WO2016194619A1 - Composition de résine colorante photosensible, motif coloré, matrice noire, filtre de couleur, dispositif d'affichage à cristaux liquides, élément d'imagerie à semi-conducteurs, et procédé de production de filtre de couleur - Google Patents

Composition de résine colorante photosensible, motif coloré, matrice noire, filtre de couleur, dispositif d'affichage à cristaux liquides, élément d'imagerie à semi-conducteurs, et procédé de production de filtre de couleur Download PDF

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Publication number
WO2016194619A1
WO2016194619A1 PCT/JP2016/064828 JP2016064828W WO2016194619A1 WO 2016194619 A1 WO2016194619 A1 WO 2016194619A1 JP 2016064828 W JP2016064828 W JP 2016064828W WO 2016194619 A1 WO2016194619 A1 WO 2016194619A1
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group
resin composition
photosensitive resin
colored photosensitive
formula
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PCT/JP2016/064828
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English (en)
Japanese (ja)
Inventor
大西　治
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住友ベークライト株式会社
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Priority to KR1020177037236A priority Critical patent/KR20180012313A/ko
Priority to CN201680031343.1A priority patent/CN107615167A/zh
Priority to JP2017521792A priority patent/JPWO2016194619A1/ja
Publication of WO2016194619A1 publication Critical patent/WO2016194619A1/fr
Priority to HK18103523.0A priority patent/HK1244066A1/zh

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    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

Definitions

  • the present invention relates to a colored photosensitive resin composition, a colored pattern or black matrix, a color filter, a liquid crystal display device or a solid-state imaging device, and a method for producing a color filter.
  • a photosensitive resin composition For various display devices such as liquid crystal display devices and organic EL elements, colored patterns, black matrices, overcoats, ribs, spacers, and the like are used, and a photosensitive resin composition is used to form these.
  • a photosensitive resin composition generally comprises a binder resin, a polyfunctional monomer, a coloring material, a photo radical initiator, other additives, a solvent, and the like, and has adhesion to a substrate, transparency, heat resistance, Various functions such as yellowing resistance and developability are required.
  • Patent Document 1 discloses an acrylic colored photosensitive composition using an acrylic polymer containing methyl methacrylate and butyl methacrylate.
  • the resin composition as disclosed in the cited document 1 has a residual acrylic resin that is thermally decomposed and adhered to the substrate in the heating process at the time of fixing the pattern for each color, for example, when manufacturing a color filter. There is a concern that it may cause an inspection, or may cause a decrease in the life of an application such as an organic light emitting diode (OLED) or a liquid crystal display panel that requires low outgassing.
  • OLED organic light emitting diode
  • liquid crystal display panel that requires low outgassing.
  • the present inventors provide a colored photosensitive resin composition that is excellent in developability, adhesion, and pattern formability by using a specific polymer as a base resin, and excellent in heat resistance when used as a cured product. And found the present invention.
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms. N is 0, 1 or 2)
  • a colored pattern or a black matrix obtained by curing the colored photosensitive resin composition.
  • a color filter provided with the above-described coloring pattern or black matrix is provided.
  • a liquid crystal display device or a solid-state imaging device provided with the above color filter is provided.
  • the colored photosensitive resin composition of the present invention is excellent in developability, adhesion, and pattern formability, and excellent in heat resistance when used as a cured product. Therefore, the colored photosensitive resin composition of the present invention can be suitably used, for example, in a color filter manufacturing process.
  • the colored photosensitive resin composition of the present embodiment includes repeating units represented by the following formulas (1) and (2a), R 5 in the formula (2a) has a radical polymerizable group, and has 2 to A polymer that is 18 organic groups; A radical photopolymerization initiator; And a colorant.
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms. N is 0, 1 or 2)
  • the colored photosensitive resin composition of the present embodiment by using the above-described polymer, in addition to exhibiting various properties such as adhesion to the support, transparency, yellowing resistance, developability, etc., at the time of thermosetting It is possible to provide a photosensitive resin composition that generates very little outgas as a result of decomposition.
