate group-containing compound, and further reacting with a polybasic acid or an anhydride thereof. It is the resin which was made to be. For example, a carboxyl group of an unsaturated monocarboxylic acid is ring-opened to an epoxy group of an epoxy resin, whereby an ethylenically unsaturated bond is added to an epoxy compound via an ester bond (—COO—). One obtained by adding one carboxy group of the polybasic acid anhydride to the hydroxyl group generated at that time. Moreover, when adding a polybasic acid anhydride, the thing added by simultaneously adding a polyhydric alcohol is also mentioned.
　また上記反応で得られた樹脂のカルボキシル基に、更に反応し得る官能基を有する化合物を反応させて得られる樹脂も、上記エポキシ（メタ）アクリレート樹脂（Ｂ１２）に含まれる。
　このように、エポキシ（メタ）アクリレート樹脂は化学構造上、実質的にエポキシ基を有さず、かつ「（メタ）アクリレート」に限定されるものではないが、エポキシ化合物（エポキシ樹脂）が原料であり、かつ、「（メタ）アクリレート」が代表例であるので慣用に従いこのように命名されている。 The epoxy (meth) acrylate resin (B12) also includes a resin obtained by reacting a compound having a functional group that can be further reacted with a carboxyl group of the resin obtained by the above reaction.
As described above, the epoxy (meth) acrylate resin has substantially no epoxy group due to its chemical structure and is not limited to “(meth) acrylate”, but the epoxy compound (epoxy resin) is used as a raw material. And "(meth) acrylate" is a representative example, and is so named according to common usage.
　ここで、エポキシ樹脂とは、熱硬化により樹脂を形成する以前の原料化合物をも含めて言うこととし、そのエポキシ樹脂としては、公知のエポキシ樹脂の中から適宜選択して用いることができる。また、エポキシ樹脂は、フェノール性化合物とエピハロヒドリンとを反応させて得られる化合物を用いることができる。フェノール性化合物としては、２価もしくは２価以上のフェノール性水酸基を有する化合物が好ましく、単量体でも重合体でもよい。
　具体的には、例えば、ビスフェノールＡエポキシ樹脂、ビスフェノールＦエポキシ樹脂、ビスフェノールＳエポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ビフェニルノボラックエポキシ樹脂、トリスフェノールエポキシ樹脂、フェノールとジシクロペンタンとの重合エポキシ樹脂、ジハイドロオキシルフルオレン型エポキシ樹脂、ジハイドロオキシルアルキレンオキシルフルオレン型エポキシ樹脂、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのジグリシジルエーテル化物、１，１－ビス（４’－ヒドロキシフェニル）アダマンタンのジグリシジルエーテル化物、などが挙げられ、このように主鎖に芳香族環を有するものを好適に用いることができる。 Here, the epoxy resin includes a raw material compound before a resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. As the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, biphenyl novolak epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane Epoxy resin, dihydroxylfluorene type epoxy resin, dihydroxylalkyleneoxylfluorene type epoxy resin, diglycidyl etherified product of 9,9-bis (4′-hydroxyphenyl) fluorene, 1,1-bis (4′-hydroxy And diglycidyl etherified products of phenyl) adamantane. Those having an aromatic ring in the main chain can be suitably used.
　中でも、高い硬化膜強度の観点から、ビスフェノールＡエポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、フェノールとジシクロペンタジエンとの重合エポキシ樹脂、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのジグリシジルエーテル化物、などが好ましく、ビスフェノールＡエポキシ樹脂が特に好ましい。
　エポキシ樹脂の具体例としては、例えば、ビスフェノールＡ型エポキシ樹脂（例えば、三菱ケミカル社製の「ｊＥＲ（登録商標、以下同じ。）８２８」、「ｊＥＲ１００１」、「ｊＥＲ１００２」、「ｊＥＲ１００４」、日本化薬社製の「ＮＥＲ－１３０２」（エポキシ当量３２３，軟化点７６℃）等）、ビスフェノールＦ型樹脂（例えば、三菱ケミカル社製の「ｊＥＲ８０７」、「ｊＥＲ４００４Ｐ」、「ｊＥＲ４００５Ｐ」、「ｊＥＲ４００７Ｐ」、日本化薬社製の「ＮＥＲ－７４０６」（エポキシ当量３５０，軟化点６６℃）等）、ビスフェノールＳ型エポキシ樹脂、ビフェニルグリシジルエーテル（例えば、三菱ケミカル社製の「ｊＥＲＹＸ－４０００」）、フェノールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ（登録商標、以下同じ。）－２０１」、三菱ケミカル社製の「ｊＥＲ１５２」、「ｊＥＲ１５４」、ダウケミカル社製の「ＤＥＮ－４３８」）、（ｏ，ｍ，ｐ－）クレゾールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＯＣＮ（登録商標、以下同じ。）－１０２Ｓ」、「ＥＯＣＮ－１０２０」、「ＥＯＣＮ－１０４Ｓ」）、トリグリシジルイソシアヌレート（例えば、日産化学社製の「ＴＥＰＩＣ（登録商標）」）、トリスフェノールメタン型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ－５０１」、「ＥＰＰＮ－５０２」、「ＥＰＰＮ－５０３」）、脂環式エポキシ樹脂（ダイセル社製の「セロキサイド（登録商標、以下同じ。）２０２１Ｐ」、「セロキサイドＥＨＰＥ」）、ジシクロペンタジエンとフェノールの反応によるフェノール樹脂をグリシジル化したエポキシ樹脂（例えば、ＤＩＣ社製の「ＥＸＡ－７２００」、日本化薬社製の「ＮＣ－７３００」）、下記一般式（ｉ－１１）～（ｉ－１４）で表されるエポキシ樹脂、等を好適に用いることができる。具体的には、下記一般式（ｉ－１１）で表されるエポキシ樹脂として日本化薬社製の「ＸＤ－１０００」、下記一般式（ｉ－１２）で表されるエポキシ樹脂として日本化薬社製の「ＮＣ－３０００」、下記一般式（ｉ－１４）で表されるエポキシ樹脂として新日鉄住金化学社製の「ＥＳＦ－３００」等が挙げられる。 Among them, bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, and 9,9-bis (4′-hydroxyphenyl) fluorene are preferred from the viewpoint of high cured film strength. Diglycidyl ether compounds are preferred, and bisphenol A epoxy resin is particularly preferred.
Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin (for example, “jER (registered trademark, the same applies hereinafter) 828”, “jER1001”, “jER1002”, “jER1004”, manufactured by Mitsubishi Chemical Corporation). Yakusha's “NER-1302” (epoxy equivalent: 323, softening point: 76 ° C.), bisphenol F type resin (for example, Mitsubishi Chemical's “jER807”, “jER4004P”, “jER4005P”, “jER4007P”, Nerika Kagaku's “NER-7406” (epoxy equivalent 350, softening point 66 ° C.), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg, “jERYX-4000” manufactured by Mitsubishi Chemical Corporation), phenol novolak Type epoxy resin (for example, Nippon Kayaku's "EPP (Registered trademark, the same applies hereinafter) -201 "," jER152 "and" jER154 "manufactured by Mitsubishi Chemical Corporation," DEN-438 "manufactured by Dow Chemical Company), (o, m, p-) cresol novolac epoxy resin (Eg, “EOCN (registered trademark, the same applies hereinafter) -102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku), triglycidyl isocyanurate (eg, “TEPIC” manufactured by Nissan Chemical Industries, Ltd.) (Registered trademark) "), a trisphenol methane type epoxy resin (for example," EPPN-501 "," EPPN-502 "," EPPN-503 "manufactured by Nippon Kayaku), an alicyclic epoxy resin (manufactured by Daicel Corporation) "Celoxide (registered trademark, the same applies hereinafter) 2021P", "Celoxide EHPE"), dicyclopentadiene and phenol Resin (for example, “EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.) obtained by glycidylation of a phenol resin according to the following general formulas (i-11) to (i-14). Epoxy resins and the like represented can be suitably used. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (i-11), and Nippon Kayaku as an epoxy resin represented by the following general formula (i-12) "NC-3000" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (i-14).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記一般式（ｉ－１１）において、ｎは平均値であり、０～１０の数を表す。Ｒ111は各々独立に水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ111は、それぞれ同じであっても異なっていてもよい。 In the above general formula (i-11), n is an average value and represents a number from 0 to 10. R 111 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. A plurality of R 111 present in one molecule may be the same or different.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記一般式（ｉ－１２）において、ｎは平均値であり、０～１０の数を表す。Ｒ121は各々独立に水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ121は、それぞれ同じであっても異なっていてもよい。 In the general formula (i-12), n is an average value and represents a number from 0 to 10. R 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R 121 present in one molecule may be the same or different.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記一般式（ｉ－１３）において、Ｘは下記一般式（ｉ－１３－１）又は（ｉ－１３－２）で表される連結基を表す。但し、分子構造中に１つ以上のアダマンタン構造を含む。ｃは２又は３を表す。 Ｘ In the above general formula (i-13), X represents a linking group represented by the following general formula (i-13-1) or (i-13-2). However, one or more adamantane structures are included in the molecular structure. c represents 2 or 3.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記一般式（ｉ－１３－１）及び（ｉ－１３－２）において、Ｒ131～Ｒ134及びＲ135～Ｒ137は、各々独立に、置換基を有していてもよいアダマンチル基、水素原子、置換基を有していてもよい炭素数１～１２のアルキル基、又は置換基を有していてもよいフェニル基を表す。＊は結合手を表す。 In the above formulas (i-13-1) and (i-13-2), R 131 to R 134 and R 135 to R 137 each independently represent an adamantyl group which may have a substituent, hydrogen Represents an atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. * Represents a bond.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記一般式（ｉ－１４）において、ｐ及びｑは各々独立に０～４の整数を表し、Ｒ141及びＲ142は各々独立に炭素数１～４のアルキル基又はハロゲン原子を表す。Ｒ143及びＲ144は各々独立に炭素数１～４のアルキレン基を表す。ｘ及びｙは各々独立に０以上の整数を表す。 In the general formula (i-14), p and q each independently represent an integer of 0 to 4, and R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. R 143 and R 144 each independently represent an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or more.
　これらの中で、一般式（ｉ－１１）～（ｉ－１４）のいずれかで表されるエポキシ樹脂を用いることが好ましい。 の Among them, it is preferable to use an epoxy resin represented by any of the general formulas (i-11) to (i-14).
　エチレン性不飽和モノカルボン酸としては、例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸等、および、ペンタエリスリトールトリ（メタ）アクリレート無水コハク酸付加物、ペンタエリスリトールトリ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水コハク酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、（メタ）アクリル酸とε－カプロラクトンとの反応生成物などが挙げられる。中でも、感度の観点から、（メタ）アクリル酸が好ましい。 Examples of the ethylenically unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, and pentaerythritol tri (meth) acrylate succinic anhydride adduct, Erythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydro Examples include phthalic anhydride adducts and reaction products of (meth) acrylic acid and ε-caprolactone. Among them, (meth) acrylic acid is preferred from the viewpoint of sensitivity.
　多塩基酸（無水物）としては、例えば、コハク酸、マレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、３－メチルテトラヒドロフタル酸、４－メチルテトラヒドロフタル酸、３－エチルテトラヒドロフタル酸、４－エチルテトラヒドロフタル酸、ヘキサヒドロフタル酸、３－メチルヘキサヒドロフタル酸、４－メチルヘキサヒドロフタル酸、３－エチルヘキサヒドロフタル酸、４－エチルヘキサヒドロフタル酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、およびそれらの無水物などが挙げられる。中でも、アウトガスの観点から、コハク酸無水物、マレイン酸無水物、テトラヒドロフタル酸無水物、またはヘキサヒドロフタル酸無水物が好ましく、コハク酸無水物又はテトラヒドロフタル酸無水物がより好ましい。 Examples of polybasic acids (anhydrides) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid Benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Above all, from the viewpoint of outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride is preferable, and succinic anhydride or tetrahydrophthalic anhydride is more preferable.
　多価アルコールを用いることで、エポキシ（メタ）アクリレート樹脂（Ｂ１２）の分子量を増大させ、分子中に分岐を導入することができ、分子量と粘度のバランスをとることができる傾向がある。また、分子中への酸基の導入率を増やすことができ、感度や密着性等のバランスがとれやすい傾向がある。
　多価アルコールとしては、例えばトリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリメチロールエタン、１，２，３－プロパントリオールの中から選ばれる１種又は２種以上の多価アルコールであることが好ましい。 By using a polyhydric alcohol, the molecular weight of the epoxy (meth) acrylate resin (B12) can be increased, a branch can be introduced into the molecule, and the molecular weight and the viscosity tend to be balanced. In addition, the rate of introduction of acid groups into the molecule can be increased, and there is a tendency that sensitivity, adhesion and the like are easily balanced.
Examples of the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably, there is.
　エポキシ（メタ）アクリレート樹脂としては、前述のもの以外に、韓国公開特許第１０－２０１３－００２２９５５号公報に記載のもの等が挙げられる。 As the epoxy (meth) acrylate resin, in addition to those described above, those described in Korean Laid-Open Patent Application No. 10-2013-0022955 can be mentioned.
　エポキシ（メタ）アクリレート樹脂（Ｂ１２）の酸価は特に限定されないが、１０ｍｇＫＯＨ／ｇ以上が好ましく、３０ｍｇＫＯＨ／ｇ以上がより好ましく、５０ｍｇＫＯＨ／ｇ以上がさらに好ましく、７０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、８０ｍｇＫＯＨ／ｇ以上が特に好ましく、また、２００ｍｇＫＯＨ／ｇ以下が好ましく、１８０ｍｇＫＯＨ／ｇ以下がより好ましく、１５０ｍｇＫＯＨ／ｇ以下がさらに好ましく、１２０ｍｇＫＯＨ／ｇ以下がよりさらに好ましく、１１０ｍｇＫＯＨ／ｇ以下が特に好ましい。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで膜強度が向上する傾向がある。エポキシ（メタ）アクリレート樹脂（Ｂ１２）の酸価は１０～２００ｍｇＫＯＨ／ｇが好ましく、３０～１８０ｍｇＫＯＨ／ｇがより好ましく、５０～１５０ｍｇＫＯＨ／ｇがさらに好ましく、７０～１２０ｍｇＫＯＨ／ｇがよりさらに好ましく、８０～１１０ｍｇＫＯＨ／ｇが特に好ましい。 The acid value of the epoxy (meth) acrylate resin (B12) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, still more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more. 80 mgKOH / g or more is particularly preferable, and 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 150 mgKOH / g or less is further preferable, 120 mgKOH / g or less is further preferable, and 110 mgKOH / g or less is particularly preferable. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the film strength tends to be improved. The acid value of the epoxy (meth) acrylate resin (B12) is preferably from 10 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g, still more preferably from 50 to 150 mgKOH / g, even more preferably from 70 to 120 mgKOH / g. Particularly preferred is １１０110 mgKOH / g.
　エポキシ（メタ）アクリレート樹脂（Ｂ１２）の重量平均分子量（Ｍｗ）は特に限定されないが、通常１０００以上、好ましくは２０００以上、より好ましくは３０００以上、さらに好ましくは３５００以上であり、また、通常３００００以下、好ましくは１５０００以下、より好ましくは１００００以下、さらに好ましくは８０００以下、特に好ましくは５０００以下である。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。エポキシ（メタ）アクリレート樹脂（Ｂ１２）の重量平均分子量（Ｍｗ）は１０００～３００００が好ましく、２０００～１５０００がより好ましく、３０００～１００００がさらに好ましく、３５００～８０００がよりさらに好ましく、３５００～５０００が特に好ましい。 The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (B12) is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, further preferably 3500 or more, and usually 30,000 or less. , Preferably 15,000 or less, more preferably 10,000 or less, further preferably 8,000 or less, particularly preferably 5,000 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced. The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (B12) is preferably from 1,000 to 30,000, more preferably from 2,000 to 15,000, still more preferably from 3,000 to 10,000, still more preferably from 3,500 to 8,000, particularly preferably from 3,500 to 5,000. preferable.
　（Ｂ）アルカリ可溶性樹脂がエポキシ（メタ）アクリレート樹脂（Ｂ１２）を含む場合、その含有割合は特に限定されないが、（Ｂ）アルカリ可溶性樹脂中に１０質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましく、３５質量％以上が特に好ましく、また、９０質量％以下が好ましく、７０質量％以下がより好ましく、５０質量％以下がさらに好ましい。前記下限値以上とすることで残渣が低減する傾向があり、また、前記上限値以下とすることで撥インク性が向上する傾向がある。（Ｂ）アルカリ可溶性樹脂がエポキシ（メタ）アクリレート樹脂（Ｂ１２）を含む場合、（Ｂ）アルカリ可溶性樹脂中の含有割合は１０～９０質量％が好ましく、２０～７０質量％がより好ましく、３０～５０質量％がさらに好ましく、３５～５０質量％が特に好ましい。 When the alkali-soluble resin (B) contains the epoxy (meth) acrylate resin (B12), its content is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more in the (B) alkali-soluble resin. Preferably, it is more preferably 30% by mass or more, particularly preferably 35% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less. When the content is not less than the lower limit, the residue tends to be reduced, and when the content is not more than the upper limit, the ink repellency tends to be improved. When the alkali-soluble resin (B) contains the epoxy (meth) acrylate resin (B12), the content in the alkali-soluble resin (B) is preferably from 10 to 90% by mass, more preferably from 20 to 70% by mass, and from 30 to 70% by mass. It is more preferably 50% by mass, particularly preferably 35 to 50% by mass.
　エポキシ（メタ）アクリレート樹脂（Ｂ１２）は、従来公知の方法により合成することができる。具体的には、前記エポキシ樹脂を有機溶剤に溶解させ、触媒と熱重合禁止剤の共存下、前記エチレン性不飽和結合を有する酸又はエステル化合物を加えて付加反応させ、更に多塩基酸又はその無水物を加えて反応を続ける方法を用いることができる。例えば日本国特許第３９３８３７５号公報、日本国特許第５１６９４２２号公報に記載されている方法が挙げられる。 Epoxy (meth) acrylate resin (B12) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having an ethylenically unsaturated bond is added to cause an addition reaction, and further, a polybasic acid or a polybasic acid or the like is added. A method in which an anhydride is added to continue the reaction can be used. For example, the methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422 are exemplified.
　ここで、反応に用いる有機溶剤としては、メチルエチルケトン、シクロヘキサノン、ジエチ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モノメチルエーテルアセテートなどの有機溶剤の１種または２種以上が挙げられる。また、上記触媒としては、トリエチルアミン、ベンジルジメチルアミン、トリベンジルアミン等の第３級アミン類、テトラメチルアンモニウムクロライド、メチルトリエチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、テトラブチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライドなどの第４級アンミニウム塩類、トリフェニルホスフィンなどの燐化合物、トリフェニルスチビンなどのスチビン類などの１種または２種以上が挙げられる。更に、熱重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノンなどの１種または２種以上が挙げられる。 Here, examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, and secondary catalysts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride and trimethylbenzylammonium chloride. One or more of quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, and stibines such as triphenylstibine are exemplified. Furthermore, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, and the like.
　また、エチレン性不飽和結合を有する酸又はエステル化合物としては、エポキシ樹脂のエポキシ基の１化学当量に対して通常０．７～１．３化学当量、好ましくは０．９～１．１化学当量となる量とすることができる。また、付加反応時の温度としては、通常６０～１５０℃、好ましくは８０～１２０℃の温度とすることができる。更に、多塩基酸（無水物）の使用量としては、前記付加反応で生じた水酸基の１化学当量に対して、通常０．１～１．２化学当量、好ましくは０．２～１．１化学当量となる量とすることができる。 The acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, per 1 equivalent of the epoxy group of the epoxy resin. Can be obtained. The temperature at the time of the addition reaction can be usually from 60 to 150 ° C, preferably from 80 to 120 ° C. Further, the amount of the polybasic acid (anhydride) to be used is generally 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents to 1 chemical equivalent of the hydroxyl group generated in the above addition reaction. The amount can be a chemical equivalent.
　エポキシ（メタ）アクリレート樹脂（Ｂ１２）の中でも、膜強度や直線性の観点から、下記一般式（ｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂、下記一般式（ｉｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂、及び下記一般式（ｉｉｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂からなる群から選ばれる少なくとも１種を含むことが好ましい。 Among the epoxy (meth) acrylate resins (B12), from the viewpoint of film strength and linearity, an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (i), represented by the following general formula (ii) It is preferable to include at least one selected from the group consisting of an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (iii) and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (iii).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　式（ｉ）中、Ｒaは水素原子又はメチル基を表し、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。式（ｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。 In the formula (i), Ra represents a hydrogen atom or a methyl group, and Rb represents a divalent hydrocarbon group which may have a substituent. The benzene ring in the formula (i) may be further substituted with any substituent. * Represents a bond.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（ｉｉ）中、Ｒcは各々独立に、水素原子又はメチル基を表す。Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。＊は結合手を表す。 In formula (ii), R c each independently represents a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（ｉｉｉ）中、Ｒeは水素原子又はメチル基を表し、γは単結合、－ＣＯ－、置換基を有していてもよいアルキレン基、又は置換基を有していてもよい２価の環状炭化水素基を表す。式（ｉｉｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。 Wherein (iii), R e represents a hydrogen atom or a methyl group, gamma is a single bond, -CO-, may have a substituent group alkylene group, or a divalent which may have a substituent Represents a cyclic hydrocarbon group. The benzene ring in the formula (iii) may be further substituted with any substituent. * Represents a bond.
　これらの中でもまず、下記一般式（ｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂（以下、「エポキシ（メタ）アクリレート樹脂（Ｂ１２－１）」と称する場合がある。）について詳述する。 Among them, first, an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (i) (hereinafter sometimes referred to as “epoxy (meth) acrylate resin (B12-1)”) is described in detail. Will be described.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　式（ｉ）中、Ｒaは水素原子又はメチル基を表し、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。式（ｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。 In the formula (i), Ra represents a hydrogen atom or a methyl group, and Rb represents a divalent hydrocarbon group which may have a substituent. The benzene ring in the formula (i) may be further substituted with any substituent. * Represents a bond.
（Ｒb）
　前記式（ｉ）において、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。
　２価の炭化水素基としては、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 (R b )
In the formula (i), R b represents a divalent hydrocarbon group which may have a substituent.
Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. No.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状のものが挙げられる。これらの中でも現像溶解性の観点からは直鎖状のものが好ましく、一方で露光部への現像液の浸透低減の観点からは環状のものが好ましい。その炭素数は通常１以上であり、３以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで撥インク性が向上する傾向がある。例えば、２価の脂肪族基の炭素数は１～２０が好ましく、１～１５がより好ましく、１～１０がさらに好ましい。 The divalent aliphatic group includes a linear, branched and cyclic divalent aliphatic group. Among these, a linear one is preferred from the viewpoint of development solubility, and a cyclic one is preferred from the viewpoint of reducing the penetration of the developer into the exposed part. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the ink repellency tends to be improved. For example, the carbon number of the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
　２価の直鎖状脂肪族基の具体例としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基等が挙げられる。これらの中でも撥インク性や製造コストの観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基の具体例としては、前述の２価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等を有する構造が挙げられる。
　２価の環状の脂肪族基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、また、通常１０以下であり、５以下が好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、２価の環状の脂肪族基が有する環の数は１～１０が好ましく、１～５がより好ましい。
　２価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等の環から水素原子を２つ除した基が挙げられる。これらの中でも膜強度と現像性の観点から、アダマンタン環から水素原子を２つ除した基が好ましい。 Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, and the like. Among these, a methylene group is preferable from the viewpoint of ink repellency and production cost.
Specific examples of the divalent branched aliphatic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group as side chains in addition to the aforementioned divalent linear aliphatic group. Group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, and preferably 5 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the divalent cyclic aliphatic group is preferably 1 to 10, more preferably 1 to 5.
Specific examples of the divalent cyclic aliphatic group include two hydrogen atoms removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a cyclododecane ring. The following groups are mentioned. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of film strength and developability.
　２価の脂肪族基が有していてもよい置換基としては、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成容易性の観点から、無置換であることが好ましい。 置換 Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.
　また、２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。その炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、２価の芳香族環基の炭素数は４～２０が好ましく、５～１５がより好ましく、６～１０がさらに好ましい。 In addition, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the carbon number of the divalent aromatic ring group is preferably from 4 to 20, more preferably from 5 to 15, and even more preferably from 6 to 10.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, a chrysene ring having two free valences. Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
　また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。これらの中でも製造コストの観点から、２個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、２個の遊離原子価を有するベンゼン環がより好ましい。 Further, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring and an indole having two free valences. Ring, carbazole ring, pyrroleimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, flopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, a benzene ring or naphthalene ring having two free valences is preferable from the viewpoint of production cost, and a benzene ring having two free valences is more preferable.
　２価の芳香族環基が有していてもよい置換基としては、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。これらの中でも硬化性の観点から、無置換が好ましい。 置換 Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. Among these, non-substitution is preferable from the viewpoint of curability.
　また、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されないが、通常１以上であり、２以上が好ましく、通常１０以下であり、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで膜強度が向上する傾向がある。例えば、２価の脂肪族基の数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましい。
　２価の芳香族環基の数は特に限定されないが、通常１以上であり、２以上が好ましく、通常１０以下であり、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、２価の芳香族環基の数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましい。 Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include one or more of the above-described divalent aliphatic groups and the above-described divalent aromatic group. Examples thereof include groups in which one or more ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the film strength tends to be improved. For example, the number of divalent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of divalent aromatic ring groups is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基の具体例としては、下記式（ｉ－Ａ）～（ｉ－Ｆ）で表される基等が挙げられる。これらの中でも骨格の剛直性と膜の疎水化の観点から、下記式（ｉ－Ａ）で表される基が好ましい。 Specific examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups represented by the following formulas (IA) to (IF). Is mentioned. Among these, a group represented by the following formula (iA) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　前記のとおり、式（ｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。
　これらの中でも硬化性の観点から、無置換であることが好ましい。 As described above, the benzene ring in the formula (i) may be further substituted with any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited either, and may be one or two or more.
Among them, unsubstituted is preferred from the viewpoint of curability.
　また、前記式（ｉ）で表される部分構造は、現像溶解性の観点から、下記式（ｉ－１）で表される部分構造であることが好ましい。 部分 In addition, the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1) from the viewpoint of development solubility.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（ｉ－１）中、Ｒa及びＲbは、前記式（ｉ）のものと同義である。ＲYは水素原子又は多塩基酸残基を表す。＊は結合手を表す。式（ｉ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。 In the formula (i-1), R a and R b have the same meanings as in the formula (i). RY represents a hydrogen atom or a polybasic acid residue. * Represents a bond. The benzene ring in the formula (i-1) may be further substituted with any substituent.
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。多塩基酸としては、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた１種又は２種以上が挙げられる。
　これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。 The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endmethylenetetrahydrophthalic acid One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, preferably, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Is tetrahydrophthalic acid or biphenyltetracarboxylic acid.
　エポキシ（メタ）アクリレート樹脂（Ｂ１２－１）１分子中に含まれる、前記式（ｉ－１）で表される繰り返し単位構造は、１種でも２種以上でもよい。 The repeating unit structure represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) may be one type or two or more types.
　また、エポキシ（メタ）アクリレート樹脂（Ｂ１２－１）１分子中に含まれる、前記式（ｉ）で表される部分構造の数は特に限定されないが、１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、８以下がさらに好ましい。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで膜強度が向上する傾向がある。例えば、エポキシ（メタ）アクリレート樹脂（Ｂ１２－１）１分子中に含まれる、前記式（ｉ）で表される部分構造の数は１～１０が好ましく、２～８がより好ましく、３～８がさらに好ましい。 The number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the film strength tends to be improved. For example, the number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 to 8 Is more preferred.
　また、エポキシ（メタ）アクリレート樹脂（Ｂ１２－１）１分子中に含まれる、前記式（ｉ－１）で表される部分構造の数は特に限定されないが、１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、８以下がさらに好ましい。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで膜強度が向上する傾向がある。例えば、エポキシ（メタ）アクリレート樹脂（Ｂ１２－１）１分子中に含まれる、前記式（ｉ－１）で表される部分構造の数は１～１０が好ましく、２～８がより好ましく、３～８がさらに好ましい。 The number of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. It is preferably 3 or more, more preferably 10 or less, and even more preferably 8 or less. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the film strength tends to be improved. For example, the number of the partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 to 3. -8 is more preferable.
　以下にエポキシ（メタ）アクリレート樹脂（Ｂ１２－１）の具体例を挙げる。 (4) Specific examples of the epoxy (meth) acrylate resin (B12-1) are shown below.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　次に、下記一般式（ｉｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂（以下、「エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）」と称する場合がある。）について詳述する。 Next, an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (ii) (hereinafter sometimes referred to as “epoxy (meth) acrylate resin (B12-2)”) will be described in detail. .
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　式（ｉｉ）中、Ｒcは各々独立に、水素原子又はメチル基を表す。Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。＊は結合手を表す。 In formula (ii), R c each independently represents a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond.
（Ｒd）
　前記式（ｉｉ）において、Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R d )
In the formula (ii), R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、また、通常１０以下であり、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、脂肪族環基が有する環の数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましい。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、脂肪族環基の炭素数は４～４０が好ましく、４～３０がより好ましく、６～２０がさらに好ましく、８～１５が特に好ましい。 The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the aliphatic cyclic group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of carbon atoms in the aliphatic ring group is preferably from 4 to 40, more preferably from 4 to 30, still more preferably from 6 to 20, and particularly preferably from 8 to 15.
　脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも膜強度と現像性の観点から、アダマンタン環が好ましい。 Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of film strength and developability.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、３以上がより好ましく、また、通常１０以下であり、５以下が好ましく、４以下がより好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、芳香族環基が有する環の数は１～１０が好ましく、１～５がより好ましく、１～４がさらに好ましく、２～４が特に好ましい。 On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, 5 or less, preferably 4 or less. Is more preferred. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 4, and particularly preferably 2 to 4.
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がよりさらに好ましく、１２以上が特に好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、芳香族環基の炭素数は４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、１０～１５がよりさらに好ましく、１２～１５が特に好ましい。 Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, and more preferably 30 or less. More preferably, it is more preferably 20 or less, particularly preferably 15 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the aromatic ring group preferably has 4 to 40 carbon atoms, more preferably has 6 to 30 carbon atoms, further preferably has 8 to 20 carbon atoms, further preferably has 10 to 15 carbon atoms, and particularly preferably has 12 to 15 carbon atoms.
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等が挙げられる。これらの中でもパターニング特性の観点から、フルオレン環が好ましい。 Specific examples of the aromatic ring in the aromatic ring group, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, And a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.
　また、環状炭化水素基を側鎖として有する２価の炭化水素基における、２価の炭化水素基は特に限定されないが、例えば、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 In the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, the divalent hydrocarbon group is not particularly limited. For example, a divalent aliphatic group, a divalent aromatic ring group, and one or more And a group obtained by linking a divalent aliphatic group with one or more divalent aromatic ring groups.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状のものが挙げられる。これらの中でも現像性の向上の観点からは直鎖状のものが好ましく、一方で膜強度の観点からは環状のものが好ましい。その炭素数は通常１以上であり、３以上が好ましく、６以上がより好ましく、また、２５以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、２価の脂肪族基の炭素数は１～２５が好ましく、３～２０がより好ましく、６～１５がさらに好ましい。 The divalent aliphatic group includes a linear, branched and cyclic divalent aliphatic group. Among these, a linear one is preferred from the viewpoint of improvement in developability, while a cyclic one is preferred from the viewpoint of film strength. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the carbon number of the divalent aliphatic group is preferably 1 to 25, more preferably 3 to 20, and still more preferably 6 to 15.
　２価の直鎖状脂肪族基の具体例としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基等が挙げられる。これらの中でも撥インク性の観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基の具体例としては、前述の２価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等を有する構造が挙げられる。 Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, and the like. Among these, a methylene group is preferable from the viewpoint of ink repellency.
Specific examples of the divalent branched aliphatic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group as side chains in addition to the aforementioned divalent linear aliphatic group. Group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
　２価の環状の脂肪族基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、また、通常１０以下であり、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、２価の環状の脂肪族基が有する環の数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、２～５が特に好ましい。 The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, 5 or less, and more preferably 3 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the divalent cyclic aliphatic group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2 to 5.
　２価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等の環から水素原子を２つ除した基が挙げられる。これらの中でも膜強度の観点から、アダマンタン環から水素原子を２つ除した基が好ましい。 Specific examples of the divalent cyclic aliphatic group include two hydrogen atoms removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a cyclododecane ring. The following groups may be mentioned. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of film strength.
　２価の脂肪族基が有していてもよい置換基としては、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成容易性の観点から、無置換であることが好ましい。 置換 Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.
　また、２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。その炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。２価の芳香族環基の炭素数は４～３０が好ましく、５～２０がより好ましく、６～１５がさらに好ましい。 In addition, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. The carbon number of the divalent aromatic ring group is preferably from 4 to 30, more preferably from 5 to 20, and even more preferably from 6 to 15.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, a chrysene ring having two free valences. Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
　また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。これらの中でも製造コストの観点から、２個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、２個の遊離原子価を有するベンゼン環がより好ましい。 Further, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroleimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, flopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, a benzene ring or naphthalene ring having two free valences is preferable from the viewpoint of production cost, and a benzene ring having two free valences is more preferable.
　２価の芳香族環基が有していてもよい置換基としては、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。これらの中でも硬化性の観点から、無置換が好ましい。 置換 Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. Among these, non-substitution is preferable from the viewpoint of curability.
　また、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されないが、通常１以上であり、２以上が好ましく、通常１０以下であり、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで膜強度が向上する傾向がある。例えば、２価の脂肪族基の数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましい。
　２価の芳香族環基の数は特に限定されないが、通常１以上であり、２以上が好ましく、通常１０以下であり、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、２価の芳香族環基の数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましい。 Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include one or more of the above-described divalent aliphatic groups and the above-described divalent aromatic group. Examples thereof include groups in which one or more ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the film strength tends to be improved. For example, the number of divalent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of divalent aromatic ring groups is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基の具体例としては、前記式（ｉ－Ａ）～（ｉ－Ｆ）で表される基等が挙げられる。これらの中でも膜強度と撥インク性の両立の観点から、前記式（ｉ－Ｃ）で表される基が好ましい。 Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (iA) to (iF). Is mentioned. Among these, a group represented by the formula (iC) is preferable from the viewpoint of achieving both film strength and ink repellency.
　これらの２価の炭化水素基に対して、側鎖である環状炭化水素基の結合態様は特に限定されないが、例えば、脂肪族基や芳香族環基の水素原子１つを該側鎖で置換した態様や、脂肪族基の炭素原子の１つを含めて側鎖である環状炭化水素基を構成した態様が挙げられる。 The bonding mode of the cyclic hydrocarbon group which is a side chain to these divalent hydrocarbon groups is not particularly limited. For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. And an embodiment in which a cyclic hydrocarbon group which is a side chain including one of the carbon atoms of the aliphatic group is constituted.
　また、前記式（ｉｉ）で表される部分構造は、撥インク性の観点から、下記式（ｉｉ－１）で表される部分構造であることが好ましい。 Further, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of ink repellency.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　式（ｉｉ－１）中、Ｒcは前記式（ｉｉ）と同義である。Ｒαは、置換基を有していてもよい１価の環状炭化水素基を表す。ｎは１以上の整数である。式（ｉｉ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。 In the formula (ii-1), R c has the same meaning as in the above formula (ii). R α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in the formula (ii-1) may be further substituted with any substituent.