  • radicals are generated from the radical photopolymerization initiator, and a crosslinking reaction proceeds between the polymers via the radical polymerizable group contained in R 5 of the polymer. To do. Due to this action, a difference in dissolution rate with respect to the developer occurs, and dissolution proceeds in the non-exposed area, whereas a pattern remains in the exposed area. In the subsequent baking step, the remaining pattern is further cross-linked, and a function as a so-called permanent film is exhibited.
  • the colored photosensitive resin composition of the present embodiment comprises (A) a copolymer having a radical polymerizability (polymer P), (B) a photo radical polymerization initiator, and (C) a colorant as essential components.
  • This colored photosensitive resin composition may further contain (D) a solvent, (E) a radical polymerizable compound, and (F) a crosslinkable compound, if necessary.
  • another component may be mix
  • blended blended.
  • the polymer P includes repeating units represented by the following formulas (1) and (2a), R 5 in the formula (2a) is an organic group having 2 to 18 carbon atoms, and has a radical polymerizable group.
  • the polymer P preferably contains a structural unit represented by the following formula (2b) as a repeating unit.
  • the acid value of the polymer can be made moderate, and the solubility in an alkali developer can be adjusted.
  • the polymer P may have a structural unit represented by the following formula (2c) and / or formula (2d).
  • R 6 and R 7 are each independently an organic group having 1 to 18 carbon atoms.
  • the organic group having 1 to 30 carbon atoms constituting R 1 , R 2 , R 3 and R 4 may contain one or more atoms selected from O, N, S, P and Si in the structure. Good. Moreover, the organic group which comprises R ⁇ 1 >, R ⁇ 2 >, R ⁇ 3 > and R ⁇ 4 > does not have any acidic functional group. Thereby, control of the acid value in the polymer P can be facilitated.
  • examples of the organic group constituting R 1 , R 2 , R 3 and R 4 include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, And heterocyclic groups.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, An octyl group, a nonyl group, and a decyl group are mentioned.
  • alkenyl group examples include allyl group, pentenyl group, and vinyl group. An ethynyl group is mentioned as an alkynyl group.
  • Examples of the alkylidene group include a methylidene group and an ethylidene group.
  • Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group.
  • Examples of the alkaryl group include a tolyl group and a xylyl group.
  • Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
  • one or more hydrogen atoms may be substituted with halogen atoms.
  • the halogen atom include fluorine, chlorine, bromine, and iodine.
  • a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable.
  • any of R 1 , R 2 , R 3 and R 4 is preferably hydrogen, and in particular, R 1 , R 2 , R 3 and R 4 are all preferably hydrogen.
  • R 5 is an organic group having 2 to 18 carbon atoms, and has a radical polymerizable group that initiates radical polymerization by a photo radical polymerization initiator.
  • R 5 preferably has a carbon-carbon double bond at the terminal, and for example, preferably contains any of a vinyl group, a vinylidene group, an acryloyl group, and a methacryloyl group.
  • R 5 include an aliphatic hydrocarbon group having 2 to 18 carbon atoms. In this case, for example, any group of the following formulas (I) and (II) can be employed as R 5 .
  • R 5 is preferably the same in the plurality of repeating units represented by the formula (2a), but may be different for each repeating unit represented by the formula (2a).
  • R 5 an organic group having 8 to 18 carbon atoms including an aromatic ring may be used.
  • a vinylaryl group (—Ar—CH ⁇ CH 2 , Ar represents an aromatic hydrocarbon group) can be employed.
  • R 5 may not contain an acidic functional group.
  • the organic group having 1 to 18 carbon atoms constituting R 6 and R 7 in the formula (2c) may contain one or more atoms of O, N, S, P, and Si in the structure. Moreover, the organic group which comprises R ⁇ 6 > and R ⁇ 7 > shall not contain an acidic functional group. Thereby, control of the acid value in the polymer P can be facilitated.
  • examples of the organic group constituting R 6 and R 7 include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and a heterocyclic group. It is done.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a heptyl group.
  • alkenyl group examples include allyl group, pentenyl group, and vinyl group.
  • An ethynyl group is mentioned as an alkynyl group.
  • Examples of the alkylidene group include a methylidene group and an ethylidene group.
  • Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group.
  • Examples of the alkaryl group include a tolyl group and a xylyl group.
  • Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
  • one or more hydrogen atoms may be substituted with halogen atoms.
  • the halogen atom include fluorine, chlorine, bromine, and iodine.
  • a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable.
  • the polymer P is an alternating copolymer in which repeating units derived from a norbornene-type monomer represented by the following formula (3) and repeating units derived from maleic anhydride represented by the following formula (4) are alternately arranged.
  • a polymer is preferred.
  • the polymer P may be a random copolymer or a block copolymer.
  • the repeating unit derived from maleic anhydride shown in the following formula (4) means a structural unit shown in the above formulas (2a) to (2d).
  • n 0, 1 or 2
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms.
  • the polymer P in the present embodiment preferably has an acid value of, for example, 15 mgKOH / g polymer or more and 65 mgKOH / g polymer or less.
  • the acid value of the polymer P is derived from the structural unit represented by the formula (2a) (provided that the structural unit represented by the formula (2d) includes the structural unit represented by the formula (2d)).
  • This is an index of the amount of carboxyl groups to be produced. That is, the amount of carboxyl groups in the polymer P can be adjusted by controlling the acid value of the polymer P. Therefore, by controlling the acid value of the polymer P, it is possible to adjust the dissolution rate of the polymer P, which varies due to the amount of carboxyl groups, in the alkaline developer. In the photolithography process, it is important to adjust the dissolution rate in an alkali developer in order to achieve desired patterning performance. By setting the acid value of the polymer P in the above range, it is possible to realize an alkali dissolution rate of the colored photosensitive resin composition particularly suitable for patterning a permanent film.
  • the polymer P in this embodiment preferably has a peak area at a molecular weight of 1000 or less of 1% or less.
  • the present inventor has found that by reducing the amount of the low molecular weight component in the polymer P, the deformation of the pattern at the time of curing can be suppressed for the film formed by the polymer P. For this reason, the pattern shape of the film made of the colored photosensitive resin composition containing the polymer P is made favorable by setting the ratio of the peak area at a molecular weight of 1000 or less in the molecular weight distribution curve obtained by GPC to the above range. Can do.
  • the operation reliability can be improved.
  • the minimum of the quantity of the low molecular weight component in the polymer P is not specifically limited.
  • the polymer P in the present embodiment allows a case where the peak area at a molecular weight of 1000 or less is 0.01% or more of the whole in a molecular weight distribution curve obtained by GPC.
  • Mw (weight average molecular weight) / Mn number average molecular weight
  • Mw / Mn degree of dispersion indicating the width of the molecular weight distribution.
  • the present inventor has found that, by controlling the molecular weight distribution in the polymer P to a certain range, the deformation of the pattern at the time of curing of the film formed from the polymer P can be suppressed. For this reason, the pattern shape of the film
  • the Mw (weight average molecular weight) of the polymer P is, for example, 5,000 or more and 30,000 or less.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw / Mn molecular weight distribution
  • the low molecular weight component amount in the polymer P is the area of the component corresponding to the molecular weight of 1000 or less, which occupies the area of the entire molecular weight distribution based on, for example, data on molecular weight obtained by GPC measurement Calculated from the percentage of the sum.
  • the polymer P in this embodiment contains an alkali metal, for example.
  • the concentration of the alkali metal in the polymer P is, for example, 10 ppm or less (here, ppm means mass ppm).
  • ppm means mass ppm.
  • the process can be performed in a short time and under mild conditions. Moreover, compared with the process of opening an anhydrous ring using an acid catalyst, control of the ring-opening rate in the polymer P becomes easy.
  • the alkali metal concentration in the polymer P is determined by measuring the alkali metal concentration with respect to the polymer solid content diluted with N-methylpyrrolidone, if necessary, using a flameless atomic absorption photometer. Obtained.
  • an alkali metal contained in the polymer P in this embodiment Na, K, or Li is mentioned, for example.
  • These alkali metals are caused by the aqueous alkali solution in the ring-opening step (treatment S2) for opening the anhydride ring in the maleic anhydride-derived structural unit described later, for example.
  • the alkali dissolution rate of the polymer P in the present embodiment is, for example, 500 K / sec or more and 25000 K / sec or less, preferably 500 K / sec or more and 20,000 K / sec or less.