（Ｒα）
　前記式（ｉｉ－１）において、Ｒαは、置換基を有していてもよい１価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R α )
In the formula (ii-1), R α represents a monovalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、また、通常６以下であり、４以下が好ましく、３以下がより好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、脂肪族環基が有する環の数は１～６が好ましく、１～４がより好ましく、１～３がさらに好ましく、２～３が特に好ましい。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、脂肪族環基の炭素数は４～４０が好ましく、４～３０がより好ましく、６～２０がさらに好ましく、８～１５が特に好ましい。 The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the aliphatic cyclic group is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 2 to 3.
The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of carbon atoms in the aliphatic ring group is preferably from 4 to 40, more preferably from 4 to 30, still more preferably from 6 to 20, and particularly preferably from 8 to 15.
　脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも膜強度と現像性の両立の観点から、アダマンタン環が好ましい。 Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring and the like. Of these, an adamantane ring is preferred from the viewpoint of achieving both film strength and developability.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、３以上がより好ましく、また、通常１０以下であり、５以下が好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、芳香族環基が有する環の数は１～１０が好ましく、１～５がより好ましく、２～５がさらに好ましい。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。芳香族環基の炭素数は４～３０が好ましく、５～２０がより好ましく、６～１５がさらに好ましい。 On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, and preferably 5 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. The number of carbon atoms in the aromatic ring group is preferably from 4 to 30, more preferably from 5 to 20, and even more preferably from 6 to 15.
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも膜強度と現像性の両立の観点から、フルオレン環が好ましい。 具体 Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Of these, a fluorene ring is preferred from the viewpoint of achieving both film strength and developability.
　環状炭化水素基が有していてもよい置換基としては、ヒドロキシル基、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、ｉｓｏ－アミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成の容易性の観点から、無置換が好ましい。 Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; Of these, non-substitution is preferred from the viewpoint of ease of synthesis.
　ｎは１以上の整数を表すが、２以上が好ましく、また、３以下が好ましい。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで膜強度が向上する傾向がある。例えば、ｎは１以上３以下の整数であることが好ましく、２以上３以下の整数であることがより好ましい。 N represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the film strength tends to be improved. For example, n is preferably an integer of 1 or more and 3 or less, and more preferably an integer of 2 or more and 3 or less.
　これらの中でも、膜強度と現像性の両立の観点から、Ｒαが１価の脂肪族環基であることが好ましく、アダマンチル基であることがより好ましい。 Among them, R α is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group, from the viewpoint of achieving both film strength and developability.
　前記のとおり、式（ｉｉ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。これらの中でも硬化性の観点から、無置換であることが好ましい。 と お り As described above, the benzene ring in the formula (ii-1) may be further substituted with any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited either, and may be one or two or more. Among them, unsubstituted is preferred from the viewpoint of curability.
　以下に前記式（ｉｉ－１）で表される部分構造の具体例を挙げる。 具体 Specific examples of the partial structure represented by the formula (ii-1) will be given below.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　また、前記式（ｉｉ）で表される部分構造は、現像密着性の観点から、下記式（ｉｉ－２）で表される部分構造であることが好ましい。 部分 In addition, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of development adhesion.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　式（ｉｉ－２）中、Ｒcは前記式（ｉｉ）と同義である。Ｒβは、置換基を有していてもよい２価の環状炭化水素基を表す。式（ｉｉ－２）中のベンゼン環は、更に任意の置換基により置換されていてもよい。 In the formula (ii-2), R c has the same meaning as in the above formula (ii). R β represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in the formula (ii-2) may be further substituted with any substituent.
（Ｒβ）
　前記式（ｉｉ－２）において、Ｒβは、置換基を有していてもよい２価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 ( Rβ )
In the formula (ii-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、また、通常１０以下であり、５以下が好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、脂肪族環基が有する環の数は１～１０が好ましく、１～５がより好ましく、２～５がさらに好ましい。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３５以下がより好ましく、３０以下がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、脂肪族環基の炭素数は４～４０が好ましく、６～３５がより好ましく、８～３０がさらに好ましい。
　脂肪族環基における脂肪族環の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも膜強度と現像性の両立の観点から、アダマンタン環が好ましい。 The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, and preferably 5 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the aliphatic cyclic group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5.
The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the carbon number of the aliphatic ring group is preferably from 4 to 40, more preferably from 6 to 35, even more preferably from 8 to 30.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Of these, an adamantane ring is preferred from the viewpoint of achieving both film strength and developability.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、３以上がより好ましく、また、通常１０以下であり、５以下が好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、芳香族環基が有する環の数は１～１０が好ましく、１～５がより好ましく、２～５がさらに好ましく、３～５が特に好ましい。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がさらに好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、芳香族環基の炭素数は４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、１０～１５が特に好ましい。 On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, and preferably 5 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, still more preferably 2 to 5, and particularly preferably 3 to 5.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Preferably, it is particularly preferably 15 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15.
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも膜強度と現像性の観点から、フルオレン環が好ましい。 具体 Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of film strength and developability.
　環状炭化水素基が有していてもよい置換基としては、ヒドロキシル基、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、ｉｓｏ－アミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成の簡易性の観点から、無置換が好ましい。 Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; Among these, non-substitution is preferred from the viewpoint of simplicity of synthesis.
　これらの中でも、膜強度と現像性の両立の観点から、Ｒβが２価の脂肪族環基であることが好ましく、２価のアダマンタン環基であることがより好ましい。
　一方で、膜強度と現像性の両立の観点から、Ｒβが２価の芳香族環基であることが好ましく、２価のフルオレン環基であることがより好ましい。 Among them, R β is preferably a divalent aliphatic ring group, more preferably a divalent adamantane ring group, from the viewpoint of achieving both film strength and developability.
On the other hand, from the viewpoint of achieving both film strength and developability, R β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
　前記のとおり、式（ｉｉ－２）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。これらの中でも硬化性の観点から、無置換であることが好ましい。 と お り As described above, the benzene ring in the formula (ii-2) may be further substituted with any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. The number of substituents is not particularly limited either, and may be one or two or more. Among them, unsubstituted is preferred from the viewpoint of curability.
　以下に前記式（ｉｉ－２）で表される部分構造の具体例を挙げる。 具体 Specific examples of the partial structure represented by the formula (ii-2) are described below.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　一方で、前記式（ｉｉ）で表される部分構造は、現像性の観点から、下記式（ｉｉ－３）で表される部分構造であることが好ましい。 On the other hand, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of developability.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
　式（ｉｉ－３）中、Ｒc及びＲdは前記式（ｉｉ）と同義である。ＲZは水素原子又は多塩基酸残基を表す。 In formula (ii-3), R c and R d have the same meanings as in formula (ii). R Z represents a hydrogen atom or a polybasic acid residue.
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。多塩基酸としては、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた１種又は２種以上が挙げられる。
　これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。 The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endmethylenetetrahydrophthalic acid One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, preferably, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Is tetrahydrophthalic acid or biphenyltetracarboxylic acid.
　エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）１分子中に含まれる、前記式（ｉｉ－３）で表される部分構造は、１種でも２種以上でもよい。 The partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) may be one type or two or more types.
　また、エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）１分子中に含まれる、前記式（ｉｉ）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）１分子中に含まれる、前記式（ｉｉ）で表される部分構造の数は１～２０が好ましく、１～１５がより好ましく、３～１０がさらに好ましい。 The number of the partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Also, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and more preferably 3 to 10 Is more preferred.
　また、エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）１分子中に含まれる、前記式（ｉｉ－１）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）１分子中に含まれる、前記式（ｉｉ－１）で表される部分構造の数は１～２０が好ましく、１～１５がより好ましく、３～１０がさらに好ましい。 The number of partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. Preferably, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of the partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
　また、エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）１分子中に含まれる、前記式（ｉｉ－２）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）１分子中に含まれる、前記式（ｉｉ－２）で表される部分構造の数は１～２０が好ましく、１～１５がより好ましく、３～１０がさらに好ましい。 The number of partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. Preferably, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
　また、エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）１分子中に含まれる、前記式（ｉｉ－３）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、エポキシ（メタ）アクリレート樹脂（Ｂ１２－２）１分子中に含まれる、前記式（ｉｉ－３）で表される部分構造の数は１～２０が好ましく、１～１５がより好ましく、３～１０がさらに好ましい。 The number of partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. Preferably, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
　次に、下記一般式（ｉｉｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂（以下、「エポキシ（メタ）アクリレート樹脂（Ｂ１２－３）」と称する場合がある。）について詳述する。 Next, an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (iii) (hereinafter sometimes referred to as “epoxy (meth) acrylate resin (B12-3)”) will be described in detail. .
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　式（ｉｉｉ）中、Ｒeは水素原子又はメチル基を表し、γは単結合、－ＣＯ－、置換基を有していてもよいアルキレン基、又は置換基を有していてもよい２価の環状炭化水素基を表す。式（ｉｉｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。 Wherein (iii), R e represents a hydrogen atom or a methyl group, gamma is a single bond, -CO-, may have a substituent group alkylene group, or a divalent which may have a substituent Represents a cyclic hydrocarbon group. The benzene ring in the formula (iii) may be further substituted with any substituent. * Represents a bond.
（γ）
　前記式（ｉｉｉ）において、γは単結合、－ＣＯ－、置換基を有していてもよいアルキレン基、又は置換基を有していてもよい２価の環状炭化水素基を表す。 (Γ)
In the formula (iii), γ represents a single bond, —CO—, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.
　アルキレン基は直鎖でも、分岐鎖でもよいが、現像溶解性の観点からは直鎖であることが好ましく、現像密着性の観点からは分岐鎖であることが好ましい。その炭素数は特に限定されないが、通常１以上であり、２以上が好ましく、また、通常６以下であり、４以下が好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、アルキレン基の炭素数は１～６が好ましく、１～４がより好ましく、２～４がさらに好ましい。 The alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility, and is preferably branched from the viewpoint of development adhesion. The number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the carbon number of the alkylene group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 2 to 4.
　アルキレン基の具体例としては、メチレン基、エチレン基、プロピレン基、ブチレン基、へキシレン基、ヘプチレン基が挙げられ、膜強度と現像性の両立の観点から、エチレン基又はプロピレン基が好ましく、プロピレン基がより好ましい。 Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and a heptylene group.From the viewpoint of achieving both film strength and developability, an ethylene group or a propylene group is preferable. Groups are more preferred.
　アルキレン基が有していてもよい置換基としては、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成容易性の観点から、無置換であることが好ましい。 Examples of the substituent which the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.
　２価の環状炭化水素基としては、２価の脂肪族環基又は２価の芳香族環基が挙げられる。 は Examples of the divalent cyclic hydrocarbon group include a divalent aliphatic ring group and a divalent aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、また、通常１０以下であり、５以下が好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、脂肪族環基が有する環の数は１～１０が好ましく、１～５がより好ましく、２～５がさらに好ましい。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３５以下がより好ましく、３０以下がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、脂肪族環基の炭素数は４～４０が好ましく、６～３５がより好ましく、８～３０がさらに好ましい。
　脂肪族環基における脂肪族環の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも膜強度と現像性の両立の観点から、アダマンタン環が好ましい。 The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, and preferably 5 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the aliphatic cyclic group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5.
The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the carbon number of the aliphatic ring group is preferably from 4 to 40, more preferably from 6 to 35, even more preferably from 8 to 30.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Of these, an adamantane ring is preferred from the viewpoint of achieving both film strength and developability.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上であり、２以上が好ましく、３以上がより好ましく、また、通常１０以下であり、５以下が好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、芳香族環基が有する環の数は１～１０が好ましく、１～５がより好ましく、２～５がさらに好ましく、３～５が特に好ましい。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がさらに好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも膜強度と現像性の両立の観点から、フルオレン環が好ましい。例えば、芳香族環基の炭素数は４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、１０～１５が特に好ましい。 On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, and preferably 5 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, still more preferably 2 to 5, and particularly preferably 3 to 5.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Preferably, it is particularly preferably 15 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Of these, a fluorene ring is preferred from the viewpoint of achieving both film strength and developability. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15.
　環状炭化水素基が有していてもよい置換基としては、ヒドロキシル基、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、ｉｓｏ－アミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成の簡易性の観点から、無置換が好ましい。 Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among these, non-substitution is preferred from the viewpoint of simplicity of synthesis.
　また、これらの中でも、現像性の観点から、γが置換基を有していてもよいアルキレン基であることが好ましく、ジメチルメチレン基であることがより好ましい。 Of these, from the viewpoint of developability, γ is preferably an alkylene group which may have a substituent, and more preferably a dimethylmethylene group.
　前記のとおり、式（ｉｉｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。これらの中でも硬化性の観点から、無置換であることが好ましい。 と お り As described above, the benzene ring in the formula (iii) may be further substituted with any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. The number of substituents is not particularly limited either, and may be one or two or more. Among them, unsubstituted is preferred from the viewpoint of curability.
　一方で、前記式（ｉｉｉ）で表される部分構造は、現像溶解性の観点から、下記式（ｉｉｉ－１）で表される部分構造であることが好ましい。 On the other hand, the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1) from the viewpoint of development solubility.
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　式（ｉｉｉ－１）中、Ｒe及びγは前記式（ｉｉｉ）と同義である。ＲWは水素原子又は多塩基酸残基を表す。＊は結合手を表す。式（ｉｉｉ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。 In the formula (iii-1), Re and γ have the same meanings as in the formula (iii). R W represents a hydrogen atom or a polybasic acid residue. * Represents a bond. The benzene ring in the formula (iii-1) may be further substituted with any substituent.
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。多塩基酸としては、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた１種又は２種以上が挙げられる。
　これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。 The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endmethylenetetrahydrophthalic acid One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, preferably, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Is tetrahydrophthalic acid or biphenyltetracarboxylic acid.
　また、エポキシ（メタ）アクリレート樹脂（Ｂ１２－３）１分子中に含まれる、前記式（ｉｉｉ）で表される繰り返し単位構造の数は特に限定されないが、１以上が好ましく、５以上がより好ましく、１０以上がさらに好ましく、また、１８以下が好ましく、１５以下がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、エポキシ（メタ）アクリレート樹脂（Ｂ１２－３）１分子中に含まれる、前記式（ｉｉｉ）で表される繰り返し単位構造の数は１～１８が好ましく、５～１５がより好ましく、１０～１５がさらに好ましい。 The number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth) acrylate resin (B12-3) is not particularly limited, but is preferably 1 or more, and more preferably 5 or more. , Preferably 10 or more, more preferably 18 or less, even more preferably 15 or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth) acrylate resin (B12-3) is preferably 1 to 18, more preferably 5 to 15, and more preferably 10 to 15 is more preferred.
　また、エポキシ（メタ）アクリレート樹脂（Ｂ１２－３）１分子中に含まれる、前記式（ｉｉｉ－１）で表される繰り返し単位構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、５以上がさらに好ましく、また、１８以下が好ましく、１５以下がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。例えば、エポキシ（メタ）アクリレート樹脂（Ｂ１２－３）１分子中に含まれる、前記式（ｉｉｉ－１）で表される繰り返し単位構造の数は１～１８が好ましく、３～１５がより好ましく、５～１５がさらに好ましい。 The number of repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-3) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. More preferably, 5 or more is more preferable, 18 or less is preferable, and 15 or less is further preferable. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved. For example, the number of the repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth) acrylate resin (B12-3) is preferably 1 to 18, more preferably 3 to 15, 5 to 15 are more preferred.
　以下にエポキシ（メタ）アクリレート樹脂（Ｂ１２－３）の具体例を挙げる。 具体 Specific examples of the epoxy (meth) acrylate resin (B12-3) are shown below.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　以上のとおり、本発明における（Ｂ）アルカリ可溶性樹脂は、アクリル共重合樹脂（Ｂ１１）や、エポキシ（メタ）アクリレート樹脂（Ｂ１２）以外に、その他のアルカリ可溶性樹脂を含んでいてもよい。 As described above, the alkali-soluble resin (B) in the present invention may include other alkali-soluble resins in addition to the acrylic copolymer resin (B11) and the epoxy (meth) acrylate resin (B12).
　また、（Ｂ）成分のアルカリ可溶性樹脂の酸価は特に限定されないが、３０ｍｇＫＯＨ／ｇ以上が好ましく、５０ｍｇＫＯＨ／ｇ以上がより好ましく、７０ｍｇＫＯＨ／ｇ以上がさらに好ましく、また、２００ｍｇＫＯＨ／ｇ以下が好ましく、１５０ｍｇＫＯＨ／ｇ以下がより好ましく、１００ｍｇＫＯＨ／ｇ以下がさらに好ましい。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで現像密着性が向上する傾向がある。なお、（Ｂ）アルカリ可溶性樹脂が２種以上の混合物の場合には、酸価は、その含有割合に応じた加重平均値を意味する。例えば、（Ｂ）成分のアルカリ可溶性樹脂の酸価は３０～２００ｍｇＫＯＨ／ｇが好ましく、５０～１５０ｍｇＫＯＨ／ｇがより好ましく、７０～１００ｍｇＫＯＨ／ｇがさらに好ましい。 The acid value of the alkali-soluble resin as the component (B) is not particularly limited, but is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, further preferably 70 mgKOH / g or more, and further preferably 200 mgKOH / g or less. , 150 mgKOH / g or less, more preferably 100 mgKOH / g or less. When the content is not less than the lower limit, the developability tends to be improved, and when the content is not more than the upper limit, the development adhesion tends to be improved. When the alkali-soluble resin (B) is a mixture of two or more kinds, the acid value means a weighted average value according to the content ratio. For example, the acid value of the alkali-soluble resin of the component (B) is preferably from 30 to 200 mgKOH / g, more preferably from 50 to 150 mgKOH / g, even more preferably from 70 to 100 mgKOH / g.
　本発明の感光性着色樹脂組成物中における（Ｂ）アルカリ可溶性樹脂の含有割合は特に限定されないが、全固形分に対して、通常５質量％以上、好ましくは１０質量％以上、より好ましくは２０質量％以上、さらに好ましくは３０質量％以上、よりさらに好ましくは４０質量％以上、特に好ましくは５０質量％以上、また、通常９０質量％以下、好ましくは８０質量％以下、より好ましくは７０質量％以下である。前記下限値以上とすることで隔壁の形状が良好となる傾向があり、また、前記上限値以下とすることで撥インク性が向上する傾向がある。例えば、感光性着色樹脂組成物の全固形分中における（Ｂ）アルカリ可溶性樹脂の含有割合は５～９０質量％が好ましく、１０～９０質量％がより好ましく、２０～８０質量％がさらに好ましく、３０～８０質量％がよりさらに好ましく、４０～７０質量％がとりわけ好ましく、５０～７０質量％が特に好ましい。 The content of the alkali-soluble resin (B) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass, based on the total solid content. % By mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass. It is as follows. When the ratio is not less than the lower limit, the shape of the partition tends to be good, and when the ratio is not more than the upper limit, the ink repellency tends to be improved. For example, the content of the alkali-soluble resin (B) in the total solid content of the photosensitive colored resin composition is preferably from 5 to 90% by mass, more preferably from 10 to 90% by mass, even more preferably from 20 to 80% by mass. It is more preferably from 30 to 80% by mass, particularly preferably from 40 to 70% by mass, particularly preferably from 50 to 70% by mass.
　また、全固形分中における（Ｃ）光重合性化合物の含有割合及び（Ｂ）アルカリ可溶性樹脂の含有割合の総和は、特に限定されないが、１０質量％以上が好ましく、３０質量％以上がより好ましく、６０質量％以上がさらに好ましく、８０質量％以上が特に好ましく、また、９５質量％以下が好ましく、９２質量％以下がより好ましく、９０質量％以下がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向があり、また、前記上限値以下とすることで隔壁の形状が良好となる傾向がある。例えば、感光性着色樹脂組成物の全固形分中における（Ｃ）光重合性化合物の含有割合及び（Ｂ）アルカリ可溶性樹脂の含有割合の総和は１０～９５質量％が好ましく、３０～９２質量％がより好ましく、６０～９０質量％がさらに好ましく、８０～９０質量％が特に好ましい。 The total content of the photopolymerizable compound (C) and the content of the alkali-soluble resin (B) in the total solid content is not particularly limited, but is preferably 10% by mass or more, and more preferably 30% by mass or more. , 60% by mass or more, still more preferably 80% by mass or more, preferably 95% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less. When the content is not less than the lower limit, the ink repellency tends to be improved, and when the content is not more than the upper limit, the shape of the partition wall tends to be good. For example, the total of the content of the photopolymerizable compound (C) and the content of the alkali-soluble resin (B) in the total solid content of the photosensitive colored resin composition is preferably 10 to 95% by mass, and 30 to 92% by mass. Is more preferably 60 to 90% by mass, and particularly preferably 80 to 90% by mass.
［１－１－３］（Ｃ）成分；光重合性化合物
　本発明の感光性着色樹脂組成物は、（Ｃ）光重合性化合物を含有する。（Ｃ）光重合性化合物を含むことで、塗膜の硬化性が上がり、また撥インク性が向上すると考えられる。
　ここで使用される光重合性化合物としては、エチレン性不飽和結合を分子内に１個以上有する化合物を意味するが、重合性、架橋性、およびそれに伴う露光部と非露光部の現像液溶解性の差異を拡大できる等の点から、エチレン性不飽和結合を分子内に２個以上有する化合物であることが好ましく、また、その不飽和結合は（メタ）アクリロイルオキシ基に由来するもの、つまり、（メタ）アクリレート化合物であることがさらに好ましい。 [1-1-3] Component (C); Photopolymerizable Compound The photosensitive colored resin composition of the present invention contains (C) a photopolymerizable compound. It is considered that by containing the photopolymerizable compound (C), the curability of the coating film is increased and the ink repellency is improved.
As used herein, the photopolymerizable compound means a compound having at least one ethylenically unsaturated bond in a molecule, and is polymerizable, crosslinkable, and dissolved in a developing solution in an exposed portion and a non-exposed portion. It is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule from the viewpoint that the difference in sex can be expanded, and the unsaturated bond is derived from a (meth) acryloyloxy group, that is, And (meth) acrylate compounds.
　本発明においては、特に、１分子中にエチレン性不飽和結合を２個以上有する多官能エチレン性単量体を使用することが望ましい。多官能エチレン性単量体が有するエチレン性不飽和基の数は特に限定されないが、好ましくは２個以上、より好ましくは３個以上、さらに好ましくは５個以上であり、また、好ましくは１５個以下、より好ましくは１０個以下、さらに好ましくは８個以下、特に好ましくは７個以下である。前記下限値以上とすることで重合性が向上して撥インク性が高くなる傾向があり、前記上限値以下とすることで現像性がより良好となる傾向がある。例えば、多官能エチレン性単量体が有するエチレン性不飽和基の数は２～１５個が好ましく、２～１０個がより好ましく、２～８個がさらに好ましく、３～７個がよりさらに好ましく、５～７個が特に好ましい。
　光重合性化合物の具体例としては、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルなどが挙げられる。 In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15 or more. The number is preferably 10 or less, more preferably 8 or less, and particularly preferably 7 or less. When the content is not less than the lower limit, the polymerizability tends to be improved and the ink repellency tends to be high. When the content is not more than the upper limit, the developability tends to be better. For example, the number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is preferably 2 to 15, more preferably 2 to 10, still more preferably 2 to 8, and still more preferably 3 to 7. And 5 to 7 are particularly preferred.
Specific examples of the photopolymerizable compound include: an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic polyhydroxy compound, and the like. And an ester obtained by an esterification reaction of the polyvalent hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.
　前記脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等の脂肪族ポリヒドロキシ化合物のアクリル酸エステル、これら例示化合物のアクリレートをメタクリレートに代えたメタクリル酸エステル、同様にイタコネートに代えたイタコン酸エステル、クロネートに代えたクロトン酸エステルもしくはマレエートに代えたマレイン酸エステル等が挙げられる。 Examples of the ester of the aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and methacrylic esters in which the acrylate of these exemplified compounds is replaced with methacrylate And itaconic acid esters, chronone Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to bets and the like.
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、ハイドロキノンジアクリレート、ハイドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレート等の芳香族ポリヒドロキシ化合物のアクリル酸エステル及びメタクリル酸エステル等が挙げられる。
　脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルとしては必ずしも単一物ではないが、代表的な具体例を挙げれば、アクリル酸、フタル酸、及びエチレングリコールの縮合物、アクリル酸、マレイン酸、及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物等が挙げられる。 Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. And the like.
As an ester obtained by an esterification reaction of a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid, the ester is not necessarily a single ester, but is typically used. Specific examples include acrylic acid, phthalic acid, and condensates of ethylene glycol, acrylic acid, maleic acid, and condensates of diethylene glycol, methacrylic acid, condensates of terephthalic acid and pentaerythritol, acrylic acid, adipic acid, And condensates of butanediol and glycerin.
　その他、本発明に用いられる多官能エチレン性単量体の例としては、ポリイソシアネート化合物と水酸基含有（メタ）アクリル酸エステル又はポリイソシアネート化合物とポリオール及び水酸基含有（メタ）アクリル酸エステルを反応させて得られるようなウレタン（メタ）アクリレート類；多価エポキシ化合物とヒドロキシ（メタ）アクリレート又は（メタ）アクリル酸との付加反応物のようなエポキシアクリレート類；エチレンビスアクリルアミド等のアクリルアミド類；フタル酸ジアリル等のアリルエステル類；ジビニルフタレート等のビニル基含有化合物等が有用である。
　上記ウレタン（メタ）アクリレート類としては、例えば、ＤＰＨＡ－４０Ｈ、ＵＸ－５０００、ＵＸ－５００２Ｄ－Ｐ２０、ＵＸ－５００３Ｄ、ＵＸ－５００５（日本化薬社製）、Ｕ－２ＰＰＡ、Ｕ－６ＬＰＡ、Ｕ－１０ＰＡ、Ｕ－３３Ｈ、ＵＡ－５３Ｈ、ＵＡ－３２Ｐ、ＵＡ－１１００Ｈ（新中村化学工業社製）、ＵＡ－３０６Ｈ、ＵＡ－５１０Ｈ、ＵＦ－８００１Ｇ（協栄社化学社製）、ＵＶ－１７００Ｂ、ＵＶ－７６００Ｂ、ＵＶ－７６０５Ｂ、ＵＶ－７６３０Ｂ、ＵＶ７６４０Ｂ（日本合成化学工業社製）等が挙げられる。 Other examples of the polyfunctional ethylenic monomer used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition products of polyvalent epoxy compounds with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; diallyl phthalate Allyl esters such as divinyl phthalate and the like are useful.
Examples of the urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (Nippon Kayaku), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.
　これらの中でも、隔壁側面の垂直性と撥インク性の観点から（Ｃ）光重合性化合物として、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルはウレタン（メタ）アクリレート類を用いることが好ましく、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、２－トリス（メタ）アクリロイロキシメチルエチルフタル酸、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートの二塩基酸無水物付加物、ペンタエリスリトールトリ（メタ）アクリレートの二塩基酸無水物付加物等を用いることがより好ましい。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Among them, urethane (meth) acrylates are preferably used as the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid as the photopolymerizable compound (C) from the viewpoint of the perpendicularity of the partition wall side and the ink repellency. Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-tris (meth) acryloyloxymethylethyl phthalate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, It is more preferable to use a dibasic acid anhydride adduct of pentaerythritol penta (meth) acrylate, a dibasic anhydride adduct of pentaerythritol tri (meth) acrylate, or the like.
These may be used alone or in combination of two or more.
　本発明において、（Ｃ）光重合性化合物の分子量は特に限定されないが、撥インク性、隔壁側面の垂直性の観点から、好ましくは１００以上、より好ましくは１５０以上で、さらに好ましくは２００以上、よりさらに好ましくは３００以上、特に好ましくは４００以上、最も好ましくは５００以上であり、好ましくは１０００以下、より好ましくは７００以下である。例えば、（Ｃ）光重合性化合物の分子量は１００～１０００が好ましく、１５０～１０００がより好ましく、２００～１０００がさらに好ましく、３００～７００がよりさらに好ましく、４００～７００がことさら好ましく、５００～７００が特に好ましい。
　また、（Ｃ）光重合性化合物の炭素数は特に限定されないが、撥インク性、隔壁側面の垂直性の観点から、好ましくは７以上、より好ましくは１０以上、さらに好ましくは１５以上、よりさらに好ましくは２０以上、特に好ましくは２５以上であり、好ましくは５０以下、より好ましくは４０以下、さらに好ましくは３５以下、特に好ましくは３０以下である。例えば、（Ｃ）光重合性化合物の炭素数は７～５０が好ましく、１０～４０がより好ましく、１５～３５がさらに好ましく、２０～３０がよりさらに好ましく、２５～３０が特に好ましい。
　また、撥インク性、隔壁側面の垂直性の観点から、エステル（メタ）アクリレート類、エポキシ（メタ）アクリレート類、およびウレタン（メタ）アクリレート類が好ましく、中でも、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートなど３官能以上のエステル（メタ）アクリレート類、２，２，２－トリス（メタ）アクリロイロキシメチルエチルフタル酸、ジペンタエリスリトールペンタ（メタ）アクリレートの二塩基酸無水物付加物等の３官能以上のエステル（メタ）アクリレート類への酸無水物の付加物が、撥インク性、隔壁側面の垂直性の面でさらに好ましい。 In the present invention, the molecular weight of the photopolymerizable compound (C) is not particularly limited, but is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, from the viewpoints of ink repellency and verticality of the side wall of the partition. It is even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1,000 or less, more preferably 700 or less. For example, the molecular weight of the photopolymerizable compound (C) is preferably from 100 to 1,000, more preferably from 150 to 1,000, still more preferably from 200 to 1,000, still more preferably from 300 to 700, still more preferably from 400 to 700, and more preferably from 500 to 700. Is particularly preferred.
The number of carbon atoms of the photopolymerizable compound (C) is not particularly limited, but is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, from the viewpoint of ink repellency and verticality of the side wall of the partition. It is preferably at least 20, more preferably at least 25, preferably at most 50, more preferably at most 40, further preferably at most 35, particularly preferably at most 30. For example, the carbon number of the photopolymerizable compound (C) is preferably from 7 to 50, more preferably from 10 to 40, still more preferably from 15 to 35, still more preferably from 20 to 30, and particularly preferably from 25 to 30.
Further, from the viewpoints of ink repellency and verticality of the side wall of the partition wall, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable, and among them, pentaerythritol tetra (meth) acrylate, pentane Trifunctional or higher functional ester (meth) acrylates such as erythritol tri (meth) acrylate dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, 2,2,2-tris (meth) acryloyloxymethylethyl An acid anhydride adduct to tri- or higher functional ester (meth) acrylates such as phthalic acid, dipentaerythritol penta (meth) acrylate dibasic acid anhydride adduct, provides ink repellency and verticality of the side wall of the partition Is more preferred in terms of
　本発明の感光性着色樹脂組成物中の（Ｃ）光重合性化合物の含有割合は、特に限定されないが、全固形分中に通常１質量％以上、好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは１５質量％以上、通常８０質量％以下、好ましくは６０質量％以下、より好ましくは４０質量％以下、さらに好ましくは３０質量％以下である。前記下限値以上とすることで露光時の隔壁側面の垂直性が良好となる傾向があり、前記上限値以下とすることで現像性が良好となる傾向がある。例えば、感光性着色樹脂組成物の全固形分中の（Ｃ）光重合性化合物の含有割合は１～８０質量％が好ましく、５～６０質量％がより好ましく、１０～４０質量％がさらに好ましく、１５～３０質量％が特に好ましい。 The content ratio of the photopolymerizable compound (C) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass in the total solid content. It is at least 15% by mass, more preferably at least 15% by mass, usually at most 80% by mass, preferably at most 60% by mass, more preferably at most 40% by mass, even more preferably at most 30% by mass. When the ratio is not less than the lower limit, the perpendicularity of the side wall of the partition during exposure tends to be good, and when the ratio is not more than the upper limit, the developability tends to be good. For example, the content of the photopolymerizable compound (C) in the total solid content of the photosensitive colored resin composition is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 40% by mass. , 15 to 30% by mass is particularly preferred.
　また、（Ｂ）アルカリ可溶性樹脂１００質量部に対する（Ｃ）光重合性化合物の含有割合は特に限定されないが、通常１質量部以上、好ましくは５質量部以上、より好ましくは１０質量部以上、さらに好ましくは１５質量部以上、特に好ましくは２０質量部以上であり、通常１５０質量部以下、好ましくは１００質量部以下、より好ましくは７０質量部以下、さらに好ましくは５０質量部以下、特に好ましくは４０質量部以下であることが好ましい。前記下限値以上とすることで撥インク性が良好となり、隔壁側面の垂直性が良好となる傾向があり、前記上限値以下とすることで現像性が良好となる傾向がある。例えば、（Ｂ）アルカリ可溶性樹脂１００質量部に対する（Ｃ）光重合性化合物の含有割合は１～１５０質量部が好ましく、５～１００質量部がより好ましく、１０～７０質量部がさらに好ましく、１５～５０質量部がよりさらに好ましく、２０～４０質量部が特に好ましい。 The content ratio of the photopolymerizable compound (C) to 100 parts by mass of the alkali-soluble resin (B) is not particularly limited, but is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and furthermore It is preferably at least 15 parts by mass, particularly preferably at least 20 parts by mass, usually at most 150 parts by mass, preferably at most 100 parts by mass, more preferably at most 70 parts by mass, still more preferably at most 50 parts by mass, particularly preferably at most 40 parts by mass. It is preferable that the amount is not more than part by mass. When the content is not less than the lower limit, the ink repellency tends to be good, and the verticality of the side wall of the partition tends to be good. When the content is not more than the upper limit, the developability tends to be good. For example, the content ratio of the photopolymerizable compound (C) to 100 parts by mass of the alkali-soluble resin (B) is preferably from 1 to 150 parts by mass, more preferably from 5 to 100 parts by mass, still more preferably from 10 to 70 parts by mass, and preferably from 15 to 70 parts by mass. The amount is more preferably from 50 to 50 parts by mass, and particularly preferably from 20 to 40 parts by mass.
［１－１－４］（Ｄ）着色剤
　本発明の感光性着色樹脂組成物は、（Ｄ）着色剤を含有する。（Ｄ）着色剤を含有することで、適度な光吸収性、特に着色隔壁などの遮光部材を形成する用途に用いる場合には適度な遮光性を得ることができる。 [1-1-4] (D) Colorant The photosensitive colored resin composition of the present invention contains (D) a colorant. (D) By containing a coloring agent, it is possible to obtain a suitable light-absorbing property, especially when used for forming a light-blocking member such as a colored partition wall.
　本発明で用いる（Ｄ）着色剤の種類は特に限定されず、顔料を用いてもよいし、染料を用いてもよい。これらの中でも、耐久性の観点から、顔料を用いることが好ましい。 種類 The type of the colorant (D) used in the present invention is not particularly limited, and a pigment or a dye may be used. Among these, it is preferable to use a pigment from the viewpoint of durability.
　（Ｄ）着色剤に含まれる顔料は、１種単独でもよいし、２種以上であってもよい。特に、可視領域において均一に遮光するとの観点からは、２種以上であることが好ましい。
　（Ｄ）着色剤として用いることができる顔料の種類は特に限定されないが、例えば、有機顔料や無機顔料が挙げられる。これらの中でも、感光性着色樹脂組成物の透過波長をコントロールして効率的に硬化させるとの観点からは、有機顔料を用いることが好ましい。
　有機顔料としては、有機着色顔料や有機黒色顔料が挙げられる。ここで、有機着色顔料とは、黒色以外の色を呈する有機顔料のことを意味し、赤色顔料、橙色顔料、青色顔料、紫色顔料、緑色顔料、黄色顔料等が挙げられる。 (D) The pigment contained in the colorant may be used alone or in combination of two or more. In particular, from the viewpoint of uniformly blocking light in the visible region, it is preferable to use two or more types.