  • the alkali dissolution rate of polymer P is, for example, that polymer P is dissolved in propylene glycol monomethyl ether acetate and a polymer solution adjusted to a solid content of 20% by weight is applied onto a silicon wafer by a spin method, and this is applied at 110 ° C. for 100 seconds. It is calculated by impregnating a polymer film obtained by soft baking with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C.
  • the alkali dissolution rate of the polymer P By setting the alkali dissolution rate of the polymer P to 500 liters / second or more, the throughput in the development process using an alkali developer can be improved. Moreover, the residual film rate after the image development process by an alkali developing solution can be improved by making the alkali dissolution rate of the polymer P 25,000 kg / second or less. For this reason, it is possible to suppress film loss due to the lithography process.
  • the polymer P according to the present embodiment is manufactured as follows, for example.
  • n and R 1 to R 4 can be the same as those in the above formula (1).
  • norbornene-type monomer represented by the formula (3) include bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), which further has an alkyl group.
  • 2-norbornene common name: 2-norbornene
  • alkenyl group such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, etc.
  • Examples of those having an alkynyl group such as 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, and the like
  • Examples of those having an aralkyl group such as -2-norbornene include 5-benzyl-2-norbornene and 5-phenethyl-2-norbornene.
  • examples of the norbornene-type monomer include functional groups such as a group having a crosslinkability or a group containing a halogen atom such as fluorine in the structure of R 1 , R 2 , R 3 , and R 4 in the formula (3).
  • bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene) is preferably used from the viewpoint of light transmittance of the polymer.
  • the norbornene type monomer represented by the formula (3) and maleic anhydride are subjected to addition polymerization.
  • a copolymer (copolymer 1) of the norbornene type monomer represented by the formula (3) and maleic anhydride is formed by radical polymerization.
  • the molar ratio of the norbornene-type monomer represented by the formula (3) to maleic anhydride is 0.5: 1 to 1: 0. .5 is preferable.
  • the number of moles of the norbornene-type monomer represented by the formula (3): the number of moles of maleic anhydride 0.8: 1 to 1: 0.8.
  • a monomer that can be copolymerized in addition to the above-described norbornene-type monomer and maleic anhydride may be added. Examples of such a monomer include compounds containing a group having an ethylenic double bond in the molecule.
  • group having an ethylenic double bond examples include an allyl group, an acrylic group, a methacryl group, a maleimide group, and an aromatic vinyl group such as a styryl group and an indenyl group.
  • the polymerization method for example, a polymerization method using a radical polymerization initiator and, if necessary, a molecular weight adjusting agent is suitable.
  • methods such as suspension polymerization, solution polymerization, dispersion polymerization, and emulsion polymerization can be employed.
  • solution polymerization is preferable.
  • all the monomers may be charged all at once, or a part of them may be charged into a reaction vessel and the rest may be dropped.
  • the norbornene-type monomer represented by the formula (3), the maleic anhydride, and the polymerization initiator are dissolved in a solvent, and then heated for a predetermined time, whereby the norbornene-type monomer represented by the formula (3), Solution polymerization is performed with maleic anhydride.
  • the heating temperature is, for example, 50 to 80 ° C., and the heating time is 10 to 20 hours.
  • any one or more of diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate and the like can be used.
  • any one or more of an azo compound and an organic peroxide can be used.
  • the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis (2-methylpropionate), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN), Any one or more of these can be used.
  • organic peroxides include hydrogen peroxide, ditertiary butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Any one or more of them can be used.
  • the amount (number of moles) of the radical polymerization initiator is preferably 1% to 10% of the total number of moles of the norbornene-type monomer represented by the formula (3) and maleic anhydride.
  • the weight average molecular weight (Mw) of the resulting polymer can be adjusted to 5000-30000 by appropriately setting the amount of the polymerization initiator within the above range and appropriately setting the reaction temperature and reaction time.
  • the copolymer 1 having a repeating unit represented by the following formula (5) and a repeating unit represented by the following formula (6) can be polymerized.
  • R 1 in the structure of the formula (6) is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R 2 to R 4 .
  • n and R 1 to R 4 are the same as those in Formula (1) above. That is, n is 0, 1, or 2.
  • R 1 to R 4 are each independently selected. Or hydrogen or an organic group having 1 to 30 carbon atoms.In formula (6), R 1 to R 4 may be the same or different.
  • the repeating unit represented by the formula (5) and the repeating unit represented by the formula (6) may be randomly arranged, or may be alternately arranged. There may be. Moreover, the norbornene-type monomer shown by Formula (3) and maleic anhydride may be block copolymerized. However, from the viewpoint of ensuring the uniformity of solubility of the colored photosensitive resin composition using the polymer P produced in this embodiment, the repeating unit represented by the formula (5) and the formula (6) are used. It is preferable that the repeating unit is alternately arranged. That is, it is preferable that the copolymer 1 has a repeating unit represented by the following formula (7).
  • n and R 1 to R 4 are the same as those in the above formula (1). That is, n is 0, 1, or 2.
  • R 1 to R 4 are hydrogen or An organic group having 1 to 30 carbon atoms, R 1 to R 4 may be the same or different, and a is an integer of 10 or more and 200 or less.
  • R 1 in the structure of the formula (7) is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R 2 to R 4 .
  • a poor solvent for example, hexane or methanol
  • low molecular weight components such as residual monomers and oligomers.
  • a low molecular weight component a residual monomer, an oligomer, a polymerization initiator, and the like are included.
  • filtration is performed, and the obtained coagulum is dried. Thereby, the polymer which has the copolymer 1 from which the low molecular weight component was removed as a main component (main product) can be obtained.
  • a metal alkoxide as a base acts on a structural unit derived from maleic anhydride.
  • the structural unit derived from maleic anhydride is esterified with an alcohol (metal alkoxide) that is used simultaneously with ring opening. Therefore, in the present specification, this step is also referred to as “esterification step”.
  • the degree of esterification of the structural unit derived from maleic anhydride is referred to as “esterification rate”.
  • reaction liquid L1 is obtained.
  • a part of the anhydride ring of the repeating unit derived from the maleic anhydride of the copolymer 1 is opened, and a part of the terminal formed by the ring opening is esterified. The remaining terminals are not esterified and have a metal salt structure.
  • the number of moles of metal alkoxide, alkali metal salt or alkali hydroxide is preferably 50% or less of the number of moles of maleic anhydride used in the polymerization step.
  • the number of moles of metal alkoxide, alkali metal salt or alkali hydroxide is preferably 40% or less of the number of moles of maleic anhydride used in the polymerization step, and more preferably 30% or less. preferable.
  • the number of moles of metal alkoxide, alkali metal salt, or alkali hydroxide can be 10% or more of the number of moles of maleic anhydride used in the polymerization step.
  • metal alkoxide those represented by M (OR 5 ) (M is a monovalent metal and R 5 is an organic group having 1 to 18 carbon atoms) are preferable.
  • the metal M include alkali metals, and sodium is preferable from the viewpoint of handleability.
  • the R 5, are the same as those for R 5 in formula (2a). Two or more different metal alkoxides may be used. However, from the viewpoint of production stability, it is preferable to use one kind of metal alkoxide.
  • the maleic anhydride-derived structure of the copolymer 1 may be opened in the presence of ( ⁇ ) an alcohol and an alkali metal hydroxide as a base.
  • an alcohol As the alkali metal salt or alkali hydroxide, sodium hydroxide or sodium acetate is preferable from the viewpoint of handleability.
  • the alcohol monovalent alcohol (R 5 OH) is preferable.
  • R 5 which is an organic group, those described above can be used.
  • Examples of the alcohol or the alcohol as a raw material for the metal alkoxide include allyl alcohol, methallyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, 4-penten-1-ol, 5 -Hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decene-1-ol, 10-undecen-1-ol, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, and 1,4-cyclohexanedimethanol monomethacrylate Doo and the like, can be used any one or more of these.
  • the repeating unit derived from maleic anhydride opened in this ring-opening step (treatment S3) has a structure represented by the following formula (8), and has a structure having a carboxyl group salt moiety. What has this structure of Formula (8) is called the copolymer 2.
  • the structure of Formula (8) and the structure shown by Formula (10), which will be described later, describe sodium ions as the corresponding metal ions, other metal ions are adopted in view of the reactivity of the metal alkoxide. You can also
  • R 5 is the same as R 5 described above, and is derived from the alcohol or metal alkoxide described above.
  • R 5 in the formula (9) is the same as R 5 mentioned above, is derived from an alcohol or a metal alkoxide mentioned above.