(D) The type of pigment that can be used as a colorant is not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, it is preferable to use an organic pigment from the viewpoint of controlling the transmission wavelength of the photosensitive colored resin composition and curing efficiently.
Examples of the organic pigment include an organic coloring pigment and an organic black pigment. Here, the organic coloring pigment means an organic pigment exhibiting a color other than black, and includes a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment, a yellow pigment, and the like.
　有機顔料の中でも、遮光性や紫外線吸収性の観点から有機着色顔料を用いることが好ましい。
　有機着色顔料は、１種を単独で使用してもよいが、２種以上を併用してもよい。特に、遮光性の用途に用いる場合には、色の異なる有機着色顔料を組み合わせて用いることがより好ましく、黒に近い色を呈する有機着色顔料の組み合わせを用いることがさらに好ましい。 Among the organic pigments, it is preferable to use an organic coloring pigment from the viewpoint of light shielding properties and ultraviolet absorbing properties.
One type of organic color pigment may be used alone, or two or more types may be used in combination. In particular, when used for light-shielding applications, it is more preferable to use a combination of organic coloring pigments having different colors, and it is even more preferable to use a combination of organic coloring pigments exhibiting a color close to black.
　これらの有機顔料の化学構造は特に限定されないが、アゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリノン系、ジオキサジン系、インダンスレン系、ペリレン系等が挙げられる。以下、使用できる顔料の具体例をピグメントナンバーで示す。以下に挙げる「Ｃ．Ｉ．ピグメントレッド２」等の用語は、カラーインデックス（Ｃ．Ｉ．）を意味する。 化学 The chemical structure of these organic pigments is not particularly limited, but examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based. Hereinafter, specific examples of pigments that can be used are shown by pigment numbers. Terms such as "CI Pigment Red 2" below refer to the color index (CI).
　赤色顔料としては、Ｃ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１２、１４、１５、１６、１７、２１、２２、２３、３１、３２、３７、３８、４１、４７、４８、４８：１、４８：２、４８：３、４８：４、４９、４９：１、４９：２、５０：１、５２：１、５２：２、５３、５３：１、５３：２、５３：３、５７、５７：１、５７：２、５８：４、６０、６３、６３：１、６３：２、６４、６４：１、６８、６９、８１、８１：１、８１：２、８１：３、８１：４、８３、８８、９０：１、１０１、１０１：１、１０４、１０８、１０８：１、１０９、１１２、１１３、１１４、１２２、１２３、１４４、１４６、１４７、１４９、１５１、１６６、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１７７、１７８、１７９、１８１、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１４、２１６、２２０、２２１、２２４、２３０、２３１、２３２、２３３、２３５、２３６、２３７、２３８、２３９、２４２、２４３、２４５、２４７、２４９、２５０、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２５９、２６０、２６２、２６３、２６４、２６５、２６６、２６７、２６８、２６９、２７０、２７１、２７２、２７３、２７４、２７５、２７６を挙げることができる。この中でも、遮光性、分散性の観点から好ましくはＣ．Ｉ．ピグメントレッド４８：１、１２２、１４９、１６８、１７７、１７９、１９４、２０２、２０６、２０７、２０９、２２４、２４２、２５４、さらに好ましくはＣ．Ｉ．ピグメントレッド１７７、２０９、２２４、２５４を挙げることができる。なお、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントレッド１７７、２５４、２７２を用いることが好ましく、感光性着色樹脂組成物を紫外線で硬化させる場合には、赤色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントレッド２５４、２７２を用いることがより好ましい。 Red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 , 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 , 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, C.I. is preferable from the viewpoint of light-shielding properties and dispersibility. I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, and 254. In addition, C.I. I. Pigment Red 177, 254, and 272 are preferred. When the photosensitive colored resin composition is cured with ultraviolet light, a red pigment having a low ultraviolet absorptivity is preferably used. . I. Pigment Red 254, 272 is more preferably used.
　橙色（オレンジ）顔料としては、Ｃ．Ｉ．ピグメントオレンジ１、２、５、１３、１６、１７、１９、２０、２１、２２、２３、２４、３４、３６、３８、３９、４３、４６、４８、４９、６１、６２、６４、６５、６７、６８、６９、７０、７１、７２、７３、７４、７５、７７、７８、７９を挙げることができる。この中でも分散性や遮光性の観点から、Ｃ．Ｉ．ピグメントオレンジ１３、４３、６４、７２を用いることが好ましく、感光性着色樹脂組成物を紫外線で硬化させる場合には、オレンジ顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントオレンジ６４、７２を用いることがより好ましい。 As orange (orange) pigments, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among them, C.I. I. Pigment Orange 13, 43, 64, and 72 are preferably used. When the photosensitive colored resin composition is cured with ultraviolet light, it is preferable to use an orange pigment having a low ultraviolet absorptivity, from this viewpoint. Is C. I. Pigment Orange 64 and 72 are more preferably used.
　青色顔料としては、Ｃ．Ｉ．ピグメントブルー１、１：２、９、１４、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、１７、１９、２５、２７、２８、２９、３３、３５、３６、５６、５６：１、６０、６１、６１：１、６２、６３、６６、６７、６８、７１、７２、７３、７４、７５、７６、７８、７９を挙げることができる。この中でも、遮光性の観点から、好ましくはＣ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、６０、さらに好ましくはＣ．Ｉ．ピグメントブルー１５：６を挙げることができる。
　なお、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントブルー１５：６、１６、６０を用いることが好ましく、感光性着色樹脂組成物を紫外線で硬化させる場合には、青色顔料としては紫外線吸収率の低いものを使用することが好ましく、かかる観点からはＣ．Ｉ．ピグメントブルー６０を用いることがより好ましい。 Blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among them, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60, and more preferably C.I. I. Pigment Blue 15: 6.
In addition, C.I. I. Pigment Blue 15: 6, 16, or 60 is preferably used. When the photosensitive colored resin composition is cured with ultraviolet light, it is preferable to use a blue pigment having a low ultraviolet absorptivity. Is C. I. Pigment Blue 60 is more preferably used.
　紫色顔料としては、Ｃ．Ｉ．ピグメントバイオレット１、１：１、２、２：２、３、３：１、３：３、５、５：１、１４、１５、１６、１９、２３、２５、２７、２９、３１、３２、３７、３９、４２、４４、４７、４９、５０を挙げることができる。この中でも、遮光性の観点から、好ましくはＣ．Ｉ．ピグメントバイオレット１９、２３、さらに好ましくはＣ．Ｉ．ピグメントバイオレット２３を挙げることができる。
　なお、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントバイオレット２３、２９を用いることが好ましく、感光性着色樹脂組成物を紫外線で硬化させる場合には、紫色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントバイオレット２９を用いることがより好ましい。 Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2: 2: 2, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among them, C.I. I. Pigment Violet 19, 23, and more preferably C.I. I. Pigment Violet 23.
In addition, C.I. I. Pigment Violet 23 or 29 is preferably used. When the photosensitive colored resin composition is cured with ultraviolet light, it is preferable to use a purple pigment having a low ultraviolet absorptivity. I. Pigment Violet 29 is more preferably used.
　赤色顔料、橙色顔料、青色顔料、紫色顔料の他に用いることができる有機着色顔料としては例えば、緑色顔料、黄色顔料などを挙げることができる。
　緑色顔料としては、Ｃ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントグリーン７、３６を挙げることができる。
　黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１、１：１、２、３、４、５、６、９、１０、１２、１３、１４、１６、１７、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４１、４２、４３、４８、５３、５５、６１、６２、６２：１、６３、６５、７３、７４、７５、８１、８３、８７、９３、９４、９５、９７、１００、１０１、１０４、１０５、１０８、１０９、１１０、１１１、１１６、１１７、１１９、１２０、１２６、１２７、１２７：１、１２８、１２９、１３３、１３４、１３６、１３８、１３９、１４２、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１５７、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１８０、１８１、１８２、１８３、１８４、１８５、１８８、１８９、１９０、１９１、１９１：１、１９２、１９３、１９４、１９５、１９６、１９７、１９８、１９９、２００、２０２、２０３、２０４、２０５、２０６、２０７、２０８を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントイエロー８３、１１７、１２９、１３８、１３９、１５０、１５４、１５５、１８０、１８５、さらに好ましくはＣ．Ｉ．ピグメントイエロー８３、１３８、１３９、１５０、１８０を挙げることができる。 Organic pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include, for example, green pigments and yellow pigments.
Green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among them, C.I. I. Pigment Green 7 and 36.
As the yellow pigment, C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Among them, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, and 180.
　これらの中でも、遮光性や、形状のコントロールの観点から、赤色顔料、橙色顔料、青色顔料及び紫色顔料からなる群から選ばれる少なくとも１種を用いることが好ましい。 中 で も Among these, it is preferable to use at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments from the viewpoint of light-shielding properties and control of the shape.
　これらの中でも、遮光性や、形状のコントロールの観点からは、以下の顔料のうち少なくとも１種以上を含有するものとすることが好ましい。
　赤色顔料：Ｃ．Ｉ．ピグメントレッド１７７、２５４、２７２
　橙色顔料：Ｃ．Ｉ．ピグメントオレンジ４３、６４、７２
　青色顔料：Ｃ．Ｉ．ピグメントブルー１５：６、６０
　紫色顔料：Ｃ．Ｉ．ピグメントバイオレット２３、２９ Among these, it is preferable to contain at least one or more of the following pigments from the viewpoint of light-shielding properties and shape control.
Red pigment: C.I. I. Pigment Red 177, 254, 272
Orange pigment: C.I. I. Pigment Orange 43, 64, 72
Blue pigment: C.I. I. Pigment Blue 15: 6, 60
Purple pigment: C.I. I. Pigment Violet 23, 29
　また、有機着色顔料を２種以上併用する場合の、有機着色顔料の組み合わせについては特に限定されないが、遮光性の観点から、赤色顔料及び橙色顔料からなる群から選ばれる少なくとも１種と、青色顔料及び紫色顔料からなる群から選ばれる少なくとも１種とを含有することが好ましい。
　なお、色の組み合わせについては特に限定されないが、遮光性の観点からは例えば、赤色顔料と青色顔料の組み合わせ、青色顔料と橙色顔料の組み合わせ、青色顔料と橙色顔料と紫色顔料の組み合わせなどが挙げられる。 When two or more organic coloring pigments are used in combination, the combination of the organic coloring pigments is not particularly limited, but from the viewpoint of light shielding properties, at least one selected from the group consisting of red pigments and orange pigments, and blue pigments And at least one member selected from the group consisting of violet pigments.
The combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment, an orange pigment, and a violet pigment are exemplified. .
　さらに、これらの有機着色顔料以外に、黒色顔料を用いてもよい。また、有機着色顔料に加えて、さらに黒色顔料を用いてもよい。
　黒色顔料としては、無機黒色顔料や有機黒色顔料が挙げられるが、遮光性の観点から、カーボンブラック及び有機黒色顔料のいずれか一方又は両方を含有することが好ましい。 Further, in addition to these organic color pigments, black pigments may be used. Further, a black pigment may be used in addition to the organic coloring pigment.
Examples of the black pigment include an inorganic black pigment and an organic black pigment. From the viewpoint of light-shielding properties, it is preferable to contain one or both of carbon black and an organic black pigment.
　黒色顔料の中でも、紫外線の吸収を抑制して形状をコントロールしやすくするとの観点からは、有機黒色顔料を用いることが好ましく、特に遮光性の観点からは、下記一般式（１）で表される化合物（以下、「化合物（１）」ともいう。）、化合物（１）の幾何異性体、化合物（１）の塩、及び化合物（１）の幾何異性体の塩からなる群から選ばれる少なくとも１種を含む有機黒色顔料（以下、「一般式（１）で表される有機黒色顔料」と称する場合がある。）を用いることが好ましい。 Among the black pigments, it is preferable to use an organic black pigment from the viewpoint of suppressing absorption of ultraviolet rays to facilitate control of the shape, and particularly from the viewpoint of light-shielding properties, represented by the following general formula (1). At least one selected from the group consisting of a compound (hereinafter, also referred to as “compound (1)”), a geometric isomer of compound (1), a salt of compound (1), and a salt of a geometric isomer of compound (1) It is preferable to use an organic black pigment containing a seed (hereinafter, may be referred to as “organic black pigment represented by the general formula (1)”).
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　式（１）中、Ｒ11及びＲ16は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ17、Ｒ18、Ｒ19及びＲ20は各々独立に、水素原子、ハロゲン原子、Ｒ21、ＣＯＯＨ、ＣＯＯＲ21、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲ21、ＣＯＮＲ21Ｒ22、ＣＮ、ＯＨ、ＯＲ21、ＣＯＣＲ21、ＯＯＣＮＨ2、ＯＯＣＮＨＲ21、ＯＯＣＮＲ21Ｒ22、ＮＯ2、ＮＨ2、ＮＨＲ21、ＮＲ21Ｒ22、ＮＨＣＯＲ22、ＮＲ21ＣＯＲ22、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲ21、Ｎ＝ＣＲ21Ｒ22、ＳＨ、ＳＲ21、ＳＯＲ21、ＳＯ2Ｒ21、ＳＯ3Ｒ21、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲ21又はＳＯ2ＮＲ21Ｒ22を表し；
Ｒ12とＲ13、Ｒ13とＲ14、Ｒ14とＲ15、Ｒ17とＲ18、Ｒ18とＲ19、及びＲ19とＲ20からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲ21ブリッジによって互いに結合してもよく；
Ｒ21及びＲ22は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。 In the formula (1), R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, a halogen atom, R 21 , COOH, COOR 21 , COO − , CONH 2 , CONHR 21 , CONR 21 R 22 , CN, OH, OR 21 , COCR 21 , OOCNH 2 , OOCNHR 21 , OOCNR 21 R 22 , NO 2 , NH 2 , NHR 21 , NR 21 R 22 , NHCOR 22 , NR 21 COR 22 , N = CH 2 , N = CHR 21 , N = CR 21 R 22 , SH, SR 21 , SOR 21 , SO 2 R 21 , SO 3 R 21 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR Represents 21 or SO 2 NR 21 R 22 ;
R 12 and R 13, at least one combination selected from R 13 and R 14, R 14 and R 15, the group consisting of R 17 and R 18, R 18, R 19, and R 19 and R 20 are each other directly May be linked together or may be linked to each other by an oxygen, sulfur, NH or NR 21 bridge;
R 21 and R 22 are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or Represents 2 to 12 alkynyl groups.
　化合物（１）及び化合物（１）の幾何異性体は、以下のコア構造を有し（ただし、構造式中の置換基は省略している）、トランス－トランス異性体が恐らく最も安定である。 Compound (1) and geometric isomers of compound (1) have the following core structure (substituents are omitted in the structural formula), and the trans-trans isomer is probably the most stable.
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
　化合物（１）がアニオン性である場合、その電荷を任意の公知の適したカチオン、例えば金属、有機、無機又は金属有機カチオン、具体的にはアルカリ金属、アルカリ土類金属、遷移金属、一級アンモニウム、二級アンモニウム、トリアルキルアンモニウムなどの三級アンモニウム、テトラアルキルアンモニウムなどの四級アンモニウム又は有機金属錯体によって補償した塩であることが好ましい。また、化合物（１）の幾何異性体がアニオン性である場合、同様の塩であることが好ましい。 When compound (1) is anionic, its charge is transferred to any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium It is preferably a salt compensated by a tertiary ammonium such as secondary ammonium, trialkylammonium and the like, a quaternary ammonium such as tetraalkylammonium or an organometallic complex. Further, when the geometric isomer of the compound (1) is anionic, it is preferably a similar salt.
　一般式（１）の置換基及びそれらの定義においては、遮蔽率が高くなる傾向があることから、以下のものが好ましい。これは、以下の置換基は吸収がなく、顔料の色相に影響しないと考えられるからである。
　Ｒ12、Ｒ14、Ｒ15、Ｒ17、Ｒ19及びＲ20は各々独立に、好ましくは水素原子、フッ素原子、又は塩素原子であり、さらに好ましくは水素原子である。
　Ｒ13及びＲ18は各々独立に、好ましくは水素原子、ＮＯ2、ＯＣＨ3、ＯＣ2Ｈ5、臭素原子、塩素原子、ＣＨ3、Ｃ2Ｈ5、Ｎ（ＣＨ3）2、Ｎ（ＣＨ3）（Ｃ2Ｈ5）、Ｎ（Ｃ2Ｈ5）2、α－ナフチル、β－ナフチル、ＳＯ3Ｈ又はＳＯ3 -であり、さらに好ましくは水素原子又はＳＯ3Ｈであり、特に好ましくは水素原子である。 In the substituents of the general formula (1) and their definitions, the followings are preferred because the shielding ratio tends to be high. This is because the following substituents have no absorption and are considered not to affect the hue of the pigment.
R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom.
R 13 and R 18 are preferably each independently a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3) (C 2 H 5) , N (C 2 H 5) 2, α- naphthyl, beta-naphthyl, SO 3 H or SO 3 - and, still more preferably a hydrogen atom or SO 3 H, and particularly preferably Is a hydrogen atom.
　Ｒ11及びＲ16は各々独立に、好ましくは水素原子、ＣＨ3又はＣＦ3であり、さらに好ましくは水素原子である。
　好ましくは、Ｒ11とＲ16、Ｒ12とＲ17、Ｒ13とＲ18、Ｒ14とＲ19、及びＲ15とＲ20からなる群から選ばれる少なくとも１つの組み合わせが同一であり、より好ましくは、Ｒ11はＲ16と同一であり、Ｒ12はＲ17と同一であり、Ｒ13はＲ18と同一であり、Ｒ14はＲ19と同一であり、かつ、Ｒ15はＲ20と同一である。 R 11 and R 16 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, more preferably R 11 is the same as R 16 , R 12 is the same as R 17 , R 13 is the same as R 18 , R 14 is the same as R 19 , and R 15 is the same as R 20 Are identical.
　炭素数１～１２のアルキル基は、例えばメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、２－メチルブチル基、ｎ－ペンチル基、２－ペンチル基、３－ペンチル基、２，２－ジメチルプロピル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、１，１，３，３－テトラメチルブチル基、２－エチルヘキシル基、ノニル基、デシル基、ウンデシル基又はドデシル基である。 The alkyl group having 1 to 12 carbon atoms includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, An ethylhexyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group.
　炭素数３～１２のシクロアルキル基は、例えば、シクロプロピル基、シクロプロピルメチル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘキシルメチル基、トリメチルシクロヘキシル基、ツジル基、ノルボルニル基、ボルニル基、ノルカリル基、カリル基、メンチル基、ノルピニル基、ピニル基、アダマンタン－１－イル基又はアダマンタン－２－イル基である。 Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tudyl group, a norbornyl group, a bornyl group, and a norcalyl group. , A caryl group, a menthyl group, a norpinyl group, a pinyl group, an adamantane-1-yl group or an adamantane-2-yl group.
　炭素数２～１２のアルケニル基は、例えば、ビニル基、アリル基、２－プロペン－２－イル基、２－ブテン－１－イル基、３－ブテン－１－イル基、１，３－ブタジエン－２－イル基、２－ペンテン－１－イル基、３－ペンテン－２－イル基、２－メンチル－１－ブテン－３－イル基、２－メチル－３－ブテン－２－イル基、３－メチル－２－ブテン－１－イル基、１，４－ペンタジエン－３－イル基、ヘキセニル基、オクテニル基、ノネニル基、デセニル基又はドデセニル基である。 Alkenyl groups having 2 to 12 carbon atoms include, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, A 3-methyl-2-buten-1-yl group, a 1,4-pentadien-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group or a dodecenyl group.
　炭素数３～１２のシクロアルケニル基は、例えば、２－シクロブテン－１－イル基、２－シクロペンテン－１－イル基、２－シクロヘキセン－１－イル基、３－シクロヘキセン－１－イル基、２，４－シクロヘキサジエン－１－イル基、１－ｐ－メンテン－８－イル基、４（１０）－ツジェン－１０－イル基、２－ノルボルネン－１－イル基、２，５－ノルボルナジエン－１－イル基、７，７－ジメチル－２，４－ノルカラジエン－３－イル基又はカンフェニル基である。 Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, and 2-cyclohexen-1-yl. 2,4-cyclohexadien-1-yl group, 1-p-menten-8-yl group, 4 (10) -tugen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 —Yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group or camphenyl group.
　炭素数２～１２のアルキニル基は、例えば、１－プロピン－３－イル基、１－ブチン－４－イル基、１－ペンチン－５－イル基、２－メチル－３－ブチン－２－イル基、１，４－ペンタジイン－３－イル基、１，３－ペンタジイン－５－イル基、１－ヘキシン－６－イル基、シス－３－メチル－２－ペンテン－４－イン－１－イル基、トランス－３－メチル－２－ペンテン－４－イン－１－イル基、１，３－ヘキサジイン－５－イル基、１－オクチン－８－イル基、１－ノニン－９－イル基、１－デシン－１０－イル基又は１－ドデシン－１２－イル基である。 The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl Group, 1,4-pentadiin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl Group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadin-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, It is a 1-decin-10-yl group or a 1-dodecin-12-yl group.
　ハロゲン原子は、例えば、フッ素原子、塩素原子、臭素原子又はヨウ素原子である。 A halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
　前記一般式（１）で表される有機黒色顔料は、好ましくは下記一般式（２）で表される化合物（以下、「化合物（２）」ともいう。）、及び化合物（２）の幾何異性体からなる群から選ばれる少なくとも１種を含む有機黒色顔料である。 The organic black pigment represented by the general formula (1) is preferably a compound represented by the following general formula (2) (hereinafter, also referred to as “compound (2)”), and geometric isomerism of the compound (2). An organic black pigment containing at least one member selected from the group consisting of a body.
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
　このような有機黒色顔料の具体例としては、商品名で、Ｉｒｇａｐｈｏｒ（登録商標）　Ｂｌａｃｋ　Ｓ　０１００　ＣＦ（ＢＡＳＦ社製）が挙げられる。
　この有機黒色顔料は、好ましくは後述される分散剤、溶剤、方法によって分散して使用される。また、分散の際に化合物（１）のスルホン酸誘導体、特に化合物（２）のスルホン酸誘導体が存在すると、分散性や保存性が向上する場合があるため、有機黒色顔料がこれらのスルホン酸誘導体を含むことが好ましい。 Specific examples of such an organic black pigment include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
This organic black pigment is preferably used after being dispersed by a dispersant, a solvent, and a method described below. Further, when the sulfonic acid derivative of the compound (1), particularly the sulfonic acid derivative of the compound (2) is present at the time of dispersion, the dispersibility and the storage stability may be improved. It is preferable to include
　前記一般式（１）で表される有機黒色顔料以外の有機黒色顔料としては、例えば、アニリンブラックやペリレンブラック等が挙げられる。 有機 Examples of the organic black pigment other than the organic black pigment represented by the general formula (1) include aniline black and perylene black.
　一方で、無機黒色顔料としては、カーボンブラック、アセチレンブラック、ランプブラック、ボーンブラック、黒鉛、鉄黒、シアニンブラック、チタンブラック等が挙げられる。これらの中でも、遮光性、画像特性の観点からカーボンブラックを好ましく用いることができる。カーボンブラックの例としては、以下のようなカーボンブラックが挙げられる。 On the other hand, examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. Among them, carbon black can be preferably used from the viewpoint of light-shielding properties and image characteristics. Examples of the carbon black include the following carbon blacks.
　三菱ケミカル社製：ＭＡ７、ＭＡ８、ＭＡ１１、ＭＡ７７、ＭＡ１００、ＭＡ１００Ｒ、ＭＡ１００Ｓ、ＭＡ２２０、ＭＡ２３０、ＭＡ６００、ＭＣＦ８８、＃５、＃１０、＃２０、＃２５、＃３０、＃３２、＃３３、＃４０、＃４４、＃４５、＃４７、＃５０、＃５２、＃５５、＃６５０、＃７５０、＃８５０、＃９００、＃９５０、＃９６０、＃９７０、＃９８０、＃９９０、＃１０００、＃２２００、＃２３００、＃２３５０、＃２４００、＃２６００、＃２６５０、＃３０３０、＃３０５０、＃３１５０、＃３２５０、＃３４００、＃３６００、＃３７５０、＃３９５０、＃４０００、＃４０１０、ＯＩＬ７Ｂ、ＯＩＬ９Ｂ、ＯＩＬ１１Ｂ、ＯＩＬ３０Ｂ、ＯＩＬ３１Ｂ
　デグサ社製：Ｐｒｉｎｔｅｘ（登録商標、以下同じ。）３、Ｐｒｉｎｔｅｘ３ＯＰ、Ｐｒｉｎｔｅｘ３０、Ｐｒｉｎｔｅｘ３０ＯＰ、Ｐｒｉｎｔｅｘ４０、Ｐｒｉｎｔｅｘ４５、Ｐｒｉｎｔｅｘ５５、Ｐｒｉｎｔｅｘ６０、Ｐｒｉｎｔｅｘ７５、Ｐｒｉｎｔｅｘ８０、Ｐｒｉｎｔｅｘ８５、Ｐｒｉｎｔｅｘ９０、Ｐｒｉｎｔｅｘ　Ａ、Ｐｒｉｎｔｅｘ　Ｌ、Ｐｒｉｎｔｅｘ　Ｇ、Ｐｒｉｎｔｅｘ　Ｐ、Ｐｒｉｎｔｅｘ　Ｕ、Ｐｒｉｎｔｅｘ　Ｖ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２Ｖ、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１８、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１８、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２００、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１６０、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１７０
　キャボット社製：Ｍｏｎａｒｃｈ（登録商標、以下同じ。）１２０、Ｍｏｎａｒｃｈ２８０、Ｍｏｎａｒｃｈ４６０、Ｍｏｎａｒｃｈ８００、Ｍｏｎａｒｃｈ８８０、Ｍｏｎａｒｃｈ９００、Ｍｏｎａｒｃｈ１０００、Ｍｏｎａｒｃｈ１１００、Ｍｏｎａｒｃｈ１３００、Ｍｏｎａｒｃｈ１４００、Ｍｏｎａｒｃｈ４６３０、ＲＥＧＡＬ（登録商標、以下同じ。）９９、ＲＥＧＡＬ９９Ｒ、ＲＥＧＡＬ４１５、ＲＥＧＡＬ４１５Ｒ、ＲＥＧＡＬ２５０、ＲＥＧＡＬ２５０Ｒ、ＲＥＧＡＬ３３０、ＲＥＧＡＬ４００Ｒ、ＲＥＧＡＬ５５Ｒ０、ＲＥＧＡＬ６６０Ｒ、ＢＬＡＣＫ　ＰＥＡＲＬＳ４８０、ＰＥＡＲＬＳ１３０、ＶＵＬＣＡＮ（登録商標、以下同じ。）　ＸＣ７２Ｒ、ＥＬＦＴＥＸ（登録商標）－８
　ビルラー社製：ＲＡＶＥＮ（登録商標、以下同じ。）１１、ＲＡＶＥＮ１４、ＲＡＶＥＮ１５、ＲＡＶＥＮ１６、ＲＡＶＥＮ２２ＲＡＶＥＮ３０、ＲＡＶＥＮ３５、ＲＡＶＥＮ４０、ＲＡＶＥＮ４１０、ＲＡＶＥＮ４２０、ＲＡＶＥＮ４５０、ＲＡＶＥＮ５００、ＲＡＶＥＮ７８０、ＲＡＶＥＮ８５０、ＲＡＶＥＮ８９０Ｈ、ＲＡＶＥＮ１０００、ＲＡＶＥＮ１０２０、ＲＡＶＥＮ１０４０、ＲＡＶＥＮ１０６０Ｕ、ＲＡＶＥＮ１０８０Ｕ、ＲＡＶＥＮ１１７０、ＲＡＶＥＮ１１９０Ｕ、ＲＡＶＥＮ１２５０、ＲＡＶＥＮ１５００、ＲＡＶＥＮ２０００、ＲＡＶＥＮ２５００Ｕ、ＲＡＶＥＮ３５００、ＲＡＶＥＮ５０００、ＲＡＶＥＮ５２５０、ＲＡＶＥＮ５７５０、ＲＡＶＥＮ７０００ Manufactured by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 , # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Degussa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, PrintexL, Printex, Printex A, Printex, Printex A, Printex, Printex L U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack6, SpecialBlack5, SpecialBlack4, ColBlack4, ColBlack4 ck FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Manufactured by Cabot: Monarch (registered trademark, hereinafter the same) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, RE, LAL, RE, LAL, RE 99, REAL, LGA, RE99, REAL, LAL, LAL, RE99, REAL, LGA, RE99, REAL, LAL, REL, RE, LAL, RE, LAL, RE, LAL, RE, LAL, RE, LAL, RE, LAL, and R). REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, same hereafter) XC72R, ELFTEX (registered trademark) -8
Biller Co .: RAVEN (registered trademark, the same applies hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVE40, RAVE410, RAVE420, RAVE450, RAVE500, RAVE780, RAVE850, RAVE890V, EN10VAVE10, RAVEN10V, RAVEN10VEN10VAVE10VENVAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVENAVEN , RAVEN1170, RAVEN1190U, RAVE1250, RAVE1500, RAVE2000, RAVE2500U, RAVE3500, RAVE5000, RAVE5250, RAVE5750, RAVE7000
　カーボンブラックは、樹脂で被覆されたものを使用してもよい。樹脂で被覆されたカーボンブラックを使用すると、ガラス基板への密着性や体積抵抗値が向上する効果がある。樹脂で被覆されたカーボンブラックとしては、例えば日本国特開平０９－７１７３３号公報に記載されているカーボンブラック等が好適に使用できる。体積抵抗や誘電率の点で、樹脂被覆カーボンブラックが好適に用いられる。 Carbon black coated with a resin may be used. The use of resin-coated carbon black has the effect of improving adhesion to a glass substrate and volume resistance. As the carbon black coated with a resin, for example, carbon black described in JP-A-09-71733 can be suitably used. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
　樹脂による被覆処理に供するカーボンブラックとしては、ＮａとＣａの合計含有量が１００ｐｐｍ以下であることが好ましい。カーボンブラックは、通常、製造時の原料油や燃焼油（又はガス）、反応停止水や造粒水、さらには反応炉の炉材等から混入したＮａやＣａ、Ｋ、Ｍｇ、Ａｌ、Ｆｅ等を組成とする灰分が含有されている。この内、ＮａやＣａは、各々数百ｐｐｍ以上含有されていることが一般的であるが、これらを少なくすることで、透明電極（ＩＴＯ）やその他の電極への浸透を抑制して、電気的短絡を防止できる傾向がある。 カ ー ボ ン The carbon black to be subjected to the resin coating treatment preferably has a total content of Na and Ca of 100 ppm or less. Carbon black is usually a raw material oil or a combustion oil (or gas) at the time of production, reaction stop water or granulation water, or Na, Ca, K, Mg, Al, Fe, or the like mixed from a furnace material of a reaction furnace. An ash component having the following composition is contained. Of these, Na and Ca are each generally contained in the amount of several hundred ppm or more, but by reducing these, the penetration into the transparent electrode (ITO) and other electrodes is suppressed, and Tends to prevent a short circuit.
　これらのＮａやＣａを含む灰分の含有量を低減する方法としては、カーボンブラックを製造する際の原料油や燃料油（又はガス）並びに反応停止水として、これらの含有量が極力少ない物を厳選すること及びストラクチャーを調整するアルカリ物質の添加量を極力少なくすることにより可能である。他の方法としては、炉から製出したカーボンブラックを水や塩酸等で洗いＮａやＣａを溶解し除去する方法が挙げられる。 As a method of reducing the content of these ash contents including Na and Ca, a material having a minimum of these contents is carefully selected as a raw material oil, a fuel oil (or a gas) and a reaction stop water in producing carbon black. This is possible by minimizing the amount of addition of an alkali substance for adjusting the structure. As another method, there is a method in which carbon black produced from a furnace is washed with water, hydrochloric acid or the like to dissolve and remove Na and Ca.
　具体的にはカーボンブラックを水、塩酸、又は過酸化水素水に混合分散させた後、水に難溶の溶媒を添加していくとカーボンブラックは溶媒側に移行し、水と完全に分離すると共にカーボンブラック中に存在した殆どのＮａやＣａは、水や酸に溶解、除去される。ＮａとＣａの合計量を１００ｐｐｍ以下に低減するためには、原材料を厳選したカーボンブラック製造過程単独、又は水や酸溶解方式単独でも可能な場合もあるが、この両方式を併用することによりさらに容易にＮａとＣａの合計量を１００ｐｐｍ以下とすることができる。 Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or aqueous hydrogen peroxide, when a solvent that is hardly soluble in water is added, the carbon black moves to the solvent side and is completely separated from water. At the same time, most of Na and Ca present in the carbon black are dissolved and removed in water or acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, the carbon black production process alone with carefully selected raw materials, or water or acid dissolving method alone may be possible. The total amount of Na and Ca can be easily reduced to 100 ppm or less.
　また樹脂被覆カーボンブラックは、ｐＨ６以下のいわゆる酸性カーボンブラックであることが好ましい。水中での分散径（アグロメレート径）が小さくなるので、微細ユニットまでの被覆が可能となり好適である。さらに平均粒子径４０ｎｍ以下、ジブチルフタレート（ＤＢＰ）吸収量１４０ｍＬ／１００ｇ以下であることが好ましい。前記範囲内とすることで、遮光性の良好な塗膜が得られる傾向がある。平均粒子径は数平均粒子径を意味し、電子顕微鏡観察により数万倍で撮影された写真を数視野撮影し、これらの写真の粒子を画像処理装置により２０００～３０００個程度計測する粒子画像解析により求められる円相当径を意味する。 Further, the resin-coated carbon black is preferably a so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is small, it is possible to coat even fine units, which is preferable. Further, the average particle size is preferably 40 nm or less, and the dibutyl phthalate (DBP) absorption amount is preferably 140 mL / 100 g or less. When the content is within the above range, a coating film having good light-shielding properties tends to be obtained. The average particle diameter means a number average particle diameter. A particle image analysis that photographs several tens of thousands of photographs taken at tens of thousands of times by observation with an electron microscope, and measures about 2,000 to 3,000 particles of these photographs by an image processing device. Means the equivalent circle diameter determined by
　樹脂で被覆されたカーボンブラックを調製する方法には特に限定がないが、例えばカーボンブラック及び樹脂の配合量を適宜調整した後、１．樹脂とシクロヘキサノン、トルエン、キシレンなどの溶剤とを混合して加熱溶解させた樹脂溶液と、カーボンブラック及び水を混合した懸濁液とを混合撹拌し、カーボンブラックと水とを分離させた後、水を除去して加熱混練して得られた組成物をシート状に成形し、粉砕した後、乾燥させる方法；２．前記と同様にして調製した樹脂溶液と懸濁液とを混合撹拌してカーボンブラック及び樹脂を粒状化した後、得られた粒状物を分離、加熱して残存する溶剤及び水を除去する方法；３．前記例示した溶剤にマレイン酸、フマル酸などのカルボン酸を溶解させ、カーボンブラックを添加、混合して乾燥させ、溶剤を除去してカルボン酸添着カーボンブラックを得た後、これに樹脂を添加してドライブレンドする方法；４．被覆させる樹脂を構成する反応性基含有モノマー成分と水とを高速撹拌して懸濁液を調製し、重合後冷却して重合体懸濁液から反応性基含有樹脂を得た後、これにカーボンブラックを添加して混練し、カーボンブラックと反応性基とを反応させ（カーボンブラックをグラフトさせ）、冷却及び粉砕する方法などを採用することができる。 方法 The method for preparing the resin-coated carbon black is not particularly limited. For example, after appropriately adjusting the blending amounts of the carbon black and the resin, Resin and cyclohexanone, toluene, mixed with a solvent such as xylene and heated and dissolved, and a mixture of carbon black and water are mixed and stirred to separate carbon black and water, 1. A method in which a composition obtained by removing water, heating and kneading is formed into a sheet, pulverized, and then dried; A method of mixing and stirring the resin solution and the suspension prepared in the same manner as above to granulate the carbon black and the resin, and then separating and heating the obtained granules to remove the remaining solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the solvent exemplified above, carbon black is added, mixed and dried, and after removing the solvent to obtain a carboxylic acid-impregnated carbon black, a resin is added thereto. 3. dry blending method; A reactive group-containing monomer component and water constituting the resin to be coated are stirred at high speed to prepare a suspension, and after the polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension. A method in which carbon black is added and kneaded to react the carbon black with a reactive group (graft the carbon black), cool and pulverize, or the like can be employed.
　被覆処理する樹脂の種類も特に限定されるものではないが、合成樹脂が一般的であり、さらに構造の中にベンゼン環を有する樹脂の方が両性系界面活性剤的な働きがより強いため、分散性及び分散安定性の点から好ましい。
　具体的な合成樹脂としては、フェノール樹脂、メラミン樹脂、キシレン樹脂、ジアリルフタレート樹脂、グリプタル樹脂、エポキシ樹脂、アルキルベンゼン樹脂等の熱硬化性樹脂や、ポリスチレン、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、変性ポリフェニレンオキサイド、ポリスルフォン、ポリパラフェニレンテレフタルアミド、ポリアミドイミド、ポリイミド、ポリアミノビスマレイミド、ポリエーテルスルフォポリフェニレンスルフォン、ポリアリレート、ポリエーテルエーテルケトン、等の熱可塑性樹脂が使用できる。被覆樹脂の量は、カーボンブラックと樹脂の合計量に対し１～３０質量％が好ましい。前記下限値以上とすることで被覆を十分なものとすることができる傾向がある。一方、前記上限値以下とすることで、樹脂同士の粘着を防ぎ、分散性が良好なものとすることができる傾向がある。 The type of the resin to be subjected to the coating treatment is not particularly limited, but a synthetic resin is generally used, and a resin having a benzene ring in the structure has a stronger function as an amphoteric surfactant. It is preferable from the viewpoint of dispersibility and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallyl phthalate resins, glyptal resins, epoxy resins, alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylene sulfone, polyarylate, and polyetheretherketone can be used. The amount of the coating resin is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin. When the content is not less than the lower limit, the coating tends to be sufficient. On the other hand, when the content is equal to or less than the upper limit value, there is a tendency that adhesion between the resins can be prevented and the dispersibility can be improved.
　このようにして樹脂で被覆処理してなるカーボンブラックは、常法に従い着色隔壁の着色剤として用いることができる。このようなカーボンブラックを用いると、高遮光率でかつ表面反射率が低い着色隔壁が低コストで形成できる傾向がある。また、カーボンブラック表面を樹脂で被覆したことにより、ＮａやＣａを含む灰分をカーボンブラック中に封じ込める働きがあることも推測される。 カ ー ボ ン The carbon black thus coated with the resin can be used as a coloring agent for the colored partition walls according to a conventional method. When such a carbon black is used, there is a tendency that a colored partition wall having a high light blocking ratio and a low surface reflectance can be formed at low cost. In addition, it is also presumed that coating the surface of the carbon black with a resin has a function of sealing ash containing Na and Ca into the carbon black.
　これらの顔料は、平均粒子径が通常１μｍ以下、好ましくは０．５μｍ以下、さらに好ましくは０．２５μｍ以下となるよう、分散して用いることが好ましい。ここで平均粒子径の基準は顔料粒子の数である。
　また、顔料の平均粒子径は、動的光散乱（ＤＬＳ）により測定された顔料粒子径から求めた値である。粒子径測定は、十分に希釈された感光性着色樹脂組成物（通常は希釈して、顔料濃度０．００５～０．２質量％程度に調製する。但し、測定機器により推奨された濃度があれば、その濃度に従う。）に対して行い、２５℃にて測定する。 These pigments are preferably dispersed and used so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Here, the standard of the average particle diameter is the number of pigment particles.
The average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). In the measurement of the particle size, a sufficiently diluted photosensitive coloring resin composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. And the concentration is determined according to the concentration).
　また、上述の有機着色顔料、黒色顔料の他に、染料を使用してもよい。着色剤として使用できる染料としては、アゾ系染料、アントラキノン系染料、フタロシアニン系染料、キノンイミン系染料、キノリン系染料、ニトロ系染料、カルボニル系染料、メチン系染料等が挙げられる。
　アゾ系染料としては、例えば、Ｃ．Ｉ．アシッドイエロー１１、Ｃ．Ｉ．アシッドオレンジ７、Ｃ．Ｉ．アシッドレッド３７、Ｃ．Ｉ．アシッドレッド１８０、Ｃ．Ｉ．アシッドブルー２９、Ｃ．Ｉ．ダイレクトレッド２８、Ｃ．Ｉ．ダイレクトレッド８３、Ｃ．Ｉ．ダイレクトイエロー１２、Ｃ．Ｉ．ダイレクトオレンジ２６、Ｃ．Ｉ．ダイレクトグリーン２８、Ｃ．Ｉ．ダイレクトグリーン５９、Ｃ．Ｉ．リアクティブイエロー２、Ｃ．Ｉ．リアクティブレッド１７、Ｃ．Ｉ．リアクティブレッド１２０、Ｃ．Ｉ．リアクティブブラック５、Ｃ．Ｉ．ディスパースオレンジ５、Ｃ．Ｉ．ディスパースレッド５８、Ｃ．Ｉ．ディスパースブルー１６５、Ｃ．Ｉ．ベーシックブルー４１、Ｃ．Ｉ．ベーシックレッド１８、Ｃ．Ｉ．モルダントレッド７、Ｃ．Ｉ．モルダントイエロー５、Ｃ．Ｉ．モルダントブラック７等が挙げられる。 Further, a dye may be used in addition to the above-mentioned organic color pigment and black pigment. Examples of the dye that can be used as the coloring agent include an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone imine dye, a quinoline dye, a nitro dye, a carbonyl dye, and a methine dye.
Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordant Red 7, C.I. I. Mordant Yellow 5, C.I. I. Mordant Black 7 and the like.
　アントラキノン系染料としては、例えば、Ｃ．Ｉ．バットブルー４、Ｃ．Ｉ．アシッドブルー４０、Ｃ．Ｉ．アシッドグリーン２５、Ｃ．Ｉ．リアクティブブルー１９、Ｃ．Ｉ．リアクティブブルー４９、Ｃ．Ｉ．ディスパースレッド６０、Ｃ．Ｉ．ディスパースブルー５６、Ｃ．Ｉ．ディスパースブルー６０等が挙げられる。
　この他、フタロシアニン系染料として、例えば、Ｃ．Ｉ．パッドブルー５等が、キノンイミン系染料として、例えば、Ｃ．Ｉ．ベーシックブルー３、Ｃ．Ｉ．ベーシックブルー９等が、キノリン系染料として、例えば、Ｃ．Ｉ．ソルベントイエロー３３、Ｃ．Ｉ．アシッドイエロー３、Ｃ．Ｉ．ディスパースイエロー６４等が、ニトロ系染料として、例えば、Ｃ．Ｉ．アシッドイエロー１、Ｃ．Ｉ．アシッドオレンジ３、Ｃ．Ｉ．ディスパースイエロー４２等が挙げられる。 Examples of the anthraquinone dye include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse Red 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like.
Other phthalocyanine dyes include, for example, C.I. I. Pad Blue 5 and the like include quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like include quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like include, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
　本発明の感光性着色樹脂組成物における（Ｄ）着色剤の含有割合は特に限定されないが、全固形分中に通常１質量％以上であり、２質量％以上が好ましく、３質量％以上がより好ましく、４質量％以上がさらに好ましい。また通常５０質量％以下であり、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下がさらに好ましく、１５質量％以下がよりさらに好ましく、１０質量％以下が特に好ましく、６質量％以下が最も好ましい。前記下限値以上とすることで遮光性を確保出来る傾向があり、前記上限値以下とすることで撥インク性が向上する傾向がある。例えば、感光性着色樹脂組成物の全固形分中における（Ｄ）着色剤の含有割合は１～５０質量％が好ましく、１～３０質量％がより好ましく、２～２５質量％がさらに好ましく、２～２０質量％がよりさらに好ましく、３～１５質量％がことさら好ましく、４～１０質量％が特に好ましい。 The content of the (D) colorant in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more in the total solid content. It is more preferably at least 4% by mass. Further, it is usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, particularly preferably 10% by mass or less, and 6% by mass or less. Most preferably, it is not more than mass%. When the amount is equal to or more than the lower limit, the light-shielding property tends to be secured, and when the amount is equal to or less than the upper limit, the ink repellency tends to be improved. For example, the content of the colorant (D) in the total solid content of the photosensitive colored resin composition is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, still more preferably 2 to 25% by mass. The content is more preferably from 20 to 20% by mass, still more preferably from 3 to 15% by mass, particularly preferably from 4 to 10% by mass.
［１－１－５］（Ｅ）成分；撥液剤
　本発明の感光性着色樹脂組成物は、（Ｅ）撥液剤として、架橋基を有するフッ素原子含有樹脂を含有する。架橋基を有するフッ素原子含有樹脂を含有することによって得られる隔壁の表面に撥インク性を付与できることから、得られる隔壁を有機層の発光部（画素）ごとの混色を防ぐものとすることができると考えられる。 [1-1-5] Component (E); Liquid Repellent The photosensitive colored resin composition of the present invention contains, as the liquid repellent (E), a fluorine atom-containing resin having a crosslinking group. It is considered that since the surface of the partition wall obtained by containing the fluorine atom-containing resin having a cross-linking group can be provided with ink repellency, the obtained partition wall can prevent color mixing of each light emitting portion (pixel) of the organic layer. Can be
　架橋基としては、エポキシ基又はエチレン性不飽和基が挙げられ、現像液の撥液成分の流出抑制の観点から、エチレン性不飽和基が好ましい。
　架橋基を有する撥液剤を用いることで、形成した塗布膜を露光する際にその表面での架橋反応を加速することができ、撥液剤が現像処理で流出しにくくなり、その結果、得られる隔壁を高い撥インク性を示すものとすることができると考えられる。 Examples of the crosslinking group include an epoxy group and an ethylenically unsaturated group, and an ethylenically unsaturated group is preferable from the viewpoint of suppressing the outflow of the liquid-repellent component of the developer.
By using a liquid repellent having a cross-linking group, a cross-linking reaction on the surface of the formed coating film can be accelerated when the formed coating film is exposed, and the liquid repellent is less likely to flow out in a development process, and as a result, the obtained partition wall Is considered to exhibit high ink repellency.
　また、フッ素原子含有樹脂であることで、該フッ素原子含有樹脂が隔壁の表面に配向して、インキのにじみや混色を防止する働きをする傾向がある。さらに詳しくは、フッ素原子を有する基が、インキをはじき、インキが隔壁を越えて隣接する領域に進入することによるインキのにじみや混色を防ぐ働きをする傾向がある。 In addition, since the resin is a fluorine atom-containing resin, the fluorine atom-containing resin tends to orient on the surface of the partition wall and work to prevent ink bleeding and color mixing. More specifically, a group having a fluorine atom tends to repel the ink and to prevent the ink from bleeding and color mixing due to the ink entering an adjacent region beyond the partition wall.
　また架橋基を有するフッ素原子含有樹脂は、パーフルオロアルキル基及びパーフルオロアルキレンエーテル鎖のいずれか一方又は両方を有することが好ましい。パーフルオロアルキル基及びパーフルオロアルキレンエーテル鎖のいずれか一方又は両方を有することで、フッ素原子含有樹脂がさらに隔壁の表面に配向しやすくなり、より高い撥インク性を示し、インキのにじみや混色をさらに防ぐ傾向がある。 It is preferable that the fluorine atom-containing resin having a cross-linking group has one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. By having one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain, the fluorine atom-containing resin is more easily oriented on the surface of the partition wall, exhibits higher ink repellency, and causes ink bleeding and color mixing. There is also a tendency to prevent.
　パーフルオロアルキル基としては、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロオクチル基などが挙げられる。パーフルオロアルキレンエーテル鎖としては、－ＣＦ2－Ｏ－、－（ＣＦ2）2－Ｏ－、－（ＣＦ2）3－Ｏ－、－ＣＦ2－Ｃ（ＣＦ3）Ｏ－、－Ｃ（ＣＦ3）－ＣＦ2－Ｏ－およびこれらの繰り返し単位をもつ２価の基が挙げられる。 Examples of the perfluoroalkyl group include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, and the like. Examples of the perfluoroalkylene ether chain include —CF 2 —O—, — (CF 2 ) 2 —O—, — (CF 2 ) 3 —O—, —CF 2 —C (CF 3 ) O—, and —C ( CF 3 ) —CF 2 —O— and a divalent group having these repeating units.
　架橋基を有するフッ素原子含有樹脂の具体例としては、例えばエポキシ基およびパーフルオロアルキル基を有するアクリル共重合樹脂、エポキシ基およびパーフルオロアルキレンエーテル鎖を有するアクリル共重合樹脂、エチレン性不飽和基およびパーフルオロアルキル基を有するアクリル共重合樹脂、エチレン性不飽和基およびパーフルオロアルキレンエーテル鎖を有するアクリル共重合樹脂、エポキシ基およびパーフルオロアルキル基を有するエポキシア（メタ）アクリレート樹脂、エポキシ基およびパーフルオロアルキレンエーテル鎖を有するエポキシア（メタ）アクリレート樹脂、エチレン性不飽和基およびパーフルオロアルキル基を有するエポキシア（メタ）アクリレート樹脂、エチレン性不飽和基およびパーフルオロアルキレンエーテル鎖を有するエポキシア（メタ）アクリレート樹脂、などが挙げられる。なかでも撥インク性の観点から、エチレン性不飽和基およびパーフルオロアルキル基を有するアクリル共重合樹脂、エチレン性不飽和基およびパーフルオロアルキレンエーテル鎖を有するアクリル共重合樹脂、が好ましく、エチレン性不飽和基およびパーフルオロアルキレンエーテル鎖を有するアクリル共重合樹脂がさらに好ましい。 Specific examples of the fluorine atom-containing resin having a crosslinking group include, for example, an acrylic copolymer resin having an epoxy group and a perfluoroalkyl group, an acrylic copolymer resin having an epoxy group and a perfluoroalkylene ether chain, an ethylenically unsaturated group and Acrylic copolymer resin having a perfluoroalkyl group, acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, epoxya (meth) acrylate resin having an epoxy group and a perfluoroalkyl group, epoxy group and perfluoro Epoxy (meth) acrylate resin having alkylene ether chain, epoxy (meth) acrylate resin having ethylenically unsaturated group and perfluoroalkyl group, ethylenically unsaturated group and perfluoroalkyl Epokishia with ether chain (meth) acrylate resins. Above all, from the viewpoint of ink repellency, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, and an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferable. Acrylic copolymer resins having a saturated group and a perfluoroalkylene ether chain are more preferred.
　これらの架橋基を有するフッ素原子含有樹脂の市販品としては、ＤＩＣ社製「メガファック（登録商標、以下同じ。）Ｆ１１６」、「メガファックＦ１２０」、「メガファックＦ１４２Ｄ」、「メガファックＦ１４４Ｄ」、「メガファックＦ１５０」、「メガファックＦ１６０」、「メガファックＦ１７１」、「メガファックＦ１７２」、「メガファックＦ１７３」、「メガファックＦ１７７」、「メガファックＦ１７８Ａ」、「メガファックＦ１７８Ｋ」、「メガファックＦ１７９」、「メガファックＦ１８３」、「メガファックＦ１８４」、「メガファックＦ１９１」、「メガファックＦ８１２」、「メガファックＦ８１５」、「メガファックＦ８２４」、「メガファックＦ８３３」、「メガファックＲＳ１０１」、「メガファックＲＳ１０２」「メガファックＲＳ１０５」、「メガファックＲＳ２０１」、「メガファックＲＳ２０２」、「メガファックＲＳ３０１」、「メガファックＲＳ３０３」「メガファックＲＳ３０４」、「メガファックＲＳ４０１」、「メガファックＲＳ４０２」、「メガファックＲＳ５０１」、「メガファックＲＳ５０２」、「メガファックＲＳ－７２－Ｋ」、「メガファックＲＳ－７８」、「ＤＥＦＥＮＳＡ（登録商標、以下同じ。）　ＭＣＦ３００」、「ＤＥＦＥＮＳＡ　ＭＣＦ３１０」、「ＤＥＦＥＮＳＡ　ＭＣＦ３１２」、「ＤＥＦＥＮＳＡ　ＭＣＦ３２３」、スリーエムジャパン社製「フロラードＦＣ４３０」、「フロラードＦＣ４３１」、「ＦＣ－４４３０」、「ＦＣ４４３２」、ＡＧＣ社製「アサヒガード（登録商標。）ＡＧ７１０」、「サーフロン（登録商標、以下同じ。）Ｓ－３８２」、「サーフロンＳＣ－１０１」、「サーフロンＳＣ－１０２」、「サーフロンＳＣ－１０３」、「サーフロンＳＣ－１０４」、「サーフロンＳＣ－１０５」、「サーフロンＳＣ－１０６」などの商品名で市販されている含フッ素有機化合物を使用することができる。
　これらの中でも、エチレン性不飽和基およびパーフルオロアルキレン基を有するアクリル共重合樹脂として、「メガファックＲＳ－７２－Ｋ」、「メガファックＲＳ－７８」などを好適に使用することができる。 Commercial products of these fluorine atom-containing resins having a crosslinking group include DIC Corporation's “MegaFac (registered trademark, the same applies hereinafter) F116”, “MegaFac F120”, “MegaFac F142D”, and “MegaFac F144D”. , "MegaFac F150", "MegaFac F160", "MegaFac F171", "MegaFac F172", "MegaFac F173", "MegaFac F177", "MegaFac F178A", "MegaFac F178K", " MegaFac F179, MegaFac F183, MegaFac F184, MegaFac F191, MegaFac F812, MegaFac F815, MegaFac F824, MegaFac F833, MegaFac RS101 ”,“ Mega Fuck RS ” 02, MegaFac RS105, MegaFac RS201, MegaFass RS202, MegaFass RS301, MegaFass RS303, MegaFass RS304, MegaFass RS401, MegaFass RS402, Megafax RS501, Megafax RS502, Megafax RS-72-K, Megafax RS-78, DEFENSA (registered trademark, same hereafter) MCF300, DEFENSA MCF310, DEFENSA MCF312 "," DEFENSA MCF323 "," FLORADE FC430 "," FLORADE FC431 "," FC-4430 "," FC4432 "manufactured by 3M Japan," Asahigard (registered trademark) AG710 "manufactured by AGC," -Suron (registered trademark, the same applies hereinafter) S-382 "," Surflon SC-101 "," Surflon SC-102 "," Surflon SC-103 "," Surflon SC-104 "," Surflon SC-105 "," A fluorine-containing organic compound commercially available under a trade name such as "Surflon SC-106" can be used.
Among them, as the acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene group, “Megafax RS-72-K”, “Megafax RS-78” and the like can be suitably used.
　架橋基を有するフッ素原子含有樹脂中のフッ素原子含有割合は特に制限されないが、架橋基を有するフッ素原子含有樹脂中５質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上がさらに好ましく、２５質量％以上がよりさらに好ましい。また、５０質量％以下が好ましく、３５質量％以下がより好ましい。前記下限値以上とすることで画素領域への流出を抑制できる傾向があり、また、前記上限値以下とすることで高い接触角を示す傾向がある。例えば、架橋基を有するフッ素原子含有樹脂中のフッ素原子含有割合は、架橋基を有するフッ素原子含有樹脂中５～５０質量％が好ましく、１０～３５質量％がより好ましく、２０～３５質量％がさらに好ましく、２５～３５質量％が特に好ましい。 The fluorine atom content in the fluorine atom-containing resin having a crosslinking group is not particularly limited, but is preferably 5% by weight or more, more preferably 10% by weight or more, and more preferably 20% by weight or more in the fluorine atom-containing resin having a crosslinking group. It is more preferably at least 25% by mass. Further, the content is preferably 50% by mass or less, more preferably 35% by mass or less. When the value is equal to or larger than the lower limit, the outflow to the pixel region tends to be suppressed, and when the value is equal to or smaller than the upper limit, a high contact angle tends to be exhibited. For example, the content of fluorine atoms in the fluorine-containing resin having a cross-linking group is preferably 5 to 50% by mass, more preferably 10 to 35% by mass, and more preferably 20 to 35% by mass in the fluorine-containing resin having a cross-linking group. More preferably, it is particularly preferably from 25 to 35% by mass.
　架橋基を有するフッ素原子含有樹脂の分子量は特に制限されず、低分子量の化合物でも、高分子量体であってもよい。高分子量体の方が、ポストベークによる流動性が抑えられ、隔壁からの流出を抑えることができるため好ましく、係る観点から、架橋基を有するフッ素原子含有樹脂の数平均分子量は、１００以上が好ましく、５００以上がより好ましく、１０００００以下が好ましく、１００００以下がより好ましい。例えば、架橋基を有するフッ素原子含有樹脂の分子量は１００～１０００００が好ましく、５００～１００００がより好ましい。 分子 The molecular weight of the fluorine-containing resin having a crosslinking group is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound. Higher molecular weight is preferred because the fluidity due to post-baking is suppressed and the outflow from the partition walls can be suppressed, and from this viewpoint, the number average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 100 or more. , 500 or more, more preferably 100,000 or less, and even more preferably 10,000 or less. For example, the molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably from 100 to 100,000, and more preferably from 500 to 10,000.
　本発明の感光性着色樹脂組成物中の（Ｅ）撥液剤の含有割合は特に限定されないが、全固形分中に通常０．０１質量％以上、好ましくは０．１質量％以上、より好ましくは０．５質量％以上であり、また、通常５質量％以下、好ましくは３質量％以下、より好ましくは２質量％以下である。前記下限値以上とすることで高い撥インク性を示す傾向があり、また、前記上限値以下とすることで画素領域への流出を抑制できる傾向がある。例えば、（Ｅ）撥液剤の含有割合は、感光性着色樹脂組成物の全固形分中０．０１～５質量％が好ましく、０．１～３質量％がより好ましく、０．５～２質量％がさらに好ましい。 The content of the liquid repellent (E) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.1% by mass or more based on the total solid content. It is 0.5% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. When the amount is equal to or more than the lower limit, high ink repellency tends to be exhibited. When the amount is equal to or less than the upper limit, outflow to the pixel region tends to be suppressed. For example, the content of the liquid repellent (E) is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and more preferably 0.5 to 2% by mass based on the total solid content of the photosensitive colored resin composition. % Is more preferred.
　また、架橋基を有するフッ素原子含有樹脂の含有割合は特に限定されないが、全固形分中に通常０．０１質量％以上、好ましくは０．１質量％以上、より好ましくは０．５質量％以上であり、また、通常５質量％以下、好ましくは３質量％以下、より好ましくは２質量％以下である。前記下限値以上とすることで高い撥インク性を示す傾向があり、また、前記上限値以下とすることで画素領域への流出を抑制できる傾向がある。例えば、架橋基を有するフッ素原子含有樹脂の含有割合は、感光性着色樹脂組成物の全固形分中０．０１～５質量％が好ましく、０．１～３質量％がより好ましく、０．５～２質量％がさらに好ましい。 The content of the fluorine-containing resin having a crosslinking group is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the total solid content. And usually at most 5% by mass, preferably at most 3% by mass, more preferably at most 2% by mass. When the amount is equal to or more than the lower limit, high ink repellency tends to be exhibited. When the amount is equal to or less than the upper limit, outflow to the pixel region tends to be suppressed. For example, the content of the fluorine atom-containing resin having a crosslinking group is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and more preferably 0.5 to 3% by mass based on the total solid content of the photosensitive colored resin composition. ～ 2% by weight is more preferred.
　一方で、本発明の感光性着色樹脂組成物においては、（Ｅ）撥液剤と共に界面活性剤を用いてもよい。界面活性剤は、感光性着色樹脂組成物の塗布液としての塗布性、および塗布膜の現像性の向上などを目的として用いることができ、中でもシリコーン系の界面活性剤や架橋基を有さないフッ素系の界面活性剤が好ましい。
　特に、現像の際、未露光部から感光性着色樹脂組成物の残渣を除去する作用があり、また、濡れ性を発現する機能を有することから、シリコーン系界面活性剤が好ましく、ポリエーテル変性シリコーン系界面活性剤がさらに好ましい。 On the other hand, in the photosensitive colored resin composition of the present invention, a surfactant may be used together with the liquid repellent (E). Surfactants can be used for the purpose of improving the coating properties of the photosensitive coloring resin composition as a coating solution, and the developability of the coating film, among which silicone surfactants and crosslinking groups are not present Fluorinated surfactants are preferred.
In particular, at the time of development, it has the effect of removing the residue of the photosensitive colored resin composition from the unexposed areas, and has a function of expressing wettability. Therefore, a silicone surfactant is preferable, and polyether-modified silicone is preferred. A system surfactant is more preferred.
　架橋基を有さないフッ素系界面活性剤としては、末端、主鎖および側鎖の少なくとも何れかの部位にフルオロアルキルまたはフルオロアルキレン基を有する化合物が好適である。
　これらの市販品としては、例えば、ＢＭ　Ｃｈｅｍｉｅ社製「ＢＭ－１０００」、「ＢＭ－１１００」、ＤＩＣ社製「メガファックＦ１４２Ｄ」、「メガファックＦ１７２」、「メガファックＦ１７３」、「メガファックＦ１８３」、「メガファックＦ４７０」、「メガファックＦ４７５」、「メガファックＦ５５４」、「メガファックＦ５５９」、スリーエムジャパン社製「ＦＣ４３０」、ネオス社製「ＤＦＸ－１８」などを挙げることができる。 As the fluorine-based surfactant having no cross-linking group, a compound having a fluoroalkyl or fluoroalkylene group at at least one of terminal, main chain and side chain is preferable.
Examples of these commercially available products include "BM-1000" and "BM-1100" manufactured by BM Chemie, "MegaFac F142D", "MegaFac F172", "MegaFac F173", and "MegaFac F183" manufactured by DIC. "MegaFac F470", "MegaFac F475", "MegaFac F554", "MegaFac F559", "FC430" manufactured by 3M Japan, "DFX-18" manufactured by Neos, and the like.
　また、シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング社製「ＤＣ３ＰＡ」、「ＳＨ７ＰＡ」、「ＤＣ１１ＰＡ」、「ＳＨ２１ＰＡ」、「ＳＨ２８ＰＡ」、「ＳＨ２９ＰＡ」、「８０３２Ａｄｄｉｔｉｖｅ」、「ＳＨ８４００」、ビックケミー社製「ＢＹＫ（登録商標、以下同じ。）３２３」、「ＢＹＫ３３０」などの市販品を挙げることができる。
　界面活性剤として、フッ素系界面活性剤及びシリコーン系界面活性剤以外のものを含んでいてもよく、その他、界面活性剤としては、ノニオン性、アニオン性、カチオン性、両性界面活性剤などが挙げられる。 Examples of the silicone surfactant include, for example, “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400” manufactured by Dow Corning Toray. Commercial products such as "BYK (registered trademark, hereinafter the same) 323" and "BYK330" manufactured by BYK-Chemie can be mentioned.
The surfactant may include other than a fluorine-based surfactant and a silicone-based surfactant, and other surfactants include nonionic, anionic, cationic, and amphoteric surfactants. Can be
　上記ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアルキルエステル類、ポリオキシエチレン脂肪酸エステル類、グリセリン脂肪酸エステル類、ポリオキシエチレングリセリン脂肪酸エステル類、ペンタエリスリット脂肪酸エステル類、ポリオキシエチレンペンタエリスリット脂肪酸エステル類、ソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタン脂肪酸エステル類、ソルビット脂肪酸エステル類、ポリオキシエチレンソルビット脂肪酸エステル類などが挙げられる。これらの市販品としては、例えば、花王社製の「エマルゲン（登録商標、以下同じ。）１０４Ｐ」、「エマルゲンＡ６０」などのポリオキシエチレン系界面活性剤などが挙げられる。 Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrit fatty acid esters, polyoxyethylene pentaerythrit fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbite fatty acid esters, polyoxy And ethylene sorbite fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen (registered trademark, the same applies hereinafter) 104P" and "Emulgen A60" manufactured by Kao Corporation.
　また、上記アニオン性界面活性剤としては、例えば、アルキルスルホン酸塩類、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、ポリオキシエチレンアルキルエーテルスルホン酸塩類、アルキル硫酸塩類、アルキル硫酸エステル塩類、高級アルコール硫酸エステル塩類、脂肪族アルコール硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸塩類、特殊高分子系界面活性剤などが挙げられる。中でも、特殊高分子系界面活性剤が好ましく、特殊ポリカルボン酸型高分子系界面活性剤がさらに好ましい。このようなアニオン性界面活性剤としては市販品を用いることができ、例えば、アルキル硫酸エステル塩類では花王社製「エマール（登録商標、以下同じ。）１０」等、アルキルナフタレンスルホン酸塩類では花王社製「ペレックス（登録商標。）ＮＢ－Ｌ」など、特殊高分子系界面活性剤では花王社製「ホモゲノール（登録商標、以下同じ。）Ｌ－１８」、「ホモゲノールＬ－１００」などが挙げられる。 Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfates, and higher alcohol sulfates. Ester salts, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, specialty Polymeric surfactants and the like can be mentioned. Among them, special polymer surfactants are preferable, and special polycarboxylic acid polymer surfactants are more preferable. Commercially available products can be used as such anionic surfactants. For example, "Emal (registered trademark, the same applies hereinafter) 10" manufactured by Kao Corporation for alkyl sulfate salts, and Kao Corporation for alkyl naphthalene sulfonates. Examples of special polymer surfactants such as "Perex (registered trademark) NB-L" manufactured by Kao Corporation include "Homogenol (registered trademark, the same applies hereinafter) L-18" and "Homogenol L-100". .
　さらに、上記カチオン性界面活性剤としては、第４級アンモニウム塩類、イミダゾリン誘導体類、アルキルアミン塩類などが、また、両性界面活性剤としては、ベタイン型化合物類、イミダゾリウム塩類、イミダゾリン類、アミノ酸類などが挙げられる。これらのうち、第４級アンモニウム塩類が好ましく、ステアリルトリメチルアンモニウム塩類がさらに好ましい。市販のものとしては、例えば、アルキルアミン塩類では花王社製「アセタミン（登録商標。）２４」など、第４級アンモニウム塩類では花王社製「コータミン（登録商標、以下同じ。）２４Ｐ」、「コータミン８６Ｗ」などが挙げられる。 Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Examples of the amphoteric surfactant include betaine-type compounds, imidazolium salts, imidazolines, and amino acids. And the like. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of commercially available products include, for example, “Acetamine (registered trademark) 24” manufactured by Kao Corporation for alkylamine salts, and “Coatamine (registered trademark, same hereafter) 24P” and “Coatamine” manufactured by Kao Corporation for quaternary ammonium salts. 86W ".
　また、界面活性剤は２種類以上の組み合わせで用いてもよく、例えば、シリコーン系界面活性剤／フッ素系界面活性剤、シリコーン系界面活性剤／特殊高分子系界面活性剤、フッ素系界面活性剤／特殊高分子系界面活性剤の組み合わせなどが挙げられる。中でも、シリコーン系界面活性剤／フッ素系界面活性剤の組み合わせが好ましい。このシリコーン系界面活性剤／フッ素系界面活性剤の組み合わせでは、例えば、ネオス社製「ＤＦＸ－１８」、ビックケミー社製「ＢＹＫ－３００」または「ＢＹＫ－３３０」／ＡＧＣセイミケミカル社製「Ｓ－３９３」、信越シリコーン社製「ＫＰ３４０」／ＤＩＣ社製「Ｆ－５５４」または「Ｆ－５５９」、東レ・ダウコーニング社製「ＳＨ７ＰＡ」／ダイキン社製「ＤＳ－４０１」、ＮＵＣ社製「Ｌ－７７」／スリーエムジャパン社製「ＦＣ４４３０」などが挙げられる。 Further, two or more surfactants may be used in combination. For example, silicone surfactants / fluorine surfactants, silicone surfactants / special polymer surfactants, fluorine surfactants / Combinations of special polymer surfactants. Among them, a combination of a silicone-based surfactant / a fluorine-based surfactant is preferable. In this combination of silicone surfactant / fluorine surfactant, for example, "DFX-18" manufactured by Neos Co., Ltd., "BYK-300" or "BYK-330" manufactured by BYK-Chemie, or "S- manufactured by AGC Seimi Chemical Co., Ltd." 393 ”, Shin-Etsu Silicone“ KP340 ”/ DIC“ F-554 ”or“ F-559 ”, Toray Dow Corning“ SH7PA ”/ Daikin“ DS-401 ”, NUC“ L ” -77 "/" FC4430 "manufactured by 3M Japan.
［１－１－６］（Ｆ）分散剤
　本発明の感光性着色樹脂組成物は、（Ｄ）着色剤を微細に分散させ、かつその分散状態を安定化させるため、（Ｆ）分散剤を含むことが好ましい。
　（Ｆ）分散剤としては、官能基を有する高分子分散剤が好ましく、さらに、分散安定性の面からカルボキシル基；リン酸基；スルホン酸基；又はこれらの塩基；一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の官能基を有する高分子分散剤が好ましい。中でも特に、一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の塩基性官能基を有する高分子分散剤が顔料を分散する際に少量の分散剤で分散することができるとの観点から特に好ましい。 [1-1-6] (F) Dispersant The photosensitive colored resin composition of the present invention contains (D) a dispersant in order to finely disperse the (D) colorant and stabilize the dispersion state. It is preferred to include.
(F) As the dispersant, a polymer dispersant having a functional group is preferable, and further from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary, or tertiary. Polymer dispersants having a functional group such as an amino group, a quaternary ammonium base, a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, and pyrazine are preferred. Among them, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine disperses the pigment. It is particularly preferable from the viewpoint that it can be dispersed with a small amount of a dispersant.
　また、高分子分散剤としては、例えばウレタン系分散剤、アクリル系分散剤、ポリエチレンイミン系分散剤、ポリアリルアミン系分散剤、アミノ基を持つモノマーとマクロモノマーからなる分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレンジエステル系分散剤、ポリエーテルリン酸系分散剤、ポリエステルリン酸系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性ポリエステル系分散剤等を挙げることができる。 Examples of the polymer dispersant include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, and a polyoxyethylene alkyl ether. Dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
　このような分散剤の具体例としては、商品名で、ＥＦＫＡ（登録商標。ＢＡＳＦ社製。）、ＤＩＳＰＥＲＢＹＫ（登録商標。ビックケミー社製。）、ディスパロン（登録商標。楠本化成社製。）、ＳＯＬＳＰＥＲＳＥ（登録商標。ルーブリゾール社製。）、ＫＰ（信越化学工業社製）、ポリフロー（共栄社化学社製）、アジスパー（登録商標。味の素社製。）等を挙げることができる。
　これらの高分子分散剤は１種を単独で使用してもよく、又は２種以上を併用してもよい。 Specific examples of such dispersants are EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Big Chemie), Dispalon (registered trademark, manufactured by Kusumoto Kasei), SOLSPERSE under trade names. (Registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Azispar (registered trademark, manufactured by Ajinomoto Co., Inc.).