  • R 5 is the same as R 5 described above.
  • the structure has a structure represented by the following formula (12).
  • the copolymer 3 obtained by acid-treating the copolymer 2 is represented by the above-described repeating unit represented by the formula (6), the repeating unit represented by the formula (5), and the formula (11). It has a repeating unit and, optionally, a structure of formula (9) and a structure of formula (12). Of the total number of structural units derived from maleic anhydride, the repeating unit represented by the formula (5) is preferably 60% or less, and more preferably 50% or less.
  • the structure has the following formulas (13) and (14) as repeating units, and a structure derived from a norbornene monomer and a structure derived from a maleic anhydride monomer are alternately arranged. .
  • n and R 1 to R 4 are the same as in the above formula (1). That is, n is 0, 1, or 2.
  • R 1 to R 4 are hydrogen or an organic group having 1 to 30 carbon atoms. R 1 to R 4 may be the same or different.
  • Z represents either one of —O—H and —O—R 5
  • W represents a structure that represents one of the other, although slightly, Z and Any structure in which W is —O—R 5 is included.
  • R 5 is the same as R 5 described above.
  • the repeating unit represented by the formula (14) may include a structure in which both Z and W are —O—H.
  • R 1 is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R 2 to R 4 .
  • R 1 is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R 2 to R 4 , W, and Z.
  • the above-described cleaning step (processing S4) is repeated, for example, 5 times or more, more preferably 10 times. Thereby, the density
  • solvent replacement step (Process S5)) After the washing step (processing S4), solvent replacement can be performed. Solvent replacement can be performed, for example, by removing the compounds used in steps S1 to S4 by distillation under reduced pressure and replacing the system while adding a product solvent such as PGMEA (propylene glycol monomethyl ether acetate). .
  • PGMEA propylene glycol monomethyl ether acetate
  • Heating step (Process S6)
  • an alkali developer of polymer P for example, TMAH (tetramethylammonium hydroxide)
  • the heating step can be performed when it is necessary to strictly adjust the dissolution rate.
  • the dissolution rate of the polymer P in the alkaline developer can be further adjusted by heating the copolymer 3.
  • the heating step (processing S6) can be performed, for example, under conditions of 100 ° C. or more and 140 ° C. or less, and 0.5 hours or more and 10 hours or less. These heat treatment conditions can be appropriately adjusted according to the desired dissolution rate.
  • this heating step (processing S6) a part of the carboxyl groups of the copolymer 3, that is, the carboxyl groups formed at the ends of the ring-opening structure of the structure derived from maleic anhydride are esterified.
  • the ring-opening structure of the structure derived from maleic anhydride of the copolymer 3 is dehydrated and closed again. Therefore, the copolymer 4 obtained through this step has a repeating unit represented by the above formula (6), a repeating unit represented by the formula (5), a repeating unit represented by the formula (11), and the following: And a repeating unit represented by the formula (15).
  • R 6 and R 7 are the same as R 6 and R 7 in the formula (2c), comprising a structure which is independent organic group having 1 to 18 carbon atoms.
  • R 7 is R 5 described above, and the organic group having 1 to 18 carbon atoms of R 6 is derived from the alcohol used in this heating step (processing S6).
  • the structure represented by the formula (15) may include the structure represented by the formula (9).
  • R 6 and R 7 in the formula (15) are the same group as R 5 shown in the formula (9).
  • the structure represented by Formula (15) may include a structure in which two carboxyl groups are esterified in Formula (12). In this case, R 6 and R 7 are both derived from the alcohol used in the main heating step (processing S6).
  • the product (polymer) which uses the copolymer 4 as a main product can be obtained.
  • the copolymer 4 preferably has a structure in which a structure derived from a norbornene monomer and a structure derived from a maleic anhydride monomer are alternately arranged. And it is preferable that the copolymer 4 has a structure shown by Formula (16) in addition to Formula (13), (14) mentioned above.
  • n and R 1 to R 4 are the same as in the above formula (1). That is, n is 0, 1, or 2.
  • R 1 to R 4 are hydrogen or an organic group having 1 to 30 carbon atoms. R 1 to R 4 may be the same or different.
  • X represents one of —O—R 6 and —O—R 7
  • Y represents the other.
  • R 6 and R 7 are the same as in the above formula (15).
  • the proportion of the polymer P in the colored photosensitive resin composition is preferably 10% by mass to 70% by mass when the total solid content of the colored photosensitive resin composition (that is, the component excluding the solvent) is 100% by mass. More preferably, it is 20% by mass to 60% by mass.
  • the colored photosensitive resin composition of this embodiment contains the photoradical polymerization initiator which generate
  • the radical photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2 -Hydroxy-2-methylpropionyl) benzyl] phenyl ⁇ -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl
  • the radical photopolymerization initiator is preferably 5 to 20 parts by mass, more preferably 8 to 15 parts by mass with respect to 100 parts by mass of the polymer P. Is preferred.
  • a sensitivity and a crosslinking degree can be further improved by using a photosensitizer and a photoradical polymerization accelerator with the said photoradical initiator.
  • a photosensitizer and a photoradical polymerization accelerator with the said photoradical initiator.
  • dye compounds such as xanthene dyes and coumarin dyes, dialkylaminobenzene compounds such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, etc.
  • mercapto-based hydrogen donors mercapto-based hydrogen donors.
  • the total amount of the photosensitizer and radical photopolymerization accelerator added is not particularly limited, but is preferably 0.001 to 5 parts by weight, preferably 100 to 5 parts by weight with respect to 100 parts by weight of the polymer P from the viewpoint of curability and economy. Is 0.01 to 1 part by weight.
  • the colored photosensitive resin composition of the present embodiment contains a conventionally known pigment or dye.
  • a pigment an organic pigment or an inorganic pigment can be used.
  • Organic pigments include azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, metal complex System, diketopyrrolopyrrole, etc.), dye lake pigments, etc. can be used.
  • Inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (yellow lead, cadmium, chrome vermilion, nickel titanium, chrome titanium) , Yellow iron oxide, bengara, zinc chromate, red lead, ultramarine, bitumen, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.), black pigment (carbon black, bone black, graphite, iron black, titanium black, etc.) Bright pigments (pearl pigments, aluminum pigments, bronze pigments, etc.) and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.
  • white and extender pigments titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.
  • the pigment colors that can be used include yellow, red, purple, blue, green, brown, black, and white.
  • dye for example, known dyes described in JP-A No. 2003-270428, JP-A No. 9-171108, JP-A No. 2008-50599 and the like can be used.
  • the above colorants can be used alone or in combination of two or more.
  • those having an appropriate average particle diameter can be used according to the purpose and application.
  • transparency such as a color resist for color filters
  • it is as small as 0.1 ⁇ m or less.
  • An average particle diameter is preferable, and when a concealing property such as a paint is required, a large average particle diameter of 0.5 ⁇ m or more is preferable.
  • the above-described coloring material is subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose and application. Also good.
  • the content ratio of the colorant in the colored photosensitive resin composition of the present embodiment may be appropriately set according to the purpose and application.
  • the colored photosensitive resin composition When the total solid content of the product (that is, the component excluding the solvent) is 100% by mass, it is preferably 3% by mass to 70% by mass, more preferably 5% by mass to 60% by mass, and even more preferably 10% by mass. % By mass to 50% by mass.
  • the colored photosensitive resin composition of the present embodiment may contain a solvent.
  • the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl n -Amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or a mixture thereof can be employed. In addition, it is not limited to what was illustrated here.
  • the colored photosensitive resin composition of the present embodiment includes a radical polymerizable compound (also referred to as a first crosslinking agent) that crosslinks with the polymer P by the radical polymerization initiator.
  • a radical polymerizable compound also referred to as a first crosslinking agent
  • the radical polymerizable compound (first crosslinking agent) is preferably a polyfunctional acrylic compound having two or more (meth) acryloyl groups.
  • ethylene glycol di (meth) acrylate diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di ( (Meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) a Lilate, dipentaerythritol hexa (meth) acrylate
  • Allyl group-containing (meth) a Polyfunctionals such as tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri (methacryloyloxyethyl) isocyanurate (Meth) acryloyl group-containing isocyanurates; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and 2-hydroxyethyl (meth) acrylate Polyfunctional urethane (meth) acrylate obtained by reaction with hydroxyl group-containing (meth) acrylic esters such as 2-hydroxypropyl (meth) acrylate Preparative like; polyfunctional aromatic vinyl compounds such
  • trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate
  • tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate
  • hexafunctional (meth) acrylates such as acrylate and dipentaerythritol hexa (meth) acrylate, and any one or more of these is preferably used.