One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.
　高分子分散剤の重量平均分子量（Ｍｗ）は通常７００以上、好ましくは１０００以上であり、また通常１０００００以下、好ましくは５００００以下である。例えば、高分子分散剤の重量平均分子量（Ｍｗ）は７００～１０００００が好ましく、１０００～５００００がより好ましい。
　これらの内、顔料の分散性の観点から、（Ｆ）分散剤は官能基を有するウレタン系高分子分散剤及びアクリル系高分子分散剤のいずれか一方又は両方を含むことが好ましく、アクリル系高分子分散剤を含むことが特に好ましい。
　また分散性、保存性の面から、塩基性官能基を有し、ポリエステル結合及びポリエーテル結合のいずれか一方又は両方を有する高分子分散剤が好ましい。 The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less. For example, the weight average molecular weight (Mw) of the polymer dispersant is preferably from 700 to 100,000, more preferably from 1,000 to 50,000.
Among these, from the viewpoint of the dispersibility of the pigment, the dispersant (F) preferably contains one or both of a urethane polymer dispersant and an acrylic polymer dispersant having a functional group. It is particularly preferred to include a molecular dispersant.
From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having one or both of a polyester bond and a polyether bond is preferable.
　ウレタン系及びアクリル系高分子分散剤としては、例えばＤＩＳＰＥＲＢＹＫ－１６０～１６７、１８２シリーズ（いずれもウレタン系）、ＤＩＳＰＥＲＢＹＫ－２０００、２００１、ＢＹＫ－ＬＰＮ２１１１６等（いずれもアクリル系）（以上すべてビックケミー社製）が挙げられる。
　ウレタン系高分子分散剤として好ましい化学構造を具体的に例示するならば、例えば、ポリイソシアネート化合物と、分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物と、同一分子内に活性水素と３級アミノ基を有する化合物とを反応させることによって得られる、重量平均分子量１０００～２０００００の分散樹脂等が挙げられる。これらをベンジルクロリド等の四級化剤で処理することで、３級アミノ基の全部又は一部を４級アンモニウム塩基にすることができる。 Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK-160 to 167 and 182 series (all are urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 and the like (all are acrylic-based). ).
Specific examples of preferable chemical structures for the urethane polymer dispersant include, for example, a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000, and And a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting an active hydrogen with a compound having a tertiary amino group. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.
　上記のポリイソシアネート化合物の例としては、パラフェニレンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、ナフタレン－１，５－ジイソシアネート、トリジンジイソシアネート等の芳香族ジイソシアネート、ヘキサメチレンジイソシアネート、リジンメチルエステルジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート等の脂肪族ジイソシアネート、イソホロンジイソシアネート、４，４’－メチレンビス（シクロヘキシルイソシアネート）、ω，ω’－ジイソシアネートジメチルシクロヘキサン等の脂環族ジイソシアネート、キシリレンジイソシアネート、α，α，α’，α’－テトラメチルキシリレンジイソシアネート等の芳香環を有する脂肪族ジイソシアネート、リジンエステルトリイソシアネート、１，６，１１－ウンデカントリイソシアネート、１，８－ジイソシアネート－４－イソシアネートメチルオクタン、１，３，６－ヘキサメチレントリイソシアネート、ビシクロヘプタントリイソシアネート、トリス（イソシアネートフェニルメタン）、トリス（イソシアネートフェニル）チオホスフェート等のトリイソシアネート、及びこれらの三量体、水付加物、及びこれらのポリオール付加物等が挙げられる。ポリイソシアネートとして好ましいのは有機ジイソシアネートの三量体で、最も好ましいのはトリレンジイソシアネートの三量体とイソホロンジイソシアネートの三量体である。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanate such as aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanate such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanate having an aromatic ring such as silylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, Examples include triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane) and tris (isocyanatephenyl) thiophosphate, and trimers, water adducts, and polyol adducts thereof. Preferred as polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate.
These may be used alone or in combination of two or more.
　イソシアネートの三量体の製造方法としては、前記ポリイソシアネート類を適当な三量化触媒、例えば第３級アミン類、ホスフィン類、アルコキシド類、金属酸化物、カルボン酸塩類等を用いてイソシアネート基の部分的な三量化を行い、触媒毒の添加により三量化を停止させた後、未反応のポリイソシアネートを溶剤抽出、薄膜蒸留により除去して目的のイソシアヌレート基含有ポリイソシアネートを得る方法が挙げられる。 As a method for producing a trimer of isocyanate, the polyisocyanate is partially reacted with an appropriate trimerization catalyst such as a tertiary amine, a phosphine, an alkoxide, a metal oxide, a carboxylate, or the like. After performing a typical trimerization and terminating the trimerization by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain a target isocyanurate group-containing polyisocyanate.
　同一分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物としては、ポリエーテルグリコール、ポリエステルグリコール、ポリカーボネートグリコール、ポリオレフィングリコール等、及びこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化されたもの及びこれら２種類以上の混合物が挙げられる。
　ポリエーテルグリコールとしては、ポリエーテルジオール、ポリエーテルエステルジオール、及びこれら２種類以上の混合物が挙げられる。ポリエーテルジオールとしては、アルキレンオキシドを単独又は共重合させて得られるもの、例えばポリエチレングリコール、ポリプロピレングリコール、ポリエチレン－プロピレングリコール、ポリオキシテトラメチレングリコール、ポリオキシヘキサメチレングリコール、ポリオキシオクタメチレングリコール及びそれらの２種以上の混合物が挙げられる。 Examples of the compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether glycols, polyester glycols, polycarbonate glycols, polyolefin glycols, and the like. Examples thereof include those alkoxylated with 25 alkyl groups and mixtures of two or more thereof.
Examples of the polyether glycol include polyether diol, polyether ester diol, and a mixture of two or more thereof. Examples of the polyether diol include those obtained by homo- or copolymerizing an alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. And mixtures of two or more of the above.
　ポリエーテルエステルジオールとしては、エーテル基含有ジオールもしくは他のグリコールとの混合物をジカルボン酸又はそれらの無水物と反応させるか、又はポリエステルグリコールにアルキレンオキシドを反応させることによって得られるもの、例えばポリ（ポリオキシテトラメチレン）アジペート等が挙げられる。ポリエーテルグリコールとして最も好ましいのはポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコール又はこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化された化合物である。 Examples of the polyetherester diol include those obtained by reacting a mixture with an ether group-containing diol or another glycol with a dicarboxylic acid or an anhydride thereof, or reacting a polyester glycol with an alkylene oxide, such as poly (poly (Oxytetramethylene) adipate and the like. The most preferred polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which a hydroxyl group at one end of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
　ポリエステルグリコールとしては、ジカルボン酸（コハク酸、グルタル酸、アジピン酸、セバシン酸、フマル酸、マレイン酸、フタル酸等）又はそれらの無水物とグリコール（エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、２－メチル－１，３－プロパンジオール、２－メチル－２－プロピル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２，５－ジメチル－２，５－ヘキサンジオール、１，８－オクタメチレングリコール、２－メチル－１，８－オクタメチレングリコール、１，９－ノナンジオール等の脂肪族グリコール、ビスヒドロキシメチルシクロヘキサン等の脂環族グリコール、キシリレングリコール、ビスヒドロキシエトキシベンゼン等の芳香族グリコール、Ｎ－メチルジエタノールアミン等のＮ－アルキルジアルカノールアミン等）とを重縮合させて得られたもの、例えばポリエチレンアジペート、ポリブチレンアジペート、ポリヘキサメチレンアジペート、ポリエチレン／プロピレンアジペート等、又は前記ジオール類又は炭素数１～２５の１価アルコールを開始剤として用いて得られるポリラクトンジオール又はポリラクトンモノオール、例えばポリカプロラクトングリコール、ポリメチルバレロラクトン及びこれらの２種以上の混合物が挙げられる。ポリエステルグリコールとして最も好ましいのはポリカプロラクトングリコール又は炭素数１～２５のアルコールを開始剤としたポリカプロラクトンである。 Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4 Pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; -N-alkyl dialkanolamine such as -methyldiethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diols or carbon number 1 to 25 1 Alcohol polylactone diol obtained by using as an initiator or polylactone monool, for example polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone with an alcohol having 1 to 25 carbon atoms as an initiator.
　ポリカーボネートグリコールとしては、ポリ（１，６－ヘキシレン）カーボネート、ポリ（３－メチル－１，５－ペンチレン）カーボネート等、ポリオレフィングリコールとしてはポリブタジエングリコール、水素添加型ポリブタジエングリコール、水素添加型ポリイソプレングリコール等が挙げられる。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Polycarbonate glycols include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, etc. Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. Is mentioned.
These may be used alone or in combination of two or more.
　同一分子内に水酸基を１個又は２個有する化合物の数平均分子量は、通常３００～１００００、好ましくは５００～６０００、さらに好ましくは１０００～４０００である。 数 The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
　同一分子内に活性水素と３級アミノ基を有する化合物を説明する。
　活性水素、即ち、酸素原子、窒素原子又は硫黄原子に直接結合している水素原子としては、水酸基、アミノ基、チオール基等の官能基中の水素原子が挙げられ、中でもアミノ基、特に１級のアミノ基の水素原子が好ましい。 A compound having active hydrogen and a tertiary amino group in the same molecule will be described.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Is preferably a hydrogen atom of the amino group.
　３級アミノ基は、特に限定されないが、例えば炭素数１～４のアルキル基を有するアミノ基、又はヘテロ環構造、より具体的にはイミダゾール環又はトリアゾール環、などが挙げられる。 The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
　このような同一分子内に活性水素と３級アミノ基を有する化合物を例示するならば、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジプロピル－１，３－プロパンジアミン、Ｎ，Ｎ－ジブチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジメチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、Ｎ，Ｎ－ジプロピルエチレンジアミン、Ｎ，Ｎ－ジブチルエチレンジアミン、Ｎ，Ｎ－ジメチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジエチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジプロピル－１，４－ブタンジアミン、Ｎ，Ｎ－ジブチル－１，４－ブタンジアミン等が挙げられる。 Examples of such a compound having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-Dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.
　また、３級アミノ基が含窒素ヘテロ環構造である場合の該含窒素ヘテロ環としては、ピラゾール環、イミダゾール環、トリアゾール環、テトラゾール環、インドール環、カルバゾール環、インダゾール環、ベンズイミダゾール環、ベンゾトリアゾール環、ベンゾオキサゾール環、ベンゾチアゾール環、ベンゾチアジアゾール環等の含窒素ヘテロ５員環、ピリジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、アクリジン環、イソキノリン環等の含窒素ヘテロ６員環が挙げられる。これらの含窒素ヘテロ環のうち好ましいものはイミダゾール環又はトリアゾール環である。 When the tertiary amino group has a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocycle include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzoidyl ring. 5-membered nitrogen-containing hetero ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, etc. Rings. Preferred among these nitrogen-containing hetero rings are an imidazole ring and a triazole ring.
　これらのイミダゾール環とアミノ基を有する化合物を具体的に例示するならば、１－（３－アミノプロピル）イミダゾール、ヒスチジン、２－アミノイミダゾール、１－（２－アミノエチル）イミダゾール等が挙げられる。また、トリアゾール環とアミノ基を有する化合物を具体的に例示するならば、３－アミノ－１，２，４－トリアゾール、５－（２－アミノ－５－クロロフェニル）－３－フェニル－１Ｈ－１，２，４－トリアゾール、４－アミノ－４Ｈ－１，２，４－トリアゾール－３，５－ジオール、３－アミノ－５－フェニル－１Ｈ－１，３，４－トリアゾール、５－アミノ－１，４－ジフェニル－１，２，３－トリアゾール、３－アミノ－１－ベンジル－１Ｈ－２，４－トリアゾール等が挙げられる。中でも、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、１－（３－アミノプロピル）イミダゾール、３－アミノ－１，２，４－トリアゾールが好ましい。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole and 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1. , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, and 3-amino-1,2,4-triazole. preferable.
These may be used alone or in combination of two or more.
　ウレタン系高分子分散剤を製造する際の原料の好ましい配合比率はポリイソシアネート化合物１００質量部に対し、同一分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物が１０～２００質量部、好ましくは２０～１９０質量部、さらに好ましくは３０～１８０質量部、同一分子内に活性水素と３級アミノ基を有する化合物が０．２～２５質量部、好ましくは０．３～２４質量部である。 The preferred compounding ratio of the raw materials for producing the urethane-based polymer dispersant is 10 to 200 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule per 100 parts by mass of the polyisocyanate compound. Parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass, of a compound having active hydrogen and a tertiary amino group in the same molecule. Parts by weight.
　ウレタン系高分子分散剤の製造はポリウレタン樹脂製造の公知の方法に従って行われる。製造する際の溶媒としては、通常、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、イソホロン等のケトン類、酢酸エチル、酢酸ブチル、酢酸セロソルブ等のエステル類、ベンゼン、トルエン、キシレン、ヘキサン等の炭化水素類、ダイアセトンアルコール、イソプロパノール、第二ブタノール、第三ブタノール等一部のアルコール類、塩化メチレン、クロロホルム等の塩化物、テトラヒドロフラン、ジエチルエーテル等のエーテル類、ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキサイド等の非プロトン性極性溶媒等が用いられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 The production of the urethane polymer dispersant is performed according to a known method for producing a polyurethane resin. As the solvent for the production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, secondary butanol, tertiary butanol, some alcohols such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl An aprotic polar solvent such as pyrrolidone and dimethyl sulfoxide is used. These may be used alone or in combination of two or more.
　上記製造に際して、通常、ウレタン化反応触媒が用いられる。この触媒としては、例えば、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジオクトエート、スタナスオクトエート等の錫系、鉄アセチルアセトナート、塩化第二鉄等の鉄系、トリエチルアミン、トリエチレンジアミン等の３級アミン系等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。 に 際 し て In the above production, usually, a urethanation reaction catalyst is used. Examples of the catalyst include tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannas octoate, iron compounds such as iron acetylacetonate and ferric chloride, and triethylamine and triethylenediamine. Secondary amines and the like. These may be used alone or in combination of two or more.
　同一分子内に活性水素と３級アミノ基を有する化合物の導入量は反応後のアミン価で１～１００ｍｇＫＯＨ／ｇの範囲に制御することが好ましい。より好ましくは５～９５ｍｇＫＯＨ／ｇの範囲である。アミン価は、塩基性アミノ基を酸により中和滴定し、酸価に対応させてＫＯＨのｍｇ数で表した値である。前記下限値以上とすることで分散能力が良化する傾向があり、また、前記上限値以下とすることで現像性が良化する傾向がある。 (4) The amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid and expressing the KOH in mg corresponding to the acid value. When the content is not less than the lower limit, the dispersing ability tends to be improved, and when the content is not more than the upper limit, the developability tends to be improved.
　なお、以上の反応で高分子分散剤にイソシアネート基が残存する場合にはさらに、アルコールやアミノ化合物でイソシアネート基を不活性化させると生成物の経時安定性が高くなるので好ましい。
　ウレタン系高分子分散剤の重量平均分子量（Ｍｗ）は通常１０００～２０００００、好ましくは２０００～１０００００、より好ましくは３０００～５００００の範囲である。前記下限値以上とすることで分散性及び分散安定性が良化する傾向があり、前記上限値以下とすることで溶解性が向上し分散性が良化する傾向がある。 In the case where the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further deactivate the isocyanate group with an alcohol or an amino compound because the stability with time of the product is increased.
The weight average molecular weight (Mw) of the urethane polymer dispersant is generally in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. The dispersibility and dispersion stability tend to be improved by setting the lower limit or more, and the solubility and dispersibility tend to be improved by setting the lower limit or less.
　アクリル系高分子分散剤としては、官能基（ここでいう官能基とは、高分子分散剤に含有される官能基として前述した官能基である。）を有する不飽和基含有単量体と、官能基を有さない不飽和基含有単量体とのランダム共重合体、グラフト共重合体、ブロック共重合体を使用することが好ましい。これらの共重合体は公知の方法で製造することができる。 As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (here, the functional group is a functional group described above as a functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, and a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.
　官能基を有する不飽和基含有単量体としては、（メタ）アクリル酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、アクリル酸ダイマー等のカルボキシル基を有する不飽和単量体、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート及びこれらの４級化物などの３級アミノ基、４級アンモニウム塩基を有する不飽和単量体が具体例として挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and 2- (meth) acrylic acid. Unsaturated monomers having a carboxyl group such as loyloxyethyl hexahydrophthalic acid and acrylic acid dimer; tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.
　官能基を有さない不飽和基含有単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシメチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリシクロデカン（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、Ｎ－ビニルピロリドン、スチレン及びその誘導体、α－メチルスチレン、Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミド、Ｎ－ベンジルマレイミドなどのＮ－置換マレイミド、アクリロニトリル、酢酸ビニル及びポリメチル（メタ）アクリレートマクロモノマー、ポリスチレンマクロモノマー、ポリ２－ヒドロキシエチル（メタ）アクリレートマクロモノマー、ポリエチレングリコールマクロモノマー、ポリプロピレングリコールマクロモノマー、ポリカプロラクトンマクロモノマーなどのマクロモノマー等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclo N-substituted maleimides such as xylmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol And macromonomers such as macromonomer, polypropylene glycol macromonomer, and polycaprolactone macromonomer. These may be used alone or in combination of two or more.
　アクリル系高分子分散剤は、特に好ましくは、官能基を有するＡブロックと官能基を有さないＢブロックからなるＡ－Ｂ又はＢ－Ａ－Ｂブロック共重合体であるが、この場合、Ａブロック中には上記官能基を含む不飽和基含有単量体由来の部分構造の他に、上記官能基を含まない不飽和基含有単量体由来の部分構造が含まれていてもよく、これらが該Ａブロック中においてランダム共重合又はブロック共重合のいずれの態様で含有されていてもよい。また、官能基を含まない部分構造の、Ａブロック中の含有量は、通常８０質量％以下であり、好ましくは５０質量％以下、さらに好ましくは３０質量％以下である。 The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block having no functional group. In addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the block may include a partial structure derived from the unsaturated group-containing monomer containing no functional group. May be contained in the A block in any mode of random copolymerization or block copolymerization. The content of the partial structure containing no functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
　Ｂブロックは、上記官能基を含まない不飽和基含有単量体由来の部分構造からなるものであるが、１つのＢブロック中に２種以上の単量体由来の部分構造が含有されていてもよく、これらは、該Ｂブロック中においてランダム共重合又はブロック共重合のいずれの態様で含有されていてもよい。
　該Ａ－Ｂ又はＢ－Ａ－Ｂブロック共重合体は、例えば、以下に示すリビング重合法にて調製される。
　リビング重合法には、アニオンリビング重合法、カチオンリビング重合法、ラジカルリビング重合法がある。 The B block is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more types of monomers. These may be contained in the B block in any mode of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method.
　このアクリル系高分子分散剤を合成するに際しては、日本国特開平９－６２００２号公報や、Ｐ．Ｌｕｔｚ，　Ｐ．Ｍａｓｓｏｎ　ｅｔ　ａｌ，　Ｐｏｌｙｍ．　Ｂｕｌｌ．　１２，　７９　（１９８４），　Ｂ．Ｃ．Ａｎｄｅｒｓｏｎ，　Ｇ．Ｄ．Ａｎｄｒｅｗｓ　ｅｔ　ａｌ，　Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，　１４，　１６０１（１９８１），　Ｋ．Ｈａｔａｄａ，　Ｋ．Ｕｔｅ，ｅｔ　ａｌ，　Ｐｏｌｙｍ．　Ｊ．　１７，　９７７（１９８５），　１８，　１０３７（１９８６），　右手浩一、畑田耕一、高分子加工、３６，　３６６（１９８７），東村敏延、沢本光男、高分子論文集、４６，　１８９（１９８９），　Ｍ．Ｋｕｒｏｋｉ，　Ｔ．Ａｉｄａ，　Ｊ．　Ａｍ．　Ｃｈｅｍ．　Ｓｉｃ，　１０９，　４７３７（１９８７）、相田卓三、井上祥平、有機合成化学、４３，　３００（１９８５），　Ｄ．Ｙ．Ｓｏｇｏｈ，　Ｗ．Ｒ．Ｈｅｒｔｌｅｒ　ｅｔ　ａｌ，　Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，　２０，　１４７３（１９８７）などに記載の公知の方法を採用することができる。 合成 When synthesizing this acrylic polymer dispersant, Japanese Patent Application Laid-Open No. 9-62002 or Lutz, P. Masson et al, Polym. {Bull. {12, {79} (1984), {B. C. Anderson, @G. D. Andrews et al, Macromolecules, 14, 14, 1601 (1981), KK. Hatada, @K. Ute, et @ al, @ Polym. {J. 17, 977 (1985), 18, 1837 (1986), Koichi Ute, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymers, 46, 189 (1989), M. Kuroki, @T. Aida, @J. {Am. {Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D. Y. Sogoh, @W. R. Known methods described in Hertler et al, Macromolecules, 20, 20, 1473 (1987) and the like can be employed.
　本発明で用いることができるアクリル系高分子分散剤はＡ－Ｂブロック共重合体であっても、Ｂ－Ａ－Ｂブロック共重合体であってもよく、その共重合体を構成するＡブロック／Ｂブロック比は１／９９～８０／２０、特に５／９５～６０／４０（質量比）であることが好ましく、この範囲内にすることで分散性と保存安定性のバランスの確保ができる傾向がある。
　また、本発明で用いることができるＡ－Ｂブロック共重合体、Ｂ－Ａ－Ｂブロック共重合体１ｇ中の４級アンモニウム塩基の量は、通常０．１～１０ｍｍｏｌであることが好ましく、この範囲内にすることで良好な分散性を確保できる傾向がある。 The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer may be used. The / B block ratio is preferably from 1/99 to 80/20, particularly preferably from 5/95 to 60/40 (mass ratio). By keeping the ratio within this range, a balance between dispersibility and storage stability can be ensured. Tend.
Further, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer which can be used in the present invention is usually preferably from 0.1 to 10 mmol. When the content is within the range, good dispersibility tends to be ensured.
　なお、このようなブロック共重合体中には、通常、製造過程で生じたアミノ基が含有される場合があるが、そのアミン価は１～１００ｍｇＫＯＨ／ｇ程度であり、分散性の観点から、好ましくは１０ｍｇＫＯＨ／ｇ以上、より好ましくは３０ｍｇＫＯＨ／ｇ以上、さらに好ましくは５０ｍｇＫＯＨ／ｇ以上、また、好ましくは９０ｍｇＫＯＨ／ｇ以下、より好ましくは８０ｍｇＫＯＨ／ｇ以下、さらに好ましくは７５ｍｇＫＯＨ／ｇ以下である。例えば、ブロック共重合体のアミン価は１０～９０ｍｇＫＯＨ／ｇが好ましく、３０～８０ｍｇＫＯＨ／ｇがより好ましく、５０～７５ｍｇＫＯＨ／ｇがさらに好ましい。
　ここで、これらのブロック共重合体等の分散剤のアミン価は、分散剤試料中の溶剤を除いた固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表し、次の方法により測定する。
　１００ｍＬのビーカーに分散剤試料の０．５～１．５ｇを精秤し、５０ｍＬの酢酸で溶解する。ｐＨ電極を備えた自動滴定装置を使って、この溶液を０．１ｍｏｌ／ＬのＨＣｌＯ4酢酸溶液にて中和滴定する。滴定ｐＨ曲線の変曲点を滴定終点とし次式によりアミン価を求める。 Incidentally, such a block copolymer usually contains an amino group generated during the production process in some cases. The amine value is about 1 to 100 mgKOH / g, and from the viewpoint of dispersibility, It is preferably at least 10 mgKOH / g, more preferably at least 30 mgKOH / g, still more preferably at least 50 mgKOH / g, preferably at most 90 mgKOH / g, more preferably at most 80 mgKOH / g, even more preferably at most 75 mgKOH / g. For example, the amine value of the block copolymer is preferably from 10 to 90 mgKOH / g, more preferably from 30 to 80 mgKOH / g, even more preferably from 50 to 75 mgKOH / g.
Here, the amine value of the dispersant such as these block copolymers is represented by the mass of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
0.5-1.5 g of the dispersant sample is precisely weighed in a 100 mL beaker, and dissolved with 50 mL of acetic acid. This solution is subjected to neutralization titration with a 0.1 mol / L HClO 4 acetic acid solution using an automatic titrator equipped with a pH electrode. The amine value is determined by the following equation using the inflection point of the titration pH curve as the end point of the titration.
　アミン価［ｍｇＫＯＨ／ｇ］＝（５６１×Ｖ）／（Ｗ×Ｓ）〔但し、Ｗ：分散剤試料秤取量［ｇ］、Ｖ：滴定終点での滴定量［ｍＬ］、Ｓ：分散剤試料の固形分濃度［質量％］を表す。〕
　また、このブロック共重合体の酸価は、その酸価の元となる酸性基の有無及び種類にもよるが、一般に低い方が好ましく、通常１０ｍｇＫＯＨ／ｇ以下であり、その重量平均分子量（Ｍｗ）は、１０００～１０００００の範囲が好ましい。前記範囲内とすることで良好な分散性を確保できる傾向がある。 Amine value [mgKOH / g] = (561 × V) / (W × S) [Where, W: weighed amount of dispersant sample [g], V: titer at the end of titration [mL], S: dispersant Indicates the solid content concentration [% by mass] of the sample. ]
The acid value of this block copolymer depends on the presence or absence and the type of the acidic group from which the acid value is derived, but is generally preferably lower, usually 10 mgKOH / g or less, and its weight average molecular weight (Mw ) Is preferably in the range of 1,000 to 100,000. When the content is in the above range, good dispersibility tends to be ensured.
　４級アンモニウム塩基を官能基として有する場合、高分子分散剤の具体的な構造については特に限定されないが、分散性の観点からは、下記式（ｉ）で表される繰り返し単位（以下、「繰り返し単位（ｉ）」ということがある。）を有することが好ましい。 When the polymer has a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited. However, from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter referred to as “repeating unit”) Unit (i) ”).
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　上記式（ｉ）中、Ｒ31～Ｒ33は各々独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表し；
Ｒ31～Ｒ33のうち２つ以上が互いに結合して環状構造を形成してもよく；
Ｒ34は水素原子又はメチル基であり；
Ｘは２価の連結基であり；
Ｙ-は対アニオンである。 In the above formula (i), R 31 to R 33 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an optionally substituted aralkyl group;
Two or more of R 31 to R 33 may combine with each other to form a cyclic structure;
R 34 is a hydrogen atom or a methyl group;
X is a divalent linking group;
Y - is a counter anion.
　上記式（ｉ）のＲ31～Ｒ33における、置換基を有していてもよいアルキル基の炭素数は特に限定されないが、１以上であって、また、１０以下であることが好ましく、６以下であることがより好ましい。例えば、アルキル基の炭素数は１～１０が好ましく、１～６がより好ましい。アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましい。また、直鎖状、分枝状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含んでもよい。 The carbon number of the optionally substituted alkyl group in R 31 to R 33 in the above formula (i) is not particularly limited, but is preferably 1 or more, and more preferably 10 or less. It is more preferred that: For example, the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. Group, pentyl group or hexyl group, more preferably methyl group, ethyl group, propyl group or butyl group. Further, it may be linear or branched. Further, it may include a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.
　上記式（ｉ）のＲ31～Ｒ33における、置換基を有していてもよいアリール基の炭素数は特に限定されないが、通常６以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましい。例えば、アリール基の炭素数は６～１６が好ましく、６～１２がより好ましい。アリール基の具体例としては、フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ナフチル基、アントラセニル基などが挙げられ、これらの中でもフェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、又はジエチルフェニル基であることが好ましく、フェニル基、メチルフェニル基、又はエチルフェニル基であることがより好ましい。 The carbon number of the optionally substituted aryl group in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 12 It is more preferred that: For example, the aryl group preferably has 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Of these, a phenyl group, a methylphenyl group, an ethylphenyl group , A dimethylphenyl group or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
　上記式（ｉ）のＲ31～Ｒ33における、置換基を有していてもよいアラルキル基の炭素数は特に限定されないが、通常７以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましい。例えば、アラルキル基の炭素数は７～１６が好ましく、７～１２がより好ましい。アラルキル基の具体例としては、フェニルメチル基（ベンジル基）、フェニルエチル基（フェネチル基）、フェニルプロピル基、フェニルブチル基、フェニルイソプロピル基などが挙げられ、これらの中でも、フェニルメチル基、フェニルエチル基、フェニルプロピル基、又はフェニルブチル基であることが好ましく、フェニルメチル基、又はフェニルエチル基であることがより好ましい。 The carbon number of the optionally substituted aralkyl group in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, and 12 It is more preferred that: For example, the aralkyl group preferably has 7 to 16 carbon atoms, and more preferably 7 to 12 carbon atoms. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. A phenylpropyl group or a phenylbutyl group, and more preferably a phenylmethyl group or a phenylethyl group.
　これらの中でも、分散性の観点から、Ｒ31～Ｒ33が各々独立に、アルキル基、又はアラルキル基であることが好ましく、具体的には、Ｒ31及びＲ33が各々独立に、メチル基、又はエチル基であり、かつ、Ｒ32がフェニルメチル基、又はフェニルエチル基であることが好ましく、Ｒ31及びＲ33がメチル基であり、かつ、Ｒ32がフェニルメチル基であることがさらに好ましい。 Among these, from the viewpoint of dispersibility, it is preferable that R 31 to R 33 are each independently an alkyl group or an aralkyl group. Specifically, R 31 and R 33 are each independently a methyl group, Or an ethyl group, and R 32 is preferably a phenylmethyl group or a phenylethyl group, and more preferably, R 31 and R 33 are a methyl group, and R 32 is a phenylmethyl group. .
　また、前記高分子分散剤が官能基として３級アミンを有する場合、分散性の観点からは、下記式（ｉｉ）で表される繰り返し単位（以下、「繰り返し単位（ｉｉ）」ということがある。）を有することが好ましい。 When the polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, a repeating unit represented by the following formula (ii) (hereinafter, referred to as a “repeating unit (ii)” may be used. ) Is preferable.
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
　上記式（ｉｉ）中、Ｒ35及びＲ36は各々独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基であり；
Ｒ35及びＲ36が互いに結合して環状構造を形成してもよく；
Ｒ37は水素原子又はメチル基であり；
Ｚは２価の連結基である。 In the formula (ii), R 35 and R 36 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An aralkyl group which may be substituted;
R 35 and R 36 may combine with each other to form a cyclic structure;
R 37 is a hydrogen atom or a methyl group;
Z is a divalent linking group.
　上記式（ｉｉ）のＲ35及びＲ36における、置換基を有していてもよいアルキル基としては、上記式（ｉ）のＲ31～Ｒ33として例示したものを好ましく採用することができる。
　上記式（ｉｉ）のＲ35及びＲ36における、置換基を有していてもよいアリール基としては、上記式（ｉ）のＲ31～Ｒ33として例示したものを好ましく採用することができる。
　上記式（ｉｉ）のＲ35及びＲ36における、置換基を有していてもよいアラルキル基としては、上記式（ｉ）のＲ31～Ｒ33として例示したものを好ましく採用することができる。 As the alkyl group which may have a substituent in R 35 and R 36 in the above formula (ii), those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.
As the optionally substituted aryl group in R 35 and R 36 in the above formula (ii), those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.
As the aralkyl group which may have a substituent in R 35 and R 36 in the above formula (ii), those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.
　これらの中でも、Ｒ35及びＲ36が各々独立に、置換基を有していてもよいアルキル基であることが好ましく、メチル基、又はエチル基であることがより好ましい。 Among them, R 35 and R 36 are each independently preferably an alkyl group which may have a substituent, more preferably a methyl group or an ethyl group.
　上記式（ｉ）のＲ31～Ｒ33及び上記式（ｉｉ）のＲ35及びＲ36におけるアルキル基、アラルキル基又はアリール基が有していてもよい置換基としては、ハロゲン原子、アルコキシ基、ベンゾイル基、水酸基などが挙げられる。 Examples of the substituent which the alkyl group, aralkyl group or aryl group of R 31 to R 33 of the above formula (i) and R 35 and R 36 of the above formula (ii) may have include a halogen atom, an alkoxy group, Examples include a benzoyl group and a hydroxyl group.
　上記式（ｉ）及び（ｉｉ）において、２価の連結基Ｘ及びＺとしては、例えば、炭素数１～１０のアルキレン基、炭素数６～１２のアリーレン基、－ＣＯＮＨ－Ｒ43－基、－ＣＯＯＲ44－基〔但し、Ｒ43及びＲ44は単結合、炭素数１～１０のアルキレン基、又は炭素数２～１０のエーテル基（アルキルオキシアルキル基）である〕等が挙げられ、好ましくは－ＣＯＯ－Ｒ44－基である。
　また、上記式（ｉ）において、対アニオンのＹ-としては、Ｃｌ-、Ｂｒ-、Ｉ-、ＣｌＯ4 -、ＢＦ4 -、ＣＨ3ＣＯＯ-、ＰＦ6 -等が挙げられる。 In the above formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 43 — group, A —COOR 44 — group (where R 43 and R 44 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), and the like; Represents a —COO—R 44 — group.
In the formula (i), examples of the counter anion Y − include Cl − , Br − , I − , ClO 4 − , BF 4 − , CH 3 COO − , and PF 6 − .
　前記式（ｉ）で表される繰り返し単位の含有割合は特に限定されないが、分散性の観点から、前記式（ｉ）で表される繰り返し単位の含有割合と前記式（ｉｉ）で表される繰り返し単位の含有割合の合計に対して、好ましくは６０モル％以下であり、より好ましくは５０モル％以下であり、さらに好ましくは４０モル％以下であり、特に好ましくは３５モル％以下であり、また、好ましくは５モル％以上であり、より好ましくは１０モル％以上であり、さらに好ましくは２０モル％以上であり、特に好ましくは３０モル％以上である。例えば、前記式（ｉ）で表される繰り返し単位の含有割合と前記式（ｉｉ）で表される繰り返し単位の含有割合の合計に対する、前記式（ｉ）で表される繰り返し単位の含有割合５～６０モル％が好ましく、１０～５０モル％がより好ましく、２０～４０モル％がさらに好ましく、３０～３５モル％が特に好ましい。 The content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (i) is represented by the formula (ii). It is preferably at most 60 mol%, more preferably at most 50 mol%, further preferably at most 40 mol%, particularly preferably at most 35 mol%, based on the total content of the repeating units. Further, it is preferably at least 5 mol%, more preferably at least 10 mol%, further preferably at least 20 mol%, particularly preferably at least 30 mol%. For example, the content ratio of the repeating unit represented by the formula (i) 5 with respect to the sum of the content ratio of the repeating unit represented by the formula (i) and the content ratio of the repeating unit represented by the formula (ii) 5 ～ 60 mol% is preferable, 10-50 mol% is more preferable, 20-40 mol% is further preferable, and 30-35 mol% is particularly preferable.
　また、高分子分散剤の全繰り返し単位に占める前記式（ｉ）で表される繰り返し単位の含有割合は特に限定されないが、分散性の観点から、１モル％以上であることが好ましく、５モル％以上であることがより好ましく、１０モル％以上であることがさらに好ましく、また、５０モル％以下であることが好ましく、３０モル％以下であることがより好ましく、２０モル％以下であることがさらに好ましく、１５モル％以下であることが特に好ましい。例えば、高分子分散剤の全繰り返し単位に占める前記式（ｉ）で表される繰り返し単位の含有割合は１～５０モル％が好ましく、５～３０モル％がより好ましく、１０～２０モル％がさらに好ましく、１０～１５モル％が特に好ましい。 The content of the repeating unit represented by the formula (i) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and preferably 5 mol%, from the viewpoint of dispersibility. %, More preferably 10 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. Is more preferable, and it is particularly preferable that it is 15 mol% or less. For example, the content of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, and more preferably 10 to 20 mol%. More preferably, 10 to 15 mol% is particularly preferable.
　また、高分子分散剤の全繰り返し単位に占める前記式（ｉｉ）で表される繰り返し単位の含有割合は特に限定されないが、分散性の観点から、５モル％以上であることが好ましく、１０モル％以上であることがより好ましく、１５モル％以上であることがさらに好ましく、２０モル％以上であることが特に好ましく、また、６０モル％以下であることが好ましく、４０モル％以下であることがより好ましく、３０モル％以下であることがさらに好ましく、２５モル％以下であることが特に好ましい。例えば、高分子分散剤の全繰り返し単位に占める前記式（ｉｉ）で表される繰り返し単位の含有割合は５～６０モル％が好ましく、１０～４０モル％がより好ましく、１５～３０モル％がさらに好ましく、２０～２５モル％が特に好ましい。 The proportion of the repeating unit represented by the formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, and preferably 10 mol%, from the viewpoint of dispersibility. %, More preferably at least 15 mol%, particularly preferably at least 20 mol%, and preferably at most 60 mol%, and at most 40 mol%. Is more preferably 30 mol% or less, and particularly preferably 25 mol% or less. For example, the content of the repeating unit represented by the formula (ii) in all the repeating units of the polymer dispersant is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and more preferably 15 to 30 mol%. More preferably, it is particularly preferably 20 to 25 mol%.
　また、高分子分散剤は、溶媒等のバインダー成分に対する相溶性を高め、分散安定性を向上させるとの観点から、下記式（ｉｉｉ）で表される繰り返し単位（以下、「繰り返し単位（ｉｉｉ）」ということがある。）を有することが好ましい。 In addition, the polymer dispersant enhances the compatibility with a binder component such as a solvent and improves the dispersion stability, so that the repeating unit represented by the following formula (iii) (hereinafter referred to as “the repeating unit (iii)”) is used. Is sometimes referred to as ")."
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　上記式（ｉｉｉ）中、Ｒ40はエチレン基又はプロピレン基であり；
Ｒ41は置換基を有していてもよいアルキル基であり；
Ｒ42は水素原子又はメチル基であり；
ｎは１～２０の整数である。 In the above formula (iii), R 40 is an ethylene group or a propylene group;
R 41 is an optionally substituted alkyl group;
R 42 is a hydrogen atom or a methyl group;
n is an integer of 1 to 20.
　上記式（ｉｉｉ）のＲ41における、置換基を有していてもよいアルキル基の炭素数は特に限定されないが、１以上であって、２以上であることが好ましく、また、１０以下であることが好ましく、６以下であることがより好ましい。アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましい。また、直鎖状、分枝状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含んでもよい。例えば、アルキル基の炭素数は１～１０が好ましく、２～６がより好ましい。 The carbon number of the alkyl group which may have a substituent in R 41 of the formula (iii) is not particularly limited, but is preferably 1 or more, preferably 2 or more, and 10 or less. And more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Group, pentyl group or hexyl group, more preferably methyl group, ethyl group, propyl group or butyl group. Further, it may be linear or branched. Further, it may include a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group. For example, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
　また、上記式（ｉｉｉ）におけるｎは溶媒等バインダー成分に対する相溶性と分散性の観点から、１以上であって、２以上であることが好ましく、また、１０以下であることが好ましく、５以下であることがより好ましい。例えば、ｎとしては、１～１０が好ましく、２～５がより好ましい。 In the formula (iii), n is 1 or more, preferably 2 or more, more preferably 10 or less, and 5 or less from the viewpoint of compatibility and dispersibility with a binder component such as a solvent. Is more preferable. For example, n is preferably 1 to 10, more preferably 2 to 5.
　また、高分子分散剤の全繰り返し単位に占める前記式（ｉｉｉ）で表される繰り返し単位の含有割合は特に限定されないが、１モル％以上であることが好ましく、２モル％以上であることがより好ましく、４モル％以上であることがさらに好ましく、また、３０モル％以下であることが好ましく、２０モル％以下であることがより好ましく、１０モル％以下であることがさらに好ましい。前記範囲内の場合には溶媒等バインダー成分に対する相溶性と分散安定性の両立が可能となる傾向がある。例えば、高分子分散剤の全繰り返し単位に占める前記式（ｉｉｉ）で表される繰り返し単位の含有割合は１～３０モル％が好ましく、２～２０モル％がより好ましく、４～１０モル％がさらに好ましい。 The content of the repeating unit represented by the formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and more preferably 2 mol% or more. More preferably, it is 4 mol% or more, further preferably, 30 mol% or less, more preferably, 20 mol% or less, further preferably, 10 mol% or less. When the content is within the above range, compatibility with a binder component such as a solvent and dispersion stability tend to be compatible. For example, the content of the repeating unit represented by the formula (iii) in the total repeating units of the polymer dispersant is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and more preferably 4 to 10 mol%. More preferred.
　また、高分子分散剤は、分散剤の溶媒等バインダー成分に対する相溶性を高め、分散安定性を向上させるという観点から、下記式（ｉｖ）で表される繰り返し単位（以下、「繰り返し単位（ｉｖ）」ということがある。）を有することが好ましい。 From the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability, the polymer dispersant has a repeating unit represented by the following formula (iv) (hereinafter referred to as a “repeating unit (iv) ) ").)).
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　上記式（ｉｖ）中、Ｒ38は置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基であり；
Ｒ39は水素原子又はメチル基である。 In the above formula (iv), R 38 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent;
R 39 is a hydrogen atom or a methyl group.
　上記式（ｉｖ）のＲ38における、置換基を有していてもよいアルキル基の炭素数は特に限定されないが、１以上であって、２以上であることが好ましく、４以上であることがより好ましく、また、１０以下であることが好ましく、８以下であることがより好ましい。アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましい。また、直鎖状、分枝状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含んでもよい。例えば、アルキル基の炭素数は１～１０が好ましく、２～８がより好ましく、４～８がさらに好ましい。 The carbon number of the optionally substituted alkyl group in R 38 in the formula (iv) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 4 or more. More preferably, it is preferably 10 or less, more preferably 8 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. Group, pentyl group or hexyl group, more preferably methyl group, ethyl group, propyl group or butyl group. Further, it may be linear or branched. Further, it may include a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group. For example, the alkyl group preferably has 1 to 10 carbon atoms, more preferably has 2 to 8 carbon atoms, and still more preferably has 4 to 8 carbon atoms.
　上記式（ｉｖ）のＲ38における、置換基を有していてもよいアリール基の炭素数は特に限定されないが、通常６以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましく、８以下であることがさらに好ましい。アリール基の具体例としては、フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ナフチル基、アントラセニル基などが挙げられ、これらの中でもフェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、又はジエチルフェニル基であることが好ましく、フェニル基、メチルフェニル基、又はエチルフェニル基であることがより好ましい。例えば、アリール基の炭素数は６～１６が好ましく、６～１２がより好ましく、８～１２がさらに好ましい。 The carbon number of the aryl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. More preferably, it is even more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Of these, a phenyl group, a methylphenyl group, an ethylphenyl group , A dimethylphenyl group or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group. For example, the aryl group preferably has 6 to 16 carbon atoms, more preferably has 6 to 12 carbon atoms, and still more preferably has 8 to 12 carbon atoms.
　上記式（ｉｖ）のＲ38における、置換基を有していてもよいアラルキル基の炭素数は特に限定されないが、通常７以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましく、１０以下であることがさらに好ましい。アラルキル基の具体例としては、フェニルメチル基（ベンジル基）、フェニルエチル基（フェネチル基）、フェニルプロピル基、フェニルブチル基、フェニルイソプロピル基などが挙げられ、これらの中でも、フェニルメチル基、フェニルエチル基、フェニルプロピル基、又はフェニルブチル基であることが好ましく、フェニルメチル基、又はフェニルエチル基であることがより好ましい。例えば、アラルキル基の炭素数は、７～１６が好ましく、７～１２がより好ましく、７～１０がさらに好ましい。 The carbon number of the aralkyl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. More preferably, it is even more preferably 10 or less. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. A phenylpropyl group or a phenylbutyl group, and more preferably a phenylmethyl group or a phenylethyl group. For example, the carbon number of the aralkyl group is preferably 7 to 16, more preferably 7 to 12, and even more preferably 7 to 10.
　これらの中でも、溶剤相溶性と分散安定性の観点から、Ｒ38がアルキル基、又はアラルキル基であることが好ましく、メチル基、エチル基、又はフェニルメチル基であることがより好ましい。
　Ｒ38における、アルキル基が有していてもよい置換基としては、ハロゲン原子、アルコキシ基等が挙げられる。また、アリール基又はアラルキル基が有していてもよい置換基としては、鎖状のアルキル基、ハロゲン原子、アルコキシ基等が挙げられる。また、Ｒ38で示される鎖状のアルキル基には、直鎖状及び分岐鎖状のいずれも含まれる。 Among them, R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethyl group, from the viewpoint of solvent compatibility and dispersion stability.
Examples of the substituent which the alkyl group may have in R 38 include a halogen atom and an alkoxy group. Examples of the substituent which the aryl group or the aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. Further, in the chain of the alkyl group represented by R 38, include any of linear and branched.
　また、高分子分散剤の全繰り返し単位に占める前記式（ｉｖ）で表される繰り返し単位の含有割合は、分散性の観点から、３０モル％以上であることが好ましく、４０モル％以上であることがより好ましく、５０モル％以上であることがさらに好ましく、また、８０モル％以下であることが好ましく、７０モル％以下であることがより好ましい。例えば、高分子分散剤の全繰り返し単位に占める前記式（ｉｖ）で表される繰り返し単位の含有割合は３０～８０モル％が好ましく、４０～７０モル％がより好ましく、５０～７０モル％がさらに好ましい。 From the viewpoint of dispersibility, the content of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, and more preferably 40 mol% or more. Is more preferably 50 mol% or more, further preferably 80 mol% or less, more preferably 70 mol% or less. For example, the content of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and more preferably 50 to 70 mol%. More preferred.
　高分子分散剤は、繰り返し単位（ｉ）、繰り返し単位（ｉｉ）、繰り返し単位（ｉｉｉ）及び繰り返し単位（ｉｖ）以外の繰り返し単位を有していてもよい。そのような繰り返し単位の例としては、スチレン、α－メチルスチレンなどのスチレン系単量体；（メタ）アクリル酸クロリドなどの（メタ）アクリル酸塩系単量体；（メタ）アクリルアミド、Ｎ－メチロールアクリルアミドなどの（メタ）アクリルアミド系単量体；酢酸ビニル；アクリロニトリル；アリルグリシジルエーテル、クロトン酸グリシジルエーテル；Ｎ－メタクリロイルモルホリン等の単量体に由来する繰り返し単位が挙げられる。 The polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii), and the repeating unit (iv). Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide; (Meth) acrylamide monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl ether crotonic acid; and repeating units derived from monomers such as N-methacryloylmorpholine.
　高分子分散剤は、分散性をより高めるとの観点から、繰り返し単位（ｉ）及び繰り返し単位（ｉｉ）を有するＡブロックと、繰り返し単位（ｉ）及び繰り返し単位（ｉｉ）を有さないＢブロックとを有する、ブロック共重合体であることが好ましい。該ブロック共重合体は、Ａ－Ｂブロック共重合体又はＢ－Ａ－Ｂブロック共重合体であることが好ましい。Ａブロックに４級アンモニウム塩基だけでなく３級アミノ基も導入することにより、意外にも、分散剤の分散能力が著しく向上する傾向がある。また、Ｂブロックが繰り返し単位（ｉｉｉ）を有することが好ましく、さらに繰り返し単位（ｉｖ）を有することがより好ましい。 From the viewpoint of further improving dispersibility, the polymer dispersant has an A block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and a repeating unit (ii). And a block copolymer having: The block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, unexpectedly, the dispersing ability of the dispersant tends to be significantly improved. The B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).
　Ａブロック中において、繰り返し単位（ｉ）及び繰り返し単位（ｉｉ）は、ランダム共重合、ブロック共重合のいずれの態様で含有されていてもよい。また、繰り返し単位（ｉ）及び繰り返し単位（ｉｉ）は、１つのＡブロック中に各々２種以上含有されていてもよく、その場合、各々の繰り返し単位は、該Ａブロック中においてランダム共重合、ブロック共重合のいずれの態様で含有されていてもよい。 In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any mode of random copolymerization and block copolymerization. Further, the repeating unit (i) and the repeating unit (ii) may each be contained in the A block in two or more types. In this case, each of the repeating units may be randomly copolymerized in the A block. It may be contained in any form of block copolymerization.
　また、繰り返し単位（ｉ）及び繰り返し単位（ｉｉ）以外の繰り返し単位が、Ａブロック中に含有されていてもよく、そのような繰り返し単位の例としては、前述の（メタ）アクリル酸エステル系単量体由来の繰り返し単位等が挙げられる。繰り返し単位（ｉ）及び繰り返し単位（ｉｉ）以外の繰り返し単位の、Ａブロック中の含有量は、好ましくは０～５０モル％、より好ましくは０～２０モル％であるが、かかる繰り返し単位はＡブロック中に含有されないことが最も好ましい。 Further, a repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block. Examples of such a repeating unit include the above-mentioned (meth) acrylate ester-based unit. And repeating units derived from monomers. The content of the repeating unit other than the repeating unit (i) and the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, it is not contained in the block.
　繰り返し単位（ｉｉｉ）及び（ｉｖ）以外の繰り返し単位がＢブロック中に含有されていてもよく、そのような繰り返し単位の例としては、スチレン、α－メチルスチレンなどのスチレン系単量体；（メタ）アクリル酸クロリドなどの（メタ）アクリル酸塩系単量体；（メタ）アクリルアミド、Ｎ－メチロールアクリルアミドなどの（メタ）アクリルアミド系単量体；酢酸ビニル；アクリロニトリル；アリルグリシジルエーテル、クロトン酸グリシジルエーテル；Ｎ－メタクリロイルモルホリン等の単量体に由来する繰り返し単位が挙げられる。繰り返し単位（ｉｉｉ）及び繰り返し単位（ｉｖ）以外の繰り返し単位の、Ｂブロック中の含有量は、好ましくは０～５０モル％、より好ましくは０～２０モル％であるが、かかる繰り返し単位はＢブロック中に含有されないことが最も好ましい。 A repeating unit other than the repeating units (iii) and (iv) may be contained in the B block, and examples of such a repeating unit include styrene monomers such as styrene and α-methylstyrene; (Meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; glycidyl crotonate Ether; a repeating unit derived from a monomer such as N-methacryloylmorpholine. The content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, it is not contained in the block.
　本発明の感光性着色樹脂組成物が（Ｆ）分散剤を含有する場合、その含有割合は特に限定されないが、感光性着色樹脂組成物の全固形分中に、０．１質量％以上が好ましく、０．５質量％以上がより好ましく、また、８質量％以下が好ましく、５質量％以下がより好ましく、３質量％以下がさらに好ましく、２質量％以下が特に好ましい。前記下限値以上とすることで凝集物による残渣発生を抑制できる傾向があり、また、前記上限値以下とすることで撥インク性や現像性が向上する傾向がある。例えば、感光性着色樹脂組成物が（Ｆ）分散剤を含有する場合、感光性着色樹脂組成物の全固形分中の（Ｆ）分散剤の含有割合は０．１～８質量％が好ましく、０．１～５質量％がより好ましく、０．５～３質量％がさらに好ましく、０．５～２質量％が特に好ましい。 When the photosensitive colored resin composition of the present invention contains (F) a dispersant, the content thereof is not particularly limited, but is preferably 0.1% by mass or more in the total solid content of the photosensitive colored resin composition. , 0.5% by mass or more, more preferably 8% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, particularly preferably 2% by mass or less. When the content is not less than the lower limit, the generation of residues due to aggregates tends to be suppressed, and when the content is not more than the upper limit, ink repellency and developability tend to be improved. For example, when the photosensitive colored resin composition contains the (F) dispersant, the content of the (F) dispersant in the total solid content of the photosensitive colored resin composition is preferably 0.1 to 8% by mass, 0.1 to 5% by mass is more preferable, 0.5 to 3% by mass is more preferable, and 0.5 to 2% by mass is particularly preferable.
［１－１－７］紫外線吸収剤
　本発明の感光性着色樹脂組成物は、紫外線吸収剤を含有してもよい。紫外線吸収剤は、露光に用いられる光源の特定の波長を紫外線吸収剤によって吸収させることにより、光硬化分布を制御する目的で添加されるものである。紫外線吸収剤の添加により、現像後の隔壁側面の垂直性を改善したり、現像後に非露光部に残る残渣をなくしたりするなどの効果が得られる。紫外線吸収剤としては、（Ａ）光重合開始剤の光吸収の阻害の観点から、例えば、波長２５０ｎｍから４００ｎｍの間に吸収極大を有する化合物を用いることができる。
　紫外線吸収剤としては、ベンゾトリアゾール系化合物及びトリアジン系化合物のいずれか一方又は両方を含むことが望ましい。ベンゾトリアゾール系化合物及びトリアジン系化合物のいずれか一方又は両方を含むことで開始剤の膜底部での光吸収率が減少し、塗膜下部の線幅が小さくなることにより隔壁側面の垂直性効果が得られると考えられる。 [1-1-7] Ultraviolet absorber The photosensitive colored resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the photo-curing distribution by absorbing a specific wavelength of a light source used for exposure with the ultraviolet absorber. By the addition of the ultraviolet absorber, effects such as improving the perpendicularity of the side wall of the partition wall after development and eliminating residues remaining in the non-exposed area after development are obtained. As the ultraviolet absorber, for example, a compound having an absorption maximum between a wavelength of 250 nm and 400 nm can be used from the viewpoint of inhibiting the light absorption of the photopolymerization initiator (A).
The ultraviolet absorber desirably contains one or both of a benzotriazole-based compound and a triazine-based compound. By including one or both of the benzotriazole-based compound and the triazine-based compound, the light absorption at the bottom of the film of the initiator is reduced, and the line width at the bottom of the coating film is reduced, so that the vertical effect on the side wall of the partition is reduced. It is thought that it can be obtained.
　ベンゾトリアゾール系化合物としては、２－（５メチル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ｔ－ブチルフェニル）－２Ｈ－ベンゾトリアゾール、３－［３－ｔｅｒｔ－ブチル－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）－４－ヒドロキシフェニル］プロピオン酸オクチル、３－［３－ｔｅｒｔ－ブチル－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）－４－ヒドロキシフェニル］プロピオン酸エチルヘキシル、２－［２－ヒドロキシ－３，５－ビス（α，α－ジメチルベンジル）フェニル］－２Ｈ－ベンゾトリアゾール、２－（３－ｔブチル－５－メチル－２－ヒドロキシフェニル）－５－クロロベンゾトリアゾール、２－（３，５－ジ－ｔ－アミル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔ－オクチルフェニル）ベンゾトリアゾール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－（１－メチル－１－フェニルエチル）－４－（１，１，３，３－テトラメチルブチル）フェノール、３－［３－ｔｅｒｔ－ブチル－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）－４－ヒドロキシフェニル］プロピオン酸とＣ７－９直鎖及び分岐アルキルアルコールのエステル化合物が挙げられる。 Benzotriazole compounds include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and 3- [3-tert-butyl- Octyl 5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) ) -4-Hydroxyphenyl] ethylhexyl propionate, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-tbutyl-5-methyl -2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxy) (Ciphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenyl) Ethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 3- [ Ester compounds of 3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and C7-9 linear and branched alkyl alcohols.
　市販されているベンゾトリアゾール系化合物としては例えば、スミソーブ（登録商標、以下同じ。）２００、スミソーブ２５０、スミソーブ３００、スミソーブ３４０、スミソーブ３５０（住友化学製）、ＪＦ７７、ＪＦ７８、ＪＦ７９、ＪＦ８０、ＪＦ８３（城北化学工業製）、ＴＩＮＵＶＩＮ（登録商標、以下同じ。）　ＰＳ、ＴＩＮＵＶＩＮ９９－２、ＴＩＮＵＶＩＮ１０９、ＴＩＮＵＶＩＮ３８４－２、ＴＩＮＵＶＩＮ　３２６、ＴＩＮＵＶＩＮ９００、「ＴＩＮＵＶＩＮ　９２８」、ＴＩＮＵＶＩＮ９２８、ＴＩＮＵＶＩＮ１１３０（ＢＡＳＦ製）、ＥＶＥＲＳＯＲＢ７０、ＥＶＥＲＳＯＲＢ７１、ＥＶＥＲＳＯＲＢ７２、ＥＶＥＲＳＯＲＢ７３、ＥＶＥＲＳＯＲＢ７４、ＥＶＥＲＳＯＲＢ７５、ＥＶＥＲＳＯＲＢ７６、ＥＶＥＲＳＯＲＢ２３４、ＥＶＥＲＳＯＲＢ７７、ＥＶＥＲＳＯＲＢ７８、ＥＶＥＲＳＯＲＢ８０、ＥＶＥＲＳＯＲＢ８１（台湾永光化学工業製）、トミソーブ（登録商標、以下同じ。）１００、トミソーブ６００（エーピーアイコーポレーション製）、ＳＥＥＳＯＲＢ（登録商標、以下同じ。）７０１、ＳＥＥＳＯＲＢ７０２、ＳＥＥＳＯＲＢ７０３、ＳＥＥＳＯＲＢ７０４、ＳＥＥＳＯＲＢ７０６、ＳＥＥＳＯＲＢ７０７、ＳＥＥＳＯＲＢ７０９（シプロ化成製）、ＲＵＶＡ－９３（大塚化学株式会社）などが挙げられる。 Examples of commercially available benzotriazole-based compounds include, for example, Sumisorb (registered trademark, the same applies hereinafter) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 ( JINHOKU INDUSTRIES), TINUVIN (registered trademark, the same applies hereinafter) @PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN @ 326, TINUVIN900, "TINUVIN @ 928", TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSOVER70BVER, 72VERVER , EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVE SORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Eiko Chemical Co., Ltd.), TOMISORB (registered trademark, the same applies hereinafter) 100, TOMISORB 600 (manufactured by API Corporation), SEESORB (registered trademark, the same applies hereinafter) 701, SEESORB702 SEESORB 703, SEESORB 704, SEESORB 706, SEESORB 707, SEESORB 709 (manufactured by Cipro Kasei), RUVA-93 (Otsuka Chemical Co., Ltd.) and the like.
　トリアジン系化合物としては、２－［４，６－ジ（２，４－キシリル）－１，３，５－トリアジン－２－イル］－５－オクチルオキシフェノール、２－［４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル］－５－［３－（ドデシルオキシ）－２－ヒドロキシプロポキシ］フェノール、２－（２，４－ジヒドロキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジンと２－エチルヘキシルグリシジルエーテルの反応生成物、２，４－ビス［２－ヒドロキシ－４－ブトキシフェニル］－６－（２，４－ジブトキシフェニル）－１，３－５－トリアジン等が挙げられる。これらの中でも、隔壁側面の垂直性と撥インク性の観点から、ヒドロキシフェニルトリアジン化合物が好ましい。
　市販されているトリアジン系化合物としては例えば、ＴＩＮＵＶＩＮ４００、ＴＩＮＵＶＩＮ４０５、ＴＩＮＵＶＩＮ４６０、ＴＩＮＵＶＩＮ４７７、ＴＩＮＵＶＩＮ４７９（ＢＡＳＦ製）などを挙げることができる。 Examples of triazine compounds include 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol and 2- [4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) -4 Reaction product of 2,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2-ethylhexyl glycidyl ether; 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- ( 2,4-dibutoxyphenyl) -1,3-5-triazine and the like. Among these, a hydroxyphenyltriazine compound is preferable from the viewpoint of the verticality of the partition wall side surface and the ink repellency.
Examples of commercially available triazine-based compounds include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (manufactured by BASF).
　その他の紫外線吸収剤としては、ベンゾフェノン化合物、ベンゾエート化合物、桂皮酸誘導体、ナフタレン誘導体、アントラセン及びその誘導体、ジナフタレン化合物、フェナントロリン化合物、染料等が挙げられる。
　より具体的には、例えば、スミソーブ１３０（住友化学製）、ＥＶＥＲＳＯＲＢ１０、ＥＶＥＲＳＯＲＢ１１、ＥＶＥＲＳＯＲＢ１２（台湾永光化学工業製）、トミソーブ８００（エーピーアイコーポレーション製）、ＳＥＥＳＯＲＢ１００、ＳＥＥＳＯＲＢ１０１、ＳＥＥＳＯＲＢ１０１Ｓ、ＳＥＥＳＯＲＢ１０２、ＳＥＥＳＯＲＢ１０３、ＳＥＥＳＯＲＢ１０５、ＳＥＥＳＯＲＢ１０６、ＳＥＥＳＯＲＢ１０７、ＳＥＥＳＯＲＢ１５１（シプロ化成製）などのベンゾフェノン化合物；スミソーブ４００（住友化学製）、サリチル酸フェニルなどのベンゾエート化合物；桂皮酸２－エチルヘキシル、パラメトキシ桂皮酸２－エチルヘキシル、メトキシケイ皮酸イソプロピル、メトキシケイ皮酸イソアミル等の桂皮酸誘導体；α－ナフトール、β－ナフトール、α－ナフトールメチルエーテル、α－ナフトールエチルエーテル、１，２－ジヒドロキシナフタレン、１，３－ジヒドロキシナフタレン、１，４－ジヒドロキシナフタレン、１，５－ジヒドロキシナフタレン、１，６－ジヒドロキシナフタレン、１，７－ジヒドロキシナフタレン、１，８－ジヒドロキシナフタレン、２，３－ジヒドロキシナフタレン、２，６－ジヒドロキシナフタレン、２，７－ジヒドロキシナフタレン等のナフタレン誘導体；アントラセン、９，１０－ジヒドロキシアントラセン等のアントラセン及びその誘導体；アゾ系染料、ベンゾフェノン系染料、アミノケトン系染料、キノリン系染料、アントラキノン系染料、ジフェニルシアノアクリレート系染料、トリアジン系染料、ｐ－アミノ安息香酸系染料等の染料；等が挙げられる。これらの中でも、撥インク性の観点から、桂皮酸誘導体、ナフタレン誘導体を用いることが好ましく、桂皮酸誘導体を用いることが特に好ましい。これらの光吸収剤は、単独又は２種以上組み合わせて用いることができる。 Other ultraviolet absorbers include benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, dyes and the like.
More specifically, for example, Sumisorb 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eiko Chemical Co., Ltd.), Tomissorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB103, SESEORB103, SESEORB103, SESEORB103 Benzophenone compounds such as SEESORB106, SEESORB107 and SEESORB151 (manufactured by Cipro Kasei); benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical) and phenyl salicylate; 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate and methoxy methoxycinnamate Cinnamic acid derivatives such as isoamyl cinnamate; α-naphthol β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene And naphthalene derivatives such as 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; and anthracene and 9,10-dihydroxyanthracene. Anthracene and its derivatives; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, etc. Dyes; and the like. Among these, from the viewpoint of ink repellency, it is preferable to use cinnamic acid derivatives and naphthalene derivatives, and it is particularly preferable to use cinnamic acid derivatives. These light absorbers can be used alone or in combination of two or more.
　これらの中でも、テーパ形状の観点から、ベンゾトリアゾール化合物及びヒドロキシフェニルトリアジン化合物のいずれか一方又は両方が好ましく、ベンゾトリアゾール化合物が特に好ましい。 中 で も Among these, from the viewpoint of the tapered shape, one or both of a benzotriazole compound and a hydroxyphenyltriazine compound are preferable, and a benzotriazole compound is particularly preferable.
　紫外線吸収剤としては１種類の化合物を単独で用いてもよいし、２種類以上の化合物を併用してもよい。 As the ultraviolet absorber, one compound may be used alone, or two or more compounds may be used in combination.
　本発明の感光性着色樹脂組成物が紫外線吸収剤を含有する場合、その含有割合は特に限定されないが、感光性着色樹脂組成物の全固形分中に、通常０．０１質量％以上、好ましくは０．０５質量％以上、より好ましくは０．１質量％以上、さらに好ましくは０．５質量％以上、特に好ましくは１質量％以上であり、また、通常１５質量％以下、好ましくは１０質量％以下、より好ましくは５質量％以下、さらに好ましくは３質量％以下である。前記下限値以上とすることで隔壁側面の垂直性が良好となる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。例えば、感光性着色樹脂組成物が紫外線吸収剤を含有する場合、感光性着色樹脂組成物の全固形分中の紫外線吸収剤の含有割合は０．０１～１５質量％が好ましく、０．０５～１０質量％がより好ましく、０．１～５質量％がさらに好ましく、０．５～３質量％がよりさらに好ましく、１～３質量％が特に好ましい。 When the photosensitive colored resin composition of the present invention contains an ultraviolet absorber, the content ratio is not particularly limited, but is usually 0.01% by mass or more, preferably 0.01% by mass or more in the total solid content of the photosensitive colored resin composition. 0.05 mass% or more, more preferably 0.1 mass% or more, further preferably 0.5 mass% or more, particularly preferably 1 mass% or more, and usually 15 mass% or less, preferably 10 mass%. Or less, more preferably 5% by mass or less, still more preferably 3% by mass or less. When the ratio is equal to or more than the lower limit, the verticality of the side wall of the partition tends to be good, and when the ratio is equal to or less than the upper limit, the ink repellency tends to increase. For example, when the photosensitive colored resin composition contains an ultraviolet absorbent, the content ratio of the ultraviolet absorbent in the total solid content of the photosensitive colored resin composition is preferably 0.01 to 15% by mass, and 0.05 to 15% by mass. 10% by mass is more preferable, 0.1 to 5% by mass is more preferable, 0.5 to 3% by mass is further preferable, and 1 to 3% by mass is particularly preferable.
　また、本発明の感光性着色樹脂組成物が紫外線吸収剤を含有する場合、（Ａ）光重合開始剤に対する配合比としては、（Ａ）光重合開始剤１００質量部に対する紫外線吸収剤の配合量として、通常１質量部以上、好ましくは１０質量部以上、より好ましくは３０質量部以上、さらに好ましくは５０質量部以上であり、特に好ましくは８０質量部以上、通常５００質量部以下、好ましくは３００質量部以下、より好ましくは２００質量部以下、さらに好ましくは１００質量部以下である。前記下限値以上とすることで隔壁側面の垂直性が良好となる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。本発明の感光性着色樹脂組成物が紫外線吸収剤を含有する場合、（Ａ）光重合開始剤１００質量部に対する紫外線吸収剤の配合量として１～５００質量部が好ましく、１０～３００質量部がより好ましく、３０～２００質量部がさらに好ましく、５０～１００質量部がよりさらに好ましく、８０～１００質量部が特に好ましい。 When the photosensitive colored resin composition of the present invention contains an ultraviolet absorber, the compounding ratio of (A) the photopolymerization initiator is as follows: (A) the compounding amount of the ultraviolet absorber to 100 parts by mass of the photopolymerization initiator. Is usually at least 1 part by mass, preferably at least 10 parts by mass, more preferably at least 30 parts by mass, even more preferably at least 50 parts by mass, particularly preferably at least 80 parts by mass, usually at most 500 parts by mass, preferably at most 300 parts by mass. It is at most 200 parts by mass, more preferably at most 100 parts by mass, even more preferably at most 100 parts by mass. When the ratio is equal to or more than the lower limit, the verticality of the side wall of the partition tends to be good, and when the ratio is equal to or less than the upper limit, the ink repellency tends to increase. When the photosensitive colored resin composition of the present invention contains an ultraviolet absorber, the amount of the ultraviolet absorber is preferably from 1 to 500 parts by mass, more preferably from 10 to 300 parts by mass, per 100 parts by mass of the photopolymerization initiator (A). It is more preferably 30 to 200 parts by mass, further preferably 50 to 100 parts by mass, and particularly preferably 80 to 100 parts by mass.
［１－１－８］重合禁止剤
　本発明の感光性着色樹脂組成物は、重合禁止剤を含有することが好ましい。重合禁止剤を含有することでそれがラジカル重合を阻害することから、得られる隔壁のテーパ角を大きくすることができる傾向がある。
　重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノン、メトキシフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－クレゾール（ＢＨＴ）などが挙げられる。これらの中でも重合禁止能力の観点から、ハイドロキノン又はメトキシフェノールが好ましく、メチルハイドロキノンがより好ましい。 [1-1-8] Polymerization Inhibitor The photosensitive colored resin composition of the present invention preferably contains a polymerization inhibitor. By containing a polymerization inhibitor, it inhibits radical polymerization, so that the taper angle of the obtained partition tends to be able to be increased.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, hydroquinone or methoxyphenol is preferred from the viewpoint of polymerization inhibition ability, and methylhydroquinone is more preferred.
　重合禁止剤は、１種又は２種以上を含有することが好ましい。通常、（Ｂ）アルカリ可溶性樹脂を製造する際に、当該樹脂中に重合禁止剤が含まれることがあり、そのまま用いてもよいし、樹脂中に含まれる重合禁止剤の他に、それと同一、又は異なる重合禁止剤を感光性着色樹脂組成物製造時に添加してもよい。 The polymerization inhibitor preferably contains one or more kinds. Usually, when producing the alkali-soluble resin (B), the polymerization inhibitor may be contained in the resin, and may be used as it is, or may be the same as the polymerization inhibitor contained in the resin. Alternatively, a different polymerization inhibitor may be added during the production of the photosensitive colored resin composition.
　感光性着色樹脂組成物が重合禁止剤を含有する場合、その含有割合は特に限定されないが、感光性着色樹脂組成物の全固形分中に、通常０．０００５質量％以上、好ましくは０．００１質量％以上、より好ましくは０．０１質量％以上であり、また通常０．１質量％以下、好ましくは０．０８質量％以下、より好ましくは０．０５質量％以下である。前記下限値以上とすることでテーパ角を高くすることができる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。例えば、感光性着色樹脂組成物が重合禁止剤を含有する場合、感光性着色樹脂組成物の全固形分中の重合禁止剤の含有割合は０．０００５質量～０．１％が好ましく、０．００１～０．０８質量％がより好ましく、０．０１～０．０５質量％がさらに好ましい。 When the photosensitive colored resin composition contains a polymerization inhibitor, its content is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass, in the total solid content of the photosensitive colored resin composition. It is at least 0.01% by mass, more preferably at least 0.01% by mass, and usually at most 0.1% by mass, preferably at most 0.08% by mass, more preferably at most 0.05% by mass. When the value is not less than the lower limit, the taper angle tends to be increased, and when the value is not more than the upper limit, the ink repellency tends to be high. For example, when the photosensitive colored resin composition contains a polymerization inhibitor, the content ratio of the polymerization inhibitor in the total solid content of the photosensitive colored resin composition is preferably 0.0005% by mass to 0.1%, more preferably 0.1% by mass. 001 to 0.08% by mass is more preferable, and 0.01 to 0.05% by mass is more preferable.
［１－１－９］熱重合開始剤
　さらに、本発明の感光性着色樹脂組成物には、熱重合開始剤が含有されていてもよい。熱重合開始剤を含有することで、膜の架橋度を高くできる傾向がある。このような熱重合開始剤の具体例としては、例えば、アゾ系化合物、有機過酸化物および過酸化水素などが挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 [1-1-9] Thermal polymerization initiator Further, the photosensitive colored resin composition of the present invention may contain a thermal polymerization initiator. By containing a thermal polymerization initiator, the degree of crosslinking of the film tends to be increased. Specific examples of such a thermal polymerization initiator include, for example, an azo compound, an organic peroxide, and hydrogen peroxide. These may be used alone or in combination of two or more.