  • the polyfunctional acrylic compound and the polymer P can be cross-linked by radicals generated by the radical polymerization initiator, and the polyfunctional acrylic compound can also be cross-linked. it can.
  • membrane with a high degree of crosslinking and high chemical resistance can be formed.
  • the content thereof is preferably 30 to 70 parts by mass, more preferably 50 to 100 parts by mass of the polymer P. It is preferably from ⁇ 60 parts by mass.
  • the colored photosensitive resin composition of the present embodiment may contain a crosslinkable compound (also referred to as a second crosslinker) different from the radical polymerizable compound (first crosslinker). .
  • This crosslinkable compound (second crosslinking agent) crosslinks with the polymer P by heat.
  • This crosslinkable compound (second crosslinker) is preferably a compound having a cyclic ether group as a reactive group, and more preferably a compound having a glycidyl group or an oxetanyl group.
  • An example of the compound having a glycidyl group is an epoxy compound. More specifically, for example, bisphenol A epoxy resin (for example, “LX-1” manufactured by Daiso Chemical Co., Ltd.), 2,2 ′-((((1- (4- (2- (4- (oxirane-2 -Ylmethoxy) phenyl) propan-2-yl) phenyl) ethane-1,1-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane) (eg Purin Co., Ltd.) "Techmore VG3101L” manufactured by Tech Co.), trimethylolpropane triglycidyl ether (for example, "TMPTGE” manufactured by CVC Specialty Chemicals), and 1,1,3,3,5,5-hexamethyl-1,5-bis ( 3- (oxiran-2-ylmethoxy) propyl) trisiloxane (for example, “DMS-E0 manufactured by Gelest
  • a polyfunctional alicyclic epoxy resin etc. can also be used from a viewpoint of the transparency of the effect material of a coloring photosensitive resin composition, and a dielectric constant improvement.
  • a polyfunctional alicyclic epoxy resin what is shown by the following chemical formula can be used, for example.
  • This epoxy resin is, for example, Poly [(2-oxylanyl) -1,2-cyclohexanediol] 2-ethyl-2- (hydroxymethyl) -1,3-propandiol ether (3: 1). Any one or more of the above can be used. In addition, it is not limited to the illustration here.
  • R 36 is a hydrocarbon group having 1 to 10 carbon atoms, s is an integer of 1 to 30, and t is an integer of 1 to 6.
  • any of the following can be used, for example.
  • the content thereof is preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polymer P. Further, it is preferably 15 to 25 parts by mass.
  • the colored photosensitive resin composition of the present embodiment includes a filler, a binder resin other than the above-mentioned polymer P, a dispersant, a heat improver, and a development aid depending on the purpose and required characteristics of each application.
  • Components other than the above essential components such as coupling agents such as silane, aluminum, and titanium, quinonediazide compounds, polyhydric phenol compounds, cationic polymerizable compounds, and acid generators may be blended.
  • the colored photosensitive resin composition of the present embodiment can be produced, for example, by subjecting a colorant to a dispersion treatment step and mixing it with other components. For example, first, a predetermined amount of each of a colorant, a dispersant, a binder resin, and a solvent is weighed, and the colorant is finely dispersed using a disperser such as a paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender, etc. Thus, a liquid colorant dispersion (mill base) is obtained.
  • a disperser such as a paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender, etc.
  • fine dispersion with a media mill such as a bead mill filled with 0.01 to 1 mm beads.
  • a transparent resist solution containing a radical polymerizable compound, a photoinitiator, a binder resin, a solvent, a leveling agent, etc., which has been separately stirred and mixed is added and mixed to obtain a uniform dispersion solution, which is colored photosensitive.
  • a resin composition is obtained.
  • the obtained colored photosensitive colored resin composition is desirably filtered through a filter or the like to remove fine dust.
  • the colored photosensitive resin composition of the present embodiment is preferably used for producing a color filter.
  • a color filter to which the colored