　なお、光重合開始剤に撥インク性の向上や膜の架橋密度の増大を期待して熱重合開始剤を併用する場合、これらの含有割合の合計が、感光性着色樹脂組成物中の光重合開始剤の含有割合となるようにすることが好ましく、また、光重合開始剤と熱重合開始剤との併用割合としては、撥インク性の観点から、光重合開始剤１００質量部に対して熱重合開始剤を５～３００質量部とすることが好ましい。 When a thermal polymerization initiator is used in combination with the photopolymerization initiator in the hope of improving the ink repellency and increasing the crosslink density of the film, the sum of the content ratios of the photopolymerization initiators in the photosensitive colored resin composition The content ratio of the initiator is preferably set to be the same as the content ratio of the photopolymerization initiator, and the combined use ratio of the photopolymerization initiator and the thermal polymerization initiator is determined based on 100 parts by mass of the photopolymerization initiator from the viewpoint of ink repellency. The polymerization initiator is preferably used in an amount of 5 to 300 parts by mass.
［１－１－１０］アミノ化合物
　本発明の感光性着色樹脂組成物には、熱硬化を促進するためにアミノ化合物が含まれていてもよい。この場合、アミノ化合物の含有割合としては、感光性着色樹脂組成物の全固形分中に、通常４０質量％以下、好ましくは３０質量％以下である。また、通常０．５質量％以上、好ましくは１質量％以上である。前記上限値以下とすることで保存安定性を維持できる傾向があり、前記下限値以上とすることで十分な熱硬化性を確保できる傾向がある。例えば、感光性着色樹脂組成物がアミノ化合物を含有する場合、感光性着色樹脂組成物の全固形分中の含有割合は、０．５～４０質量％が好ましく、１～３０質量％がより好ましい。 [1-1-10] Amino compound The photosensitive colored resin composition of the present invention may contain an amino compound for accelerating thermosetting. In this case, the content ratio of the amino compound is usually 40% by mass or less, preferably 30% by mass or less in the total solid content of the photosensitive colored resin composition. Further, it is usually 0.5% by mass or more, preferably 1% by mass or more. When the content is equal to or less than the upper limit, storage stability tends to be maintained, and when the content is equal to or more than the lower limit, sufficient thermosetting property tends to be secured. For example, when the photosensitive colored resin composition contains an amino compound, the content of the photosensitive colored resin composition in the total solid content is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass. .
　アミノ化合物としては、例えば、官能基としてメチロール基、それを炭素数１～８のアルコール縮合変性したアルコキシメチル基を少なくとも２個有するアミノ化合物が挙げられる。具体的には、例えば、メラミンとホルムアルデヒドとを重縮合させたメラミン樹脂；ベンゾグアナミンとホルムアルデヒドとを重縮合させたベンゾグアナミン樹脂；グリコールウリルとホルムアルデヒドとを重縮合させたグリコールウリル樹脂；尿素とホルムアルデヒドとを重縮合させた尿素樹脂；メラミン、ベンゾグアナミン、グリコールウリル、または尿素などの２種以上とホルムアルデヒドとを共重縮合させた樹脂；上述の樹脂のメチロール基をアルコール縮合変性した変性樹脂などが挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。アミノ化合物としては中でも、メラミン樹脂およびその変性樹脂が好ましく、メチロール基の変性割合が、７０％以上の変性樹脂が更に好ましく、８０％以上の変性樹脂が特に好ましい。 Examples of the amino compound include, for example, an amino compound having a methylol group as a functional group and at least two alkoxymethyl groups obtained by subjecting it to alcohol condensation with 1 to 8 carbon atoms. Specifically, for example, melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; urea and formaldehyde Polycondensed urea resins; resins obtained by copolycondensation of two or more kinds of melamine, benzoguanamine, glycoluril or urea with formaldehyde; and modified resins obtained by subjecting the above-mentioned resin to alcohol condensation modification of a methylol group. These may be used alone or in combination of two or more. Among the amino compounds, a melamine resin and a modified resin thereof are preferable, a modified resin having a methylol group modification ratio of 70% or more is more preferable, and a modified resin of 80% or more is particularly preferable.
　上記アミノ化合物の具体例として、メラミン樹脂およびその変性樹脂としては、例えば、サイテック社製の「サイメル」（登録商標、以下同じ。）３００、３０１、３０３、３５０、７３６、７３８、３７０、７７１、３２５、３２７、７０３、７０１、２６６、２６７、２８５、２３２、２３５、２３８、１１４１、２７２、２５４、２０２、１１５６、１１５８、および、三和ケミカル社製の「ニカラック」（登録商標、以下同じ。）ＭＷ－３９０、ＭＷ－１００ＬＭ、ＭＸ－７５０ＬＭ、ＭＷ－３０Ｍ、ＭＸ－４５、ＭＸ－３０２などが挙げられる。また、上記ベンゾグアナミン樹脂およびその変性樹脂としては、例えば、サイテック社製の「サイメル」１１２３、１１２５、１１２８などが挙げられる。また、上記グリコールウリル樹脂およびその変性樹脂としては、例えば、サイテック社製の「サイメル」１１７０、１１７１、１１７４、１１７２、および、三和ケミカル社製の「ニカラック」ＭＸ－２７０などが挙げられる。また、上記尿素樹脂およびその変性樹脂としては、例えば、サイテック社製の「ＵＦＲ」（登録商標）６５、３００、および、三和ケミカル社製の「ニカラック」ＭＸ－２９０などが挙げられる。 As specific examples of the amino compound, melamine resins and modified resins thereof include, for example, “Symel” (registered trademark, the same applies hereinafter) 300, 301, 303, 350, 736, 738, 370, 771, manufactured by Cytec Corporation. 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "Nikarac" (registered trademark, the same hereinafter) manufactured by Sanwa Chemical Co., Ltd. ) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302 and the like. Examples of the benzoguanamine resin and its modified resin include “CYMEL” 1123, 1125, and 1128 manufactured by Cytec Corporation. Examples of the glycoluril resin and its modified resin include “Symel” 1170, 1171, 1174, and 1172 manufactured by Cytec, and “Nikalac” MX-270 manufactured by Sanwa Chemical Co., Ltd. Examples of the urea resin and its modified resin include “UFR” (registered trademark) 65, 300 manufactured by Scitech, and “Nikalac” MX-290 manufactured by Sanwa Chemical Co., Ltd.
［１－１－１１］シランカップリング剤
　本発明の感光性着色樹脂組成物には、基板との密着性を改善するため、シランカップリング剤を添加することも好ましい。シランカップリング剤の種類としては、エポキシ系、メタクリル系、アミノ系、イミダゾール系など種々の物が使用できるが、密着性向上の観点から、特にエポキシ系、イミダゾール系のシランカップリング剤が好ましい。その含有量は、密着性の観点から、感光性着色樹脂組成物の全固形分中に、通常２０質量％以下、好ましくは１５質量％以下である。 [1-1-11] Silane Coupling Agent It is also preferable to add a silane coupling agent to the photosensitive colored resin composition of the present invention in order to improve adhesion to a substrate. As the type of the silane coupling agent, various types such as an epoxy type, a methacrylic type, an amino type, and an imidazole type can be used. From the viewpoint of improving the adhesion, an epoxy type or imidazole type silane coupling agent is particularly preferable. The content thereof is usually 20% by mass or less, preferably 15% by mass or less in the total solid content of the photosensitive colored resin composition from the viewpoint of adhesion.
［１－１－１２］無機充填剤
　また、本発明の感光性着色樹脂組成物は、さらに、硬化物としての強度の向上と共に、アルカリ可溶性樹脂との適度な相互作用（マトリックス構造の形成）による塗布膜の優れた垂直性とテーパ角の向上等を目的として、無機充填剤を含有していてもよい。そのような無機充填剤としては、例えば、タルク、シリカ、アルミナ、硫酸バリウム、酸化マグネシウム、酸化チタン、或いは、これらを各種シランカップリング剤により表面処理したものなどが挙げられる。 [1-1-12] Inorganic Filler The photosensitive colored resin composition of the present invention is further improved in strength as a cured product, and has an appropriate interaction with an alkali-soluble resin (formation of a matrix structure). For the purpose of improving the perpendicularity and the taper angle of the coating film, an inorganic filler may be contained. Examples of such an inorganic filler include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, and those obtained by treating these with various silane coupling agents.
　これら無機充填剤の平均粒子径としては、通常０．００５～２μｍ、好ましくは０．０１～１μｍである。ここで本実施の形態にいう平均粒子径とは、ベックマン・コールター社製などのレーザ回折散乱粒度分布測定装置にて測定した値である。これらの無機充填剤のうち、特に、シリカゾルおよびシリカゾル変性物は、分散安定性と共にテーパ角の向上効果に優れる傾向があるため、好ましく配合される。本発明の感光性着色樹脂組成物がこれらの無機充填剤を含む場合、その含有量としては、撥インク性の観点から、全固形分中に、通常５質量％以上、好ましくは１０質量％以上であり、通常８０質量％以下、好ましくは７０質量％以下である。例えば、感光性着色樹脂組成物が無機充填剤を含む場合、感光性着色樹脂組成物の全固形分中の含有割合は５～８０質量％が好ましく、１０～７０質量％がより好ましい。 The average particle size of these inorganic fillers is usually 0.005 to 2 μm, preferably 0.01 to 1 μm. Here, the average particle size referred to in the present embodiment is a value measured by a laser diffraction scattering particle size distribution measuring device such as manufactured by Beckman Coulter. Of these inorganic fillers, silica sol and silica sol-modified products are particularly preferred because they tend to have an excellent effect of improving the taper angle together with the dispersion stability. When the photosensitive colored resin composition of the present invention contains these inorganic fillers, the content thereof is usually 5% by mass or more, preferably 10% by mass or more in the total solid content from the viewpoint of ink repellency. And is usually 80% by mass or less, preferably 70% by mass or less. For example, when the photosensitive colored resin composition contains an inorganic filler, the content of the photosensitive colored resin composition in the total solid content is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass.
［１－１－１３］密着性向上剤
　本発明の感光性着色樹脂組成物には、基板との密着性を付与する目的でリン酸系のエチレン性単量体を含有させてもよい。リン酸系のエチレン性単量体としては、（メタ）アクリロイルオキシ基含有ホスフェート類が好ましく、下記一般式（ｇ１）、（ｇ２）、（ｇ３）で表されるものが好ましい。 [1-1-13] Adhesion improver The photosensitive colored resin composition of the present invention may contain a phosphoric acid-based ethylenic monomer for the purpose of imparting adhesion to a substrate. As the phosphoric acid-based ethylenic monomer, (meth) acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2), and (g3) are preferable.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
［上記一般式（ｇ１）、（ｇ２）、（ｇ３）において、Ｒ51は水素原子又はメチル基を示し、ｌ及びｌ’は１～１０の整数、ｍは１、２又は３である。］ [In the general formulas (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2 or 3. ]
　これらのリン酸系エチレン性単量体は、１種類を単独で用いても、２種以上を組み合わせて使用してもよい。これらリン酸系エチレン性単量体用いる場合の含有割合は、感光性着色樹脂組成物の全固形分中に通常０．０２質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上がさらに好ましく、０．２質量％以上が特に好ましい。また４質量％以下が好ましく、３質量％以下がより好ましく、２質量％以下がさらに好ましく、１質量％以下が特に好ましい。前記下限値以上とすることで基板との密着性の改善効果が十分となる傾向があり、一方上記上限値以下とすることで基板との密着性の悪化を抑制しやすい傾向がある。例えば、感光性着色樹脂組成物がリン酸系エチレン性単量体を含む場合、感光性着色樹脂組成物の全固形分中の含有割合は０．０２～４質量％が好ましく、０．０５～３質量％がより好ましく、０．１～２質量％がさらに好ましく、０．２～１質量％が特に好ましい。 は These phosphoric ethylenic monomers may be used alone or in combination of two or more. When the phosphoric acid-based ethylenic monomer is used, the content ratio is usually preferably 0.02% by mass or more, more preferably 0.05% by mass or more, based on the total solid content of the photosensitive colored resin composition. 1% by mass or more is more preferable, and 0.2% by mass or more is particularly preferable. Further, it is preferably 4% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, particularly preferably 1% by mass or less. When the content is not less than the lower limit, the effect of improving the adhesion to the substrate tends to be sufficient, and when the content is not more than the above upper limit, deterioration of the adhesion to the substrate tends to be easily suppressed. For example, when the photosensitive colored resin composition contains a phosphoric acid ethylenic monomer, the content of the photosensitive colored resin composition in the total solid content is preferably 0.02 to 4% by mass, and 0.05 to 4% by mass. The content is more preferably 3% by mass, further preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass.
［１－１－１４］溶剤
　本発明の感光性着色樹脂組成物は、通常溶剤を含有し、前述の各成分を溶剤に溶解または分散させた状態で使用される。その溶剤としては、特に制限は無いが、例えば、以下に記載する有機溶剤が挙げられる。 [1-1-14] Solvent The photosensitive colored resin composition of the present invention usually contains a solvent, and is used in a state where the above-mentioned components are dissolved or dispersed in the solvent. The solvent is not particularly limited, and examples thereof include the organic solvents described below.
　エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、３－メチル－３－メトキシブタノール、３－メトキシ－１－ブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類；
エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類；
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、３－メトキシ－１－ブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、３－メチル－３－メトキシブチルアセテートのようなグリコールアルキルエーテルアセテート類；
エチレングリコールジアセテート、プロピレングリコールジアセテート、１，３－ブチレングリコールジアセテート、１，４－ブタンジオールジアセテート、１，６－ヘキサノールジアセテートなどのグリコールジアセテート類；
シクロヘキサノールアセテートなどのアルキルアセテート類；
アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類；
アセトン、メチルエチルケトン、メチルイソプロピルケトン、メチルアミルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノンのようなケトン類；
メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような１価又は多価アルコール類；
ｎ－ペンタン、ｎ－オクタン、ジイソブチレン、ｎ－ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類；
シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類；
ベンゼン、トルエン、キシレン、クメンのような芳香族炭化水素類；
アミルホルメート、エチルホルメート、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸アミル、メチルイソブチレート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、安息香酸エチル、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、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－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、γ－ブチロラクトンのような鎖状又は環状エステル類；
３－メトキシプロピオン酸、３－エトキシプロピオン酸のようなアルコキシカルボン酸類；
ブチルクロライド、アミルクロライドのようなハロゲン化炭化水素類；
メトキシメチルペンタノンのようなエーテルケトン類；
アセトニトリル、ベンゾニトリルのようなニトリル類；
テトラヒドロフラン、ジメチルテトラヒドロフラン、ジメトキシテトラヒドロフランのようなテトラヒドロフラン類などである。 Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, Triethylene glycol mono Chirueteru, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, 3- Methoxy-1-butyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate Tate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, and 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy methyl pentanone Ketones;
Mono- or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol Kind;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, benzoate Such as ethyl acrylate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone Linear or cyclic esters;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile;
And tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran and dimethoxytetrahydrofuran.
　上記に該当する市販の溶剤としては、ミネラルスピリット、バルソル＃２、アプコ＃１８ソルベント、アプコシンナー、ソーカルソルベントＮｏ．１およびＮｏ．２、ソルベッソ＃１５０、シェルＴＳ２８　ソルベント、カルビトール、エチルカルビトール、ブチルカルビトール、メチルセロソルブ、エチルセロソルブ、エチルセロソルブアセテート、メチルセロソルブアセテート、ジグライム（いずれも商品名）などが挙げられる。 市 販 As the commercially available solvents corresponding to the above, mineral spirits, Valsol # 2, Apco # 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso # 150, Shell TS28 # Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all of which are trade names).
　上記溶剤は、感光性着色樹脂組成物中の各成分を溶解または分散させることができるもので、本発明の感光性着色樹脂組成物の使用方法に応じて選択されるが、塗布性の観点から、大気圧下における沸点が６０～２８０℃の範囲のものを選択することが好ましい。より好ましくは７０℃以上、２６０℃以下の沸点をもつものであり、例えばプロピレングリコールモノメチルエーテル、３－メトキシ－１－ブタノール、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－１－ブチルアセテート、が好ましい。 The solvent, which can dissolve or disperse each component in the photosensitive colored resin composition, is selected according to the method of using the photosensitive colored resin composition of the present invention, from the viewpoint of applicability It is preferable to select one having a boiling point in the range of 60 to 280 ° C. under atmospheric pressure. More preferably, it has a boiling point of 70 ° C. or more and 260 ° C. or less, for example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate.
　これらの溶剤は１種を単独でもしくは２種以上を混合して使用することができる。また、これらの溶剤は、感光性着色樹脂組成物中の全固形分の割合が、通常１０質量％以上、好ましくは１５質量％以上、より好ましくは２０質量％以上、さらに好ましくは２５質量％以上、通常９０質量％以下、好ましくは５０質量％以下、より好ましくは４０質量％以下、さらに好ましくは３５質量％以下となるように使用されることが好ましい。前記下限値以上とすることで塗布ムラの発生を抑制できる傾向があり、また、前記上限値以下とすることで異物、ハジキ等の発生を抑制できる傾向がある。例えば、溶剤は、感光性着色樹脂組成物中の全固形分の割合が、好ましくは１０～９０質量％、より好ましくは１５～５０質量％、さらに好ましくは２０～４０質量％、特に好ましくは２５～３５質量％となるように使用されることが好ましい。 These solvents can be used alone or in combination of two or more. In these solvents, the proportion of the total solid content in the photosensitive colored resin composition is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more. It is preferably used so as to be usually 90% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less. When the amount is equal to or more than the lower limit, the occurrence of coating unevenness tends to be suppressed, and when the amount is equal to or less than the upper limit, the occurrence of foreign matter, repelling, or the like tends to be suppressed. For example, the proportion of the solvent in the photosensitive colored resin composition is preferably from 10 to 90% by mass, more preferably from 15 to 50% by mass, still more preferably from 20 to 40% by mass, particularly preferably from 25 to 40% by mass. Preferably, it is used in an amount of up to 35% by mass.
［１－２］感光性着色樹脂組成物の調製方法
　本発明の感光性着色樹脂組成物は、上記の各成分を撹拌機で混合することにより調製される。
　例えば、（Ｄ）着色剤として顔料等の溶剤不溶成分を含む場合には、予めペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザー等を用いて分散処理することが好ましい。分散処理により（Ｄ）着色剤が微粒子化されるため、感光性着色樹脂組成物の塗布特性が向上する。 [1-2] Method for Preparing Photosensitive Colored Resin Composition The photosensitive colored resin composition of the present invention is prepared by mixing the above components with a stirrer.
For example, in the case where (D) a solvent or a solvent-insoluble component such as a pigment is contained as a colorant, it is preferable to carry out a dispersion treatment in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the colorant (D) is finely divided by the dispersion treatment, the coating properties of the photosensitive colored resin composition are improved.
　分散処理は、通常、（Ｄ）着色剤、溶剤、及び（Ｆ）分散剤、並びに（Ｂ）アルカリ可溶性樹脂の一部又は全部を併用した系にて行うことが好ましい（以下、分散処理に供する混合物、及び該処理にて得られた組成物を「インク」又は「顔料分散液」と称することがある）。特に（Ｆ）分散剤として高分子分散剤を用いると、得られたインク及び感光性着色樹脂組成物の経時の増粘が抑制される（分散安定性に優れる）ので好ましい。
　このように、感光性着色樹脂組成物を製造する工程において、（Ｄ）着色剤、溶剤、及び（Ｆ）分散剤を少なくとも含有する顔料分散液を製造することが好ましい。
　顔料分散液に用いることができる（Ｄ）着色剤、有機溶剤、及び（Ｆ）分散剤としては、それぞれ感光性着色樹脂組成物に用いることができるものとして記載したものを好ましく採用することができる。また、顔料分散液における（Ｄ）着色剤の各着色剤の含有割合としても、感光性着色樹脂組成物における含有割合として記載したものを好ましく採用することができる。 Usually, the dispersion treatment is preferably performed in a system in which (D) a colorant, a solvent, and (F) a dispersant, and (B) a part or all of an alkali-soluble resin are used in combination (hereinafter referred to as dispersion treatment). The mixture and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”). In particular, it is preferable to use a polymer dispersant as the dispersant (F) because the obtained ink and the photosensitive colored resin composition are prevented from thickening with time (excellent in dispersion stability).
Thus, in the step of producing the photosensitive colored resin composition, it is preferable to produce a pigment dispersion containing at least (D) a colorant, a solvent, and (F) a dispersant.
As the (D) colorant, organic solvent, and (F) dispersant that can be used in the pigment dispersion, those described as being usable in the photosensitive coloring resin composition can be preferably used. . As the content ratio of each colorant in the colorant (D) in the pigment dispersion, those described as the content ratio in the photosensitive colored resin composition can be preferably employed.
　サンドグラインダーで（Ｄ）着色剤を分散させる場合には、０．１～８ｍｍ程度の粒子径のガラスビーズ又はジルコニアビーズが好ましく用いられる。分散処理条件は、温度は通常０℃から１００℃であり、好ましくは室温から８０℃の範囲である。分散時間は液の組成及び分散処理装置のサイズ等により適正時間が異なるため適宜調節する。感光性着色樹脂組成物の２０度鏡面光沢度（ＪＩＳ　Ｚ８７４１）が５０～３００の範囲となるように、インキの光沢を制御することが分散の目安である。 (4) When the colorant (D) is dispersed by a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. The dispersing conditions are generally such that the temperature is from 0 ° C to 100 ° C, preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, and the like. Controlling the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the photosensitive colored resin composition falls within the range of 50 to 300 is a measure of dispersion.
　また、インク中に分散した顔料の分散粒径は通常０．０３～０．３μｍであり、動的光散乱法等により測定される。
　次に、上記分散処理により得られたインクと、感光性着色樹脂組成物中に含まれる、上記の他の成分を混合し、均一な溶液とする。感光性着色樹脂組成物の製造工程においては、微細なゴミが液中に混じることがあるため、得られた感光性着色樹脂組成物はフィルター等により濾過処理することが望ましい。 The dispersed particle size of the pigment dispersed in the ink is usually from 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment and the other components contained in the photosensitive colored resin composition are mixed to form a uniform solution. In the manufacturing process of the photosensitive colored resin composition, fine dust may be mixed in the liquid. Therefore, it is desirable that the obtained photosensitive colored resin composition is subjected to a filtration treatment with a filter or the like.
［２］隔壁及びその形成方法
　本発明の感光性着色樹脂組成物を硬化させることで、本発明の硬化物を得ることができる。本発明の感光性着色樹脂組成物は隔壁を形成するために用いることができ、特に有機電界発光素子の有機層を区画するための隔壁を形成するために好適に用いることができる。
　以上説明した感光性着色樹脂組成物を用いて隔壁を形成する方法は特に限定されず、従来公知の方法を採用することができる。隔壁の形成方法としては、例えば、感光性着色樹脂組成物を、基板上に塗布し、感光性着色樹脂組成物層を形成する塗布工程と、感光性着色樹脂組成物層を露光する露光工程と、を含む方法が挙げられる。このようなバンクの形成方法の具体例としては、インクジェット法とフォトリソグラフィー法とが挙げられる。 [2] Partition wall and method for forming the same By curing the photosensitive colored resin composition of the present invention, the cured product of the present invention can be obtained. The photosensitive colored resin composition of the present invention can be used for forming a partition, and can be particularly suitably used for forming a partition for partitioning an organic layer of an organic electroluminescent element.
The method for forming the partition wall using the photosensitive colored resin composition described above is not particularly limited, and a conventionally known method can be employed. As a method of forming the partition, for example, a photosensitive colored resin composition is applied on a substrate, a coating step of forming a photosensitive colored resin composition layer, and an exposure step of exposing the photosensitive colored resin composition layer And a method including: Specific examples of the method for forming such a bank include an inkjet method and a photolithography method.
　インクジェット法では、溶剤による希釈等により粘度調整された感光性着色樹脂組成物をインクとして用い、所定の隔壁のパターンに沿ってインクジェット法によりインク液滴を基板上に吐出することで感光性着色樹脂組成物を基板上に塗布して未硬化の隔壁のパターンを形成する。そして、未硬化の隔壁のパターンを露光して、基板上に硬化した隔壁を形成する。未硬化の隔壁のパターンの露光は、マスクを用いないことの他は、後述するフォトリソグラフィー法における露光工程と同様に行われる。 In the ink-jet method, a photosensitive colored resin composition whose viscosity is adjusted by dilution with a solvent or the like is used as an ink, and ink droplets are ejected onto a substrate by an ink-jet method along a predetermined partition pattern to form a photosensitive colored resin. The composition is applied on a substrate to form an uncured partition pattern. Then, the pattern of the uncured partition is exposed to form a cured partition on the substrate. The exposure of the uncured partition wall pattern is performed in the same manner as the exposure step in the photolithography method described below, except that a mask is not used.
　フォトリソグラフィー法では、感光性着色樹脂組成物を、基板の隔壁が形成される領域全面に塗布して感光性着色樹脂組成物層を形成する。形成された感光性着色樹脂組成物層を、所定の隔壁のパターンに応じて露光した後、露光された感光性着色樹脂組成物層を現像して、基板上に隔壁が形成される。 In the photolithography method, the photosensitive colored resin composition is applied to the entire surface of the substrate where the partition is to be formed to form a photosensitive colored resin composition layer. After the formed photosensitive colored resin composition layer is exposed according to a predetermined partition pattern, the exposed photosensitive colored resin composition layer is developed to form a partition on the substrate.
　フォトリソグラフィー法における、感光性着色樹脂組成物を基板上に塗布する塗布工程では、隔壁が形成されるべき基板上に、ロールコーター、リバースコーター、バーコーター等の接触転写型塗布装置やスピンナー（回転式塗布装置）、カーテンフローコーター等の非接触型塗布装置を用いて感光性着色樹脂組成物を塗布し、必要に応じて、乾燥により溶媒を除去して、感光性着色樹脂組成物層を形成する。 In the application step of applying the photosensitive colored resin composition on the substrate in the photolithography method, a contact transfer type application device such as a roll coater, a reverse coater, a bar coater, or a spinner (rotating) is applied on the substrate on which the partition is to be formed. Type coating apparatus), applying the photosensitive colored resin composition using a non-contact type coating apparatus such as a curtain flow coater, and, if necessary, removing the solvent by drying to form a photosensitive colored resin composition layer. I do.
　次いで、露光工程では、ネガ型のマスクを利用して、感光性着色樹脂組成物に紫外線、エキシマレーザー光等の活性エネルギー線を照射し、感光性着色樹脂組成物層をバンクのパターンに応じて部分的に露光する。露光には、高圧水銀灯、超高圧水銀灯、キセノンランプ、カーボンアーク灯等の紫外線を発する光源を用いることができる。露光量は感光性着色樹脂組成物の組成によっても異なるが、例えば１０～４００ｍＪ／ｃｍ2程度が好ましい。 Next, in the exposure step, the photosensitive colored resin composition is irradiated with active energy rays such as ultraviolet rays and excimer laser light using a negative type mask, and the photosensitive colored resin composition layer is formed in accordance with the pattern of the bank. Expose partially. For the exposure, a light source that emits ultraviolet light such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The exposure amount varies depending on the composition of the photosensitive colored resin composition, but is preferably, for example, about 10 to 400 mJ / cm 2 .
　次いで、現像工程では、隔壁のパターンに応じて露光された感光性着色樹脂組成物層を現像液で現像することにより隔壁を形成する。現像方法は特に限定されず、浸漬法、スプレー法等を用いることができる。現像液の具体例としては、ジメチルベンジルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の有機系のものや、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、アンモニア、４級アンモニウム塩等の水溶液が挙げられる。又、現像液には、消泡剤や界面活性剤を添加することもできる。 Next, in the developing step, the photosensitive colored resin composition layer exposed according to the pattern of the partition is developed with a developer to form the partition. The developing method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developing solution include organic ones such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. No. Further, an antifoaming agent or a surfactant can be added to the developer.
　その後、現像後の隔壁にポストベークを施して加熱硬化する。ポストベークは、１５０～２５０℃で１５～６０分間が好ましい。 Thereafter, post-baking is applied to the partition walls after development, and heat curing is performed. Post-baking is preferably performed at 150 to 250 ° C. for 15 to 60 minutes.
　隔壁の形成に用いる基板は特に限定されず、隔壁が形成された基板を用いて製造される有機電界発光素子の種類に合わせて適宜選択される。好適な基板の材料としては、ガラスや、各種の樹脂材料が挙げられる。樹脂材料の具体例としては、ポリエチレンテレフタレート等のポリエステル；ポリエチレン、及びポリプロピレン等のポリオレフィン；ポリカーボネート；ポリ（メタ）メタアクリル樹脂；ポリスルホン；ポリイミドが挙げられる。これらの基板の材料の中では、耐熱性に優れることからガラス、及びポリイミドが好ましい。また、製造される有機電界発光素子の種類に応じて、隔壁が形成される基板の表面には、予めＩＴＯやＺｎＯ等の透明電極層を設けておいてもよい。 (4) The substrate used for forming the partition is not particularly limited, and is appropriately selected according to the type of the organic electroluminescent device manufactured using the substrate on which the partition is formed. Suitable substrate materials include glass and various resin materials. Specific examples of the resin material include polyester such as polyethylene terephthalate; polyolefin such as polyethylene and polypropylene; polycarbonate; poly (meth) methacrylic resin; polysulfone; and polyimide. Among these materials for the substrate, glass and polyimide are preferable because of their excellent heat resistance. In addition, a transparent electrode layer of ITO, ZnO, or the like may be provided in advance on the surface of the substrate on which the partition wall is formed, depending on the type of the organic electroluminescent device to be manufactured.
［３］有機電界発光素子
　本発明の有機電界発光素子は、前述の感光性着色樹脂組成物で構成される隔壁を備える。
　以上説明した方法により製造された隔壁パターンを備える基板を用いて、種々の有機電界発光素子が製造される。有機電界発光素子を形成する方法は特に限定されないが、好ましくは、上記方法により基板上に隔壁のパターンを形成した後に、基板上の隔壁により囲まれた領域内にインクを注入して画素等の有機層を形成することによって、有機電界発光素子が製造される。 [3] Organic electroluminescent device The organic electroluminescent device of the present invention includes a partition wall composed of the above-described photosensitive colored resin composition.
Various organic electroluminescent devices are manufactured using the substrate provided with the partition pattern manufactured by the method described above. The method of forming the organic electroluminescent element is not particularly limited, but preferably, after forming a pattern of the partition on the substrate by the above-described method, injecting ink into a region surrounded by the partition on the substrate to form a pixel or the like. By forming an organic layer, an organic electroluminescent device is manufactured.
　隔壁がすそ引き形状である場合、有機層形成用のインクが隔壁のすそ部分で弾かれるため、隔壁により囲まれた領域内が有機層形成用のインクにより十分に被覆されない場合がある。それに対して、すそ引きのない良好な形状とすることで、隔壁により囲まれた領域内を有機層形成用のインクにより十分に被覆することができる。これにより、例えば、有機ＥＬ表示素子におけるハレーションの問題を解消することができる。 (4) When the partition has a skirt shape, the ink for forming the organic layer is repelled at the skirt portion of the partition, so that the region surrounded by the partition may not be sufficiently covered with the ink for forming the organic layer. On the other hand, by forming a good shape without tailing, the area surrounded by the partition can be sufficiently covered with the ink for forming an organic layer. Thereby, for example, the problem of halation in the organic EL display element can be solved.
　有機層形成用のインクを形成する際に使用される溶媒としては、水、有機溶剤、及びこれらの混合溶剤を用いることができる。有機溶剤は、インクの注入後に形成された皮膜から除去可能であれば特に限定されない。有機溶剤の具体例としては、トルエン、キシレン、アニソール、メシチレン、テトラリン、シクロヘキシルベンゼン、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、メタノール、エタノール、イソプロピルアルコール、酢酸エチル、及び酢酸ブチル、３－フェノキシトルエン、等が挙げられる。また、インクには、界面活性剤、酸化防止剤、粘度調整剤、紫外線吸収剤等を添加することができる。 溶媒 Water, an organic solvent, and a mixed solvent thereof can be used as a solvent used when forming an ink for forming an organic layer. The organic solvent is not particularly limited as long as it can be removed from the film formed after the injection of the ink. Specific examples of the organic solvent include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, and butyl acetate, 3-phenoxytoluene, And the like. Further, a surfactant, an antioxidant, a viscosity modifier, an ultraviolet absorber, and the like can be added to the ink.
　隔壁により囲まれた領域内にインクを注入する方法としては、少量のインクを所定の個所に容易に注入可能であることから、インクジェット法が好ましい。有機層の形成に使用されるインクは、製造される有機電界発光素子の種類に応じて適宜選択される。インクをインクジェット法により注入する場合、インクの粘度はインクをインクジェットヘッドから良好に吐出できる限り特に限定されないが、４～２０ｍＰａ・ｓが好ましく、５～１０ｍＰａ・ｓがより好ましい。インクの粘度は、インク中の固形分含有量の調整、溶媒の変更、粘度調整剤の添加等により調整することができる。 イ ン ク ジ ェ ッ ト As a method of injecting ink into the region surrounded by the partition, an ink jet method is preferable because a small amount of ink can be easily injected into a predetermined place. The ink used to form the organic layer is appropriately selected according to the type of the organic electroluminescent device to be manufactured. When the ink is injected by an ink-jet method, the viscosity of the ink is not particularly limited as long as the ink can be discharged well from the ink-jet head, but is preferably 4 to 20 mPa · s, more preferably 5 to 10 mPa · s. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, and the like.
　有機電界発光素子のタイプとしては、ボトムエミッション型やトップエミッション型が挙げられる。
　ボトムエミッション型では、例えば、透明電極を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に正孔輸送層、発光層、電子輸送層、金属電極層を積層して作成される。一方でトップエミッション型では、例えば、金属電極層を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に電子輸送層、発光層、正孔輸送層、透明電極層を積層して作成される。
　なお、発光層としては、日本国特開２００９－１４６６９１号公報や日本国特許第５７３４６８１号公報に記載されているような有機電界発光層が挙げられる。また、日本国特許第５６５３３８７号公報や日本国特許第５６５３１０１号公報に記載されているような量子ドットを用いてもよい。 Examples of the type of the organic electroluminescent device include a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer are laminated on an opening surrounded by the partition. You. On the other hand, in the top emission type, for example, a partition is formed on a glass substrate on which a metal electrode layer is stacked, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the partition. Created.
As the light emitting layer, an organic electroluminescent layer as described in Japanese Patent Application Laid-Open No. 2009-146691 or Japanese Patent No. 5734681 can be used. Further, quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
［４］画像表示装置
　本発明の画像表示装置は、本発明の硬化物を含むものであり、特に本発明の有機電界発光素子を含むものが挙げられる。有機電界発光素子を含む画像表示装置としては、画像表示装置の型式や構造については特に制限はなく、例えばアクティブ駆動型有機電界発光素子を用いて常法に従って組み立てることができる。例えば、「有機ＥＬディスプレイ」（オーム社、平成１６年８月２０日発行、時任静士、安達千波矢、村田英幸著）に記載されているような方法で、本発明の画像表示装置を形成することができる。例えば、白色光を発光する有機電界発光素子とカラーフィルターとを組み合わせて画像表示させてもよいし、ＲＧＢ等の発光色の異なる有機電界発光素子を組み合わせて画像表示させてもよい。 [4] Image Display Device The image display device of the present invention includes the cured product of the present invention, and particularly includes the organic display device of the present invention. There is no particular limitation on the type and structure of the image display device including the organic electroluminescent device, and the image display device can be assembled in a usual manner using, for example, an active driving type organic electroluminescent device. For example, the image display device of the present invention is formed by a method as described in “Organic EL Display” (Ohm Co., published on August 20, 2004, Shizuki Tokito, Chihaya Adachi, Hideyuki Murata). can do. For example, an image may be displayed by combining an organic electroluminescent element that emits white light and a color filter, or may be displayed by combining organic electroluminescent elements that emit light of different colors such as RGB.
［５］照明
　本発明の照明は、本発明の硬化物を含むものであり、特に本発明の有機電界発光素子を含むものが挙げられる。型式や構造については特に制限はなく、本発明の有機電界発光素子を用いて常法に従って組み立てることができる。有機電界発光素子としては、単純マトリックス駆動方式としてもよいし、アクティブマトリックス駆動方式としてもよい。
　本発明の照明が白色光を発光するものとするために、白色光を発光する有機電界発光素子を用いてもよい。また、発光色の異なる有機電界発光素子を組み合わせて、各色が混色して白色となるよう構成してもよいし、混色比率を調整できるように構成して調色機能を付与してもよい。 [5] Illumination The illumination of the present invention includes the cured product of the present invention, and particularly includes the organic electroluminescent device of the present invention. The type and structure are not particularly limited, and can be assembled according to a conventional method using the organic electroluminescent device of the present invention. The organic electroluminescent element may be of a simple matrix drive type or of an active matrix drive type.
In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. Further, organic electroluminescent elements having different emission colors may be combined to be configured so that the respective colors are mixed to form white, or a configuration in which the mixture ratio can be adjusted to provide a toning function.
　以下、本発明の感光性着色樹脂組成物について、具体的な実施例を挙げて説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。 Hereinafter, the photosensitive colored resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples unless it exceeds the gist.
＜アルカリ可溶性樹脂－Ｉ＞
　ジシクロペンタニルメタクリレート／スチレン／グリシジルメタクリレート（モル比：０．３／０．１／０．６）を構成モノマーとする共重合樹脂に、アクリル酸をグリシジルメタクリレートと等量付加反応させ、さらに無水テトラヒドロフタル酸を上記の共重合樹脂１モルに対してモル比０．３９になるように付加した、アルカリ可溶性のアクリル共重合樹脂。ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）は９０００、酸価は８０ｍｇＫＯＨ／ｇ。これにＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）を加え、固形分濃度４２．７質量％とした。 <Alkali-soluble resin-I>
An equal amount of acrylic acid and glycidyl methacrylate are added to a copolymer resin containing dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.3 / 0.1 / 0.6) as a constituent monomer. An alkali-soluble acrylic copolymer resin in which tetrahydrophthalic acid is added in a molar ratio of 0.39 with respect to 1 mol of the above copolymer resin. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 9000, and the acid value was 80 mgKOH / g. PGMEA (propylene glycol monomethyl ether acetate) was added thereto to obtain a solid content concentration of 42.7% by mass.
＜アルカリ可溶性樹脂－ＩＩ＞
　日本化薬社製「ＺＣＲ－１６４２Ｈ」（重量平均分子量（Ｍｗ）＝６５００、酸価＝９８ｍｇＫＯＨ／ｇ）。これにＰＧＭＥＡを加え、固形分濃度４０．０質量％とした。 <Alkali-soluble resin-II>
“ZCR-1642H” manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight (Mw) = 6500, acid value = 98 mg KOH / g). PGMEA was added to this to give a solid concentration of 40.0% by mass.
＜分散剤－Ｉ＞
　ビックケミー社製「ＢＹＫ－ＬＰＮ２１１１６」（側鎖に４級アンモニウム塩基及び３級アミノ基を有するＡブロックと、４級アンモニウム塩基及び３級アミノ基を有さないＢブロックからなる、アクリル系Ａ－Ｂブロック共重合体。アミン価は７０ｍｇＫＯＨ／ｇ。酸価は１ｍｇＫＯＨ／ｇ以下。）
　分散剤－ＩのＡブロック中には、下記式（１ａ）及び（２ａ）の繰り返し単位が含まれ、Ｂブロック中には下記式（３ａ）の繰り返し単位が含まれる。分散剤－Ｉの全繰り返し単位に占める下記式（１ａ）、（２ａ）、及び（３ａ）の繰り返し単位の含有割合はそれぞれ１１．１モル％、２２．２モル％、及び６．７モル％である。 <Dispersant-I>
"BYK-LPN21116" manufactured by BYK-Chemie (acrylic AB comprising an A block having a quaternary ammonium base and a tertiary amino group in a side chain and a B block having no quaternary ammonium base and a tertiary amino group) (Block copolymer, amine value 70 mgKOH / g, acid value 1 mgKOH / g or less.)
The A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains a repeating unit of the following formula (3a). The content of the repeating units of the following formulas (1a), (2a) and (3a) in the total repeating units of Dispersant-I was 11.1 mol%, 22.2 mol% and 6.7 mol%, respectively. It is.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
＜溶剤－Ｉ＞
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
＜溶剤－ＩＩ＞
　ＭＢ：３－メトキシ－１－ブタノール
＜光重合性化合物－Ｉ＞
　ＤＰＨＡ：日本化薬社製　ジペンタエリスリトールヘキサアクリレート
　　＜光重合性化合物－ＩＩ＞
　　　ＴＭＰ―Ａ：共栄社化学社製　トリメチロールプロパントリアクリレート <Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II>
MB: 3-methoxy-1-butanol <photopolymerizable compound-I>
DPHA: Nippon Kayaku Co. dipentaerythritol hexaacrylate <Photopolymerizable compound-II>
TMP-A: Trimethylolpropane triacrylate manufactured by Kyoeisha Chemical Co., Ltd.
＜光重合開始剤－１＞
　以下の化学構造を有する化合物を用いた。この化合物をＰＧＭＥＡに対し０．０１質量％の濃度になるように溶解させたとき、波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）である３６８ｎｍにおける吸光度に対して３４％であった。オキシムエステル系光重合開始剤（Ａ１）に該当する。 <Photopolymerization initiator-1>
A compound having the following chemical structure was used. When this compound was dissolved in PGMEA to a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm was 34 times the absorbance at 368 nm, which is the maximum absorption wavelength (λ max ) between 300 and 400 nm. %Met. This corresponds to the oxime ester-based photopolymerization initiator (A1).
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
＜光重合開始剤－２＞
　ＢＡＳＦ社製　ＩＲＧＡＣＵＲＥ（登録商標、以下同じ。）　ＯＸＥ－０１を用いた。この化合物をＰＧＭＥＡに対し０．０１質量％の濃度になるように溶解させたとき、波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）である３２９ｎｍにおける吸光度に対して０．７％であった。オキシムエステル系光重合開始剤（Ａ２）に該当する。 <Photopolymerization initiator-2>
IRGACURE (registered trademark, the same applies hereinafter) OXE-01 manufactured by BASF was used. When this compound was dissolved in PGMEA to a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm was 0% relative to the absorbance at 329 nm, which is the maximum absorption wavelength (λ max ) between 300 and 400 nm. 0.7%. This corresponds to the oxime ester-based photopolymerization initiator (A2).
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
＜光重合開始剤－３＞
　常州強力電子新材料社製　ＴＲＯＮＬＹ（登録商標。）　ＴＲ－ＰＢＧ－３０５を用いた。この化合物をＰＧＭＥＡに対し０．０１質量％の濃度になるように溶解させたとき、波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）である３２９ｎｍにおける吸光度に対して０．６％であった。オキシムエステル系光重合開始剤（Ａ２）に該当する。 <Photopolymerization initiator-3>
TRONLY (registered trademark) TR-PBG-305 manufactured by Changzhou Strong Electronic New Materials Co., Ltd. was used. When this compound was dissolved in PGMEA to a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm was 0% relative to the absorbance at 329 nm, which is the maximum absorption wavelength (λ max ) between 300 and 400 nm. 0.6%. This corresponds to the oxime ester-based photopolymerization initiator (A2).
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
＜光重合開始剤－４＞
　日本国特開２０１８－００２９６２号公報の合成例２に記載の方法で得た、以下の化学構造を有する化合物を用いた。波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λmax）である３６８ｎｍにおける吸光度に対して３３％であった。オキシムエステル系光重合開始剤（Ａ１）に該当する。 <Photopolymerization initiator-4>
A compound having the following chemical structure, obtained by the method described in Synthesis Example 2 of JP-A-2018-002962, was used. The absorbance at a wavelength of 400 nm was 33% of the absorbance at 368 nm, which is the maximum absorption wavelength (λ max ) between 300 and 400 nm. This corresponds to the oxime ester-based photopolymerization initiator (A1).
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
＜光重合開始剤－５＞
　以下の化学構造を有する化合物を用いた。この化合物をＰＧＭＥＡに対し０．０１質量％の濃度になるように溶解させたとき、波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λｍａｘ）である３２８ｎｍにおける吸光度に対して１．１％であった。オキシムエステル系光重合開始剤（Ａ２）に該当する。 <Photopolymerization initiator-5>
A compound having the following chemical structure was used. When this compound was dissolved in PGMEA at a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm was 1% of the absorbance at 328 nm, which is the maximum absorption wavelength (λ max ) between 300 and 400 nm. 0.1%. This corresponds to the oxime ester-based photopolymerization initiator (A2).
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
＜光重合開始剤－６＞
　ＢＡＳＦ社製　ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２を用いた。この化合物をＰＧＭＥＡに対し０．０１質量％の濃度になるように溶解させたとき、波長４００ｎｍにおける吸光度は、波長３００～４００ｎｍ間の極大吸収波長（λｍａｘ）である３３６ｎｍにおける吸光度に対して０．１％であった。オキシムエステル系光重合開始剤（Ａ２）に該当する。 <Photopolymerization initiator-6>
An IRGACURE OXE-02 manufactured by BASF was used. When this compound is dissolved in PGMEA at a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm is 0% relative to the absorbance at 336 nm, which is the maximum absorption wavelength (λ max ) between 300 and 400 nm. 0.1%. This corresponds to the oxime ester-based photopolymerization initiator (A2).
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
＜撥液剤－Ｉ＞
　ＤＩＣ社製　メガファック　ＲＳ－７２－ｋ（架橋基としてエチレン性二重結合を有するフッ素原子含有オリゴマー）
＜添加剤－Ｉ＞
　日本化薬社製　ＫＡＹＡＭＥＲ（登録商標。）　ＰＭ－２１ <Liquid repellent-I>
Megafax RS-72-k (manufactured by DIC) (fluorine atom-containing oligomer having an ethylenic double bond as a crosslinking group)
<Additive-I>
Nippon Kayaku KAYAMER (registered trademark) PM-21
＜顔料分散液１の調製＞
　表１に記載の顔料、分散剤、アルカリ可溶性樹脂、及び溶剤を、表１に記載の質量比となるように混合した。なお表１中の分散剤及びアルカリ可溶性樹脂の量は固形分量であり、溶剤の量には分散剤及びアルカリ可溶性樹脂由来の溶剤量も含まれる。
　この溶液をペイントシェーカーにより２５～４５℃の範囲で３時間分散処理を行った。ビーズとしては、０．５ｍｍφのジルコニアビーズを用い、分散液の２．５倍の質量を加えた。分散処理終了後、フィルターによりビーズと分散液を分離して、顔料分散液１を調製した。 <Preparation of pigment dispersion liquid 1>
The pigment, the dispersant, the alkali-soluble resin, and the solvent shown in Table 1 were mixed so as to have the mass ratio shown in Table 1. The amounts of the dispersant and the alkali-soluble resin in Table 1 are solid contents, and the amount of the solvent includes the amount of the dispersant and the solvent derived from the alkali-soluble resin.
This solution was subjected to a dispersion treatment at 25 to 45 ° C. for 3 hours using a paint shaker. As the beads, zirconia beads having a diameter of 0.5 mm were used, and a mass 2.5 times that of the dispersion was added. After the completion of the dispersion treatment, the beads and the dispersion were separated by a filter to prepare a pigment dispersion 1.
Figure JPOXMLDOC01-appb-T000066
Figure JPOXMLDOC01-appb-T000066
＜感光性着色樹脂組成物の調製＞
　上記調製した顔料分散液１を用いて、全固形分中の各成分の固形分の含有割合が表２に記載のとおりとなるように各成分を加え、さらに全固形分の含有割合が３１質量％であり、かつ、全溶剤中において溶剤－Ｉ／溶剤－ＩＩ＝８０／２０（質量比）となるように各溶剤を加えて希釈し、攪拌、溶解させて、実施例１～４及び比較例１～３の感光性着色樹脂組成物を調製した。得られた感光性着色樹脂組成物を用いて、後述する方法で評価を行った。
　なお、表中、４００ｎｍ吸光度の加重平均値（％）は、本発明の第２の態様における、オキシムエステル系光重合開始剤（Ａ３）の波長４００ｎｍにおける吸光度の値（％）を示す。 <Preparation of photosensitive colored resin composition>
Using the above-prepared pigment dispersion liquid 1, each component was added such that the solid content of each component in the total solid content was as shown in Table 2, and the total solid content content was 31 mass%. %, And each solvent was added and diluted so that the solvent-I / solvent-II = 80/20 (mass ratio) in all the solvents, and the mixture was stirred and dissolved. The photosensitive colored resin compositions of Examples 1 to 3 were prepared. The obtained photosensitive colored resin composition was evaluated by the method described below.
In the table, the weighted average value (%) of the absorbance at 400 nm indicates the value (%) of the absorbance at a wavelength of 400 nm of the oxime ester-based photopolymerization initiator (A3) in the second embodiment of the present invention.
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000067
　実施例１の光重合性化合物－Ｉ　２２．３４質量部を、光重合性化合物－Ｉ　１１．１７質量部及び光重合性化合物－ＩＩ　１１．１７質量部に変更し、それ以外は実施例１と同じ配合の感光性着色樹脂組成物を実施例５として作成した。 22.34 parts by mass of the photopolymerizable compound-I of Example 1 was changed to 11.17 parts by mass of the photopolymerizable compound-I and 11.17 parts by mass of the photopolymerizable compound-II. A photosensitive colored resin composition having the same composition as in Example 5 was prepared as Example 5.
　以下に性能評価の方法を説明する。 性能 The method of performance evaluation is described below.
＜接触角測定用基板の作成＞
　ガラス基板上にスピナーを用いて、加熱硬化後に６．０μｍの厚みになるように感光性着色樹脂組成物を塗布した。その後１００℃にて９０秒間ホットプレート上で加熱乾燥して塗膜基板を得た。次に、得られた塗膜基板を紫外線露光することなく、０．０４質量％のＫＯＨ、０．０７質量％のエマルゲンＡ－６０（花王(株)製　界面活性剤）を溶解した水溶液を現像液として用いて２４℃でスプレー現像し、完全に塗膜が現像除去される時間を読み取りそれをブレークタイムとした。
　次に、前記条件と同じ条件にて別に準備した塗膜基板に、マスクを使用せずに、高圧水銀灯を用いて露光量５０ｍＪ／ｃｍ2で紫外線露光した。この時の波長３６５ｎｍにおける強度は４５ｍＷ／ｃｍ2であった。これを前記と同じ現像液及び現像条件にて、ブレークタイムの１．６倍の現像時間で現像処理した後、純水で１０秒間洗浄した。この基板を、オーブン中２３０℃で３０分間加熱硬化させ、接触角測定用基板を得た。 <Preparation of contact angle measurement board>
Using a spinner, a photosensitive colored resin composition was applied on a glass substrate so as to have a thickness of 6.0 μm after heat curing. Then, it was dried by heating on a hot plate at 100 ° C. for 90 seconds to obtain a coated substrate. Next, an aqueous solution in which 0.04% by mass of KOH and 0.07% by mass of Emulgen A-60 (a surfactant manufactured by Kao Corporation) were dissolved was developed without exposing the obtained coated substrate to ultraviolet light. The solution was spray-developed at 24 ° C., and the time required for complete development and removal of the coating film was read and defined as the break time.
Next, the coating substrate separately prepared under the same conditions as above was exposed to ultraviolet light at an exposure amount of 50 mJ / cm 2 using a high-pressure mercury lamp without using a mask. At this time, the intensity at a wavelength of 365 nm was 45 mW / cm 2 . This was subjected to a developing process for 1.6 times the break time under the same developing solution and developing conditions as described above, and then washed with pure water for 10 seconds. This substrate was cured by heating at 230 ° C. for 30 minutes in an oven to obtain a substrate for measuring a contact angle.
＜ＰＧＭＥＡ接触角の測定＞
　協和界面科学社製接触角測定装置Ｄｒｏｐ　Ｍａｓｔｅｒ　５００により、２３℃、湿度５０％の条件下で、前記接触角測定用基板にＰＧＭＥＡを０．７μＬ滴下した１秒後の接触角を測定し、結果を表２に示した。接触角が大きいほど撥インク性が高いことを表す。 <Measurement of PGMEA contact angle>
Using a contact angle measurement device Drop Master 500 manufactured by Kyowa Interface Science Co., Ltd., the contact angle was measured one second after 0.7 μL of PGMEA was dropped on the substrate for contact angle measurement under the conditions of 23 ° C. and 50% humidity. Are shown in Table 2. The larger the contact angle, the higher the ink repellency.
＜ライン状パターン基板の作成＞
　ガラス基板上にスピナーを用いて、加熱硬化後に６．０μｍの厚みになるように前記感光性着色樹脂組成物を塗布した。その後１００℃にて９０秒間ホットプレート上で加熱乾燥して塗膜基板を得た。次に、得られた塗膜基板にフォトマスクを用いて高圧水銀灯にて紫外線露光を行った。露光量は５０ｍＪ／ｃｍ2で、露光ギャップは１３０μｍとした。この時の波長３６５ｎｍにおける強度は４５ｍＷ／ｃｍ2であった。フォトマスクは開口幅５～５０μｍ（５～２０μｍ：１μｍおき、２５～５０μｍ：５μｍおき）の各種幅のライン状開口部を有する露光マスクを使用した。次いで、前記＜接触角測定用基板の作成＞と同様に、ブレークタイムの１．６倍の現像時間で現像処理を行った後、純水で１０秒間洗浄し、オーブン中２３０℃で３０分間加熱硬化させ、隔壁を想定したライン状パターン基板を作成した。 <Creation of linear pattern substrate>
The photosensitive colored resin composition was applied on a glass substrate using a spinner so as to have a thickness of 6.0 μm after heat curing. Then, it was dried by heating on a hot plate at 100 ° C. for 90 seconds to obtain a coated substrate. Next, the obtained coated substrate was exposed to ultraviolet light with a high-pressure mercury lamp using a photomask. The exposure amount was 50 mJ / cm 2 and the exposure gap was 130 μm. At this time, the intensity at a wavelength of 365 nm was 45 mW / cm 2 . The photomask used was an exposure mask having line-shaped openings of various widths with an opening width of 5 to 50 μm (5 to 20 μm: every 1 μm, 25 to 50 μm: every 5 μm). Next, in the same manner as in <Preparation of Contact Angle Measurement Substrate>, a development process is performed for a development time 1.6 times the break time, followed by washing with pure water for 10 seconds and heating in an oven at 230 ° C. for 30 minutes. After curing, a linear pattern substrate assuming partition walls was prepared.
＜テーパの垂直性の評価＞
　前記ライン状パターン基板のうち、開口幅が２０μｍのライン状開口部に対応するパターンの断面を５０００倍でＳＥＭ観察した。図１の概念図に示すように、基板表面に平行なパターン幅のうち最小値４の幅を最小幅とし、最小幅よりも上部に存在する最大値３の幅を最大幅とした。そして最大幅と最小幅の差によってライン状パターンのテーパの垂直性を評価し、結果を表２に示した。最大幅と最小幅の差が小さいほど隔壁が垂直に形成されることを示す。 <Evaluation of perpendicularity of taper>
A cross section of a pattern corresponding to a linear opening having an opening width of 20 μm in the linear pattern substrate was observed by SEM at 5,000 times. As shown in the conceptual diagram of FIG. 1, the width of the minimum value 4 in the pattern width parallel to the substrate surface was set as the minimum width, and the width of the maximum value 3 existing above the minimum width was set as the maximum width. Then, the perpendicularity of the taper of the linear pattern was evaluated based on the difference between the maximum width and the minimum width, and the results are shown in Table 2. The smaller the difference between the maximum width and the minimum width, the more vertically the partition wall is formed.
　表２の実施例１～４と比較例１～２の比較から明らかなように、オキシムエステル系光重合開始剤（Ａ１）に、オキシムエステル系光重合開始剤（Ａ２）を組み合わせることによって、それぞれを単独で用いる場合と比べて、撥インク性と隔壁のテーパの垂直性を両立することができている。 As is clear from the comparison between Examples 1 to 4 and Comparative Examples 1 and 2 in Table 2, by combining the oxime ester-based photopolymerization initiator (A1) with the oxime ester-based photopolymerization initiator (A2), Can achieve both ink repellency and perpendicularity of the taper of the partition wall, as compared with the case of using alone.
　撥インク性を確保するためには、隔壁の表面に撥液剤を固定させることが必要になる。しかしながら、紫外線露光後の塗膜の硬化度が不十分だと、次に行う現像処理の際に膜表面の一部が溶解し、撥液剤が現像液に流れ出てしまう。光重合開始剤として、主にｉ線を利用するオキシムエステル系光重合開始剤（Ａ２）を１種類単独で用いた場合には、例えば、比較例２のように紫外線露光後の硬化が不十分なため撥インク性が損なわれる。 液 In order to ensure ink repellency, it is necessary to fix a liquid repellent on the surface of the partition. However, if the degree of curing of the coating film after the exposure to ultraviolet light is insufficient, a part of the film surface will be dissolved in the next developing treatment, and the lyophobic agent will flow out into the developing solution. When one kind of the oxime ester-based photopolymerization initiator (A2) mainly using i-ray is used alone as the photopolymerization initiator, for example, the curing after the ultraviolet exposure is insufficient as in Comparative Example 2. Therefore, the ink repellency is impaired.
　一方で、膜厚が５μｍ以上の厚膜パターンを形成する場合、紫外線露光時に塗膜表面から侵入した紫外線は、塗膜に含まれる光重合開始剤や着色剤等によって吸収され、塗膜内部まで透過しにくく、塗膜上部に比べて塗膜下部の硬化度が低くなりやすい。そのため、現像処理時に硬化度の低い塗膜下部が過度に現像されてそのパターン幅が細くなるという問題がある。 On the other hand, when a thick film pattern having a film thickness of 5 μm or more is formed, ultraviolet light that has penetrated from the surface of the coating film when exposed to ultraviolet light is absorbed by a photopolymerization initiator, a coloring agent, and the like included in the coating film, and reaches the inside of the coating film. It is difficult to penetrate, and the degree of hardening of the lower part of the coating film tends to be lower than that of the upper part of the coating film. For this reason, there is a problem in that the lower part of the coating film having a low degree of curing is excessively developed during the development processing, and the pattern width becomes narrow.
　比較例２に対して比較例３のように、オキシムエステル系光重合開始剤（Ａ２）の中でも感度の高いものをさらに併用した場合、撥インク性は良好になったが、塗膜下部のパターン幅がより細くなり、テーパの垂直性が悪くなってしまった。これは、オキシムエステル系光重合開始剤（Ａ２）の中でも感度の高いものを用いることで塗膜上部の硬化性が高くなり、隔壁の表面に撥液剤を固定させることができたものの、主にｉ線を利用するものであることに起因して塗膜下部の硬化性を高くすることはできず、塗膜下部に比べて塗膜上部のパターン幅が太くなったからだと考えられる。 As compared with Comparative Example 2, when a highly sensitive oxime ester-based photopolymerization initiator (A2) was additionally used as in Comparative Example 3, the ink repellency was improved, but the pattern at the lower part of the coating film was improved. The width became narrower, and the perpendicularity of the taper deteriorated. This is because although the use of a highly sensitive oxime ester-based photopolymerization initiator (A2) increases the curability of the upper part of the coating film and enables the liquid repellent to be fixed to the surface of the partition wall, it is mainly used. It is considered that the curability of the lower portion of the coating film could not be increased due to the use of the i-line, and the pattern width of the upper portion of the coating film was larger than that of the lower portion of the coating film.
　一方で、紫外線露光による硬化度を上げる他の方法として、ｉ線に吸収帯を有するオキシムエステル系光重合開始剤の中でも、ｈ線も利用可能なもの、つまり、波長４００ｎｍにおける吸光度が十分に高いオキシムエステル系光重合開始剤（Ａ１）を用いる方法が挙げられる。 On the other hand, among other methods for increasing the degree of curing by ultraviolet exposure, among oxime ester-based photopolymerization initiators having an absorption band at i-line, those that can also use h-line, that is, the absorbance at a wavelength of 400 nm is sufficiently high A method using an oxime ester-based photopolymerization initiator (A1) is exemplified.
　撥インク性を確保するためにオキシムエステル系光重合開始剤（Ａ１）を用いた場合、高感度であることによって塗膜上部の硬化度が高くなり、上部のパターン幅はより太くなる。しかしながら、オキシムエステル系光重合開始剤（Ａ１）の高感度化に寄与しているｈ線に着目すると、オキシムエステル系光重合開始剤（Ａ１）を単独で使用した場合にはｈ線の多くが塗膜上部でオキシムエステル系光重合開始剤（Ａ１）に吸われてしまい、塗膜下部に到達するｈ線はより少なくなり、塗膜下部のパターン幅はより細くなり、テーパの垂直性がさらに損なわれる傾向がある。この傾向は比較例１の結果から明らかである。 (4) When the oxime ester-based photopolymerization initiator (A1) is used to secure the ink repellency, the degree of curing at the top of the coating film is increased due to the high sensitivity, and the width of the pattern at the top is increased. However, focusing on the h-line which contributes to the increase in sensitivity of the oxime ester-based photopolymerization initiator (A1), when the oxime ester-based photopolymerization initiator (A1) is used alone, most of the h-rays are used. Absorbed by the oxime ester-based photopolymerization initiator (A1) at the upper part of the coating film, the h-line reaching the lower part of the coating film becomes smaller, the pattern width at the lower part of the coating film becomes narrower, and the perpendicularity of the taper is further increased. Tends to be impaired. This tendency is clear from the results of Comparative Example 1.
　これに対して実施例１～４のように、オキシムエステル系光重合開始剤（Ａ１）とオキシムエステル系光重合開始剤（Ａ２）を組み合わせることで、オキシムエステル系光重合開始剤（Ａ１）単独の場合に比べて、塗膜上部におけるｈ線の吸収率を相対的に低くできる、つまり、塗膜下部までｈ線を透過させることができ、オキシムエステル系光重合開始剤（Ａ１）によって塗膜下部でのｈ線を利用した硬化が推進され、隔壁のテーパの垂直性が良好になると考えられる。また、オキシムエステル系光重合開始剤（Ａ１）とオキシムエステル系光重合開始剤（Ａ２）とを併用することで、膜表面近傍ではｉ線及びｈ線を利用した硬化が行われ、撥インク性も十分となると考えられる。 On the other hand, by combining the oxime ester-based photopolymerization initiator (A1) and the oxime ester-based photopolymerization initiator (A2) as in Examples 1 to 4, the oxime ester-based photopolymerization initiator (A1) alone is used. The absorption rate of h-rays in the upper part of the coating film can be made relatively lower than that in the case of (i), that is, the h-rays can be transmitted to the lower part of the coating film, and the coating film can be formed It is considered that the curing using the h-line at the lower portion is promoted, and the perpendicularity of the taper of the partition wall is improved. In addition, by using the oxime ester-based photopolymerization initiator (A1) and the oxime ester-based photopolymerization initiator (A2) in combination, curing using i-line and h-line is performed near the film surface, and the ink repellency is improved. Is also considered to be sufficient.
１　パターン
２　ガラス基板
３　パターン幅の最大値（最大幅）
４　パターン幅の最小値（最小幅） 1 pattern 2 glass substrate 3 maximum value of pattern width (maximum width)
4 Minimum pattern width (minimum width)

Claims (12)

  1. 　（Ａ）光重合開始剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、（Ｄ）着色剤、及び（Ｅ）撥液剤を含有する感光性着色樹脂組成物であって、
    　前記（Ａ）光重合開始剤が、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して２０％以上であるオキシムエステル系光重合開始剤（Ａ１）と、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して１０％以下であるオキシムエステル系光重合開始剤（Ａ２）を含有し、
    　前記（Ｅ）撥液剤が、架橋基を有するフッ素原子含有樹脂を含有することを特徴とする感光性着色樹脂組成物。     A photosensitive colored resin composition comprising (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent,
    (A) an oxime ester-based photopolymerization initiator (A1), wherein the photopolymerization initiator has an absorbance at a wavelength of 400 nm of 20% or more with respect to the absorbance at a maximum absorption wavelength (λ max ) of 300 to 400 nm. An oxime ester-based photopolymerization initiator (A2) whose absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a maximum absorption wavelength (λ max ) between 300 and 400 nm,
    (E) The photosensitive colored resin composition, wherein the liquid repellent comprises a fluorine atom-containing resin having a crosslinking group.
  2. 　前記オキシムエステル系光重合開始剤（Ａ１）が、ニトロ基及びカルバゾール骨格を有するオキシムエステル系光重合開始剤を含む、請求項１に記載の感光性着色樹脂組成物。 The photosensitive colored resin composition according to claim 1, wherein the oxime ester-based photopolymerization initiator (A1) includes an oxime ester-based photopolymerization initiator having a nitro group and a carbazole skeleton.
  3. 　前記オキシムエステル系光重合開始剤（Ａ２）が、下記一般式（Ａ２－１）で表される化合物を含む、請求項１又は２に記載の感光性着色樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式（Ａ２－１）中、Ｒ13Aは、置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。
    　Ｒ14Aは、アルキル基、又は芳香族環基を表す。
    　Ｒ15Aは、１価の置換基を表す。
    　ｎは０又は１を表す。
    　ｈは０～２の整数を表す。）     3. The photosensitive colored resin composition according to claim 1, wherein the oxime ester-based photopolymerization initiator (A2) contains a compound represented by the following general formula (A2-1).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (A2-1), R 13A represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
    R 14A represents an alkyl group or an aromatic ring group.
    R 15A represents a monovalent substituent.
    n represents 0 or 1.
    h represents an integer of 0 to 2. )
  4. 　前記式（Ａ２－１）において、Ｒ14Aが芳香族環基である、請求項３に記載の感光性着色樹脂組成物。 4. The photosensitive colored resin composition according to claim 3, wherein in the formula (A2-1), R 14A is an aromatic ring group.
  5. 　（Ａ）光重合開始剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、（Ｄ）着色剤、及び（Ｅ）撥液剤を含有する感光性着色樹脂組成物であって、
    　前記（Ａ）光重合開始剤が、波長４００ｎｍにおける吸光度が、波長３００～４００ｎｍ間の極大吸収波長（λmax）における吸光度に対して８～３０％であるオキシムエステル系光重合開始剤（Ａ３）を含有し、
    　前記（Ｅ）撥液剤が、架橋基を有するフッ素原子含有樹脂を含有することを特徴とする感光性着色樹脂組成物。     A photosensitive colored resin composition comprising (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent,
    The oxime ester-based photopolymerization initiator (A3), wherein the photopolymerization initiator (A) has an absorbance at a wavelength of 400 nm of 8 to 30% of an absorbance at a maximum absorption wavelength (λ max ) of 300 to 400 nm. Containing
    (E) The photosensitive colored resin composition, wherein the liquid repellent comprises a fluorine atom-containing resin having a crosslinking group.
  6. 　前記架橋基を有するフッ素原子含有樹脂が、パーフルオロアルキル基及びパーフルオロアルキレンエーテル鎖のいずれか一方又は両方を有する、請求項１～５のいずれか１項に記載の感光性着色樹脂組成物。 The photosensitive colored resin composition according to any one of claims 1 to 5, wherein the fluorine atom-containing resin having a crosslinking group has one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain.
  7. 　前記（Ｄ）着色剤が、赤色顔料及び橙色顔料からなる群から選ばれる少なくとも１種と、青色顔料及び紫色顔料からなる群から選ばれる少なくとも１種とを含有する、請求項１～６のいずれか１項に記載の感光性着色樹脂組成物。 The colorant according to any one of claims 1 to 6, wherein the colorant (D) contains at least one selected from the group consisting of red pigments and orange pigments, and at least one kind selected from the group consisting of blue pigments and purple pigments. The photosensitive colored resin composition according to claim 1 or 2.
  8. 　前記（Ｄ）着色剤が、下記一般式（１）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含む有機黒色顔料を含有する、請求項１～７のいずれか１項に記載の感光性着色樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
     （式（１）中、Ｒ11及びＲ16は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
    Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ17、Ｒ18、Ｒ19及びＲ20は各々独立に、水素原子、ハロゲン原子、Ｒ21、ＣＯＯＨ、ＣＯＯＲ21、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲ21、ＣＯＮＲ21Ｒ22、ＣＮ、ＯＨ、ＯＲ21、ＣＯＣＲ21、ＯＯＣＮＨ2、ＯＯＣＮＨＲ21、ＯＯＣＮＲ21Ｒ22、ＮＯ2、ＮＨ2、ＮＨＲ21、ＮＲ21Ｒ22、ＮＨＣＯＲ22、ＮＲ21ＣＯＲ22、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲ21、Ｎ＝ＣＲ21Ｒ22、ＳＨ、ＳＲ21、ＳＯＲ21、ＳＯ2Ｒ21、ＳＯ3Ｒ21、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲ21又はＳＯ2ＮＲ21Ｒ22を表し；
    Ｒ12とＲ13、Ｒ13とＲ14、Ｒ14とＲ15、Ｒ17とＲ18、Ｒ18とＲ19、及びＲ19とＲ20からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲ21ブリッジによって互いに結合してもよく；
    Ｒ21及びＲ22は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。）     The colorant (D) is at least one selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. The photosensitive colored resin composition according to any one of claims 1 to 7, comprising an organic black pigment containing:
    Figure JPOXMLDOC01-appb-C000002
     (In the formula (1), R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
    R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, a halogen atom, R 21 , COOH, COOR 21 , COO − , CONH 2 , CONHR 21 , CONR 21 R 22 , CN, OH, OR 21 , COCR 21 , OOCNH 2 , OOCNHR 21 , OOCNR 21 R 22 , NO 2 , NH 2 , NHR 21 , NR 21 R 22 , NHCOR 22 , NR 21 COR 22 , N = CH 2 , N = CHR 21 , N = CR 21 R 22 , SH, SR 21 , SOR 21 , SO 2 R 21 , SO 3 R 21 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR Represents 21 or SO 2 NR 21 R 22 ;
    R 12 and R 13, at least one combination selected from R 13 and R 14, R 14 and R 15, the group consisting of R 17 and R 18, R 18, R 19, and R 19 and R 20 are each other directly May be linked together or may be linked to each other by an oxygen, sulfur, NH or NR 21 bridge;
    R 21 and R 22 are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or Represents 2 to 12 alkynyl groups. )
  9. 　隔壁形成用である、請求項１～８のいずれか１項に記載の感光性着色樹脂組成物。 The photosensitive colored resin composition according to any one of claims 1 to 8, which is used for forming a partition.
  10. 　請求項１～９のいずれか１項に記載の感光性着色樹脂組成物を硬化させた硬化物。 A cured product obtained by curing the photosensitive colored resin composition according to any one of claims 1 to 9.
  11. 　請求項１０に記載の硬化物を含む画像表示装置。 An image display device comprising the cured product according to claim 10.
  12. 　請求項１０に記載の硬化物を含む照明。 An illumination comprising the cured product according to claim 10.
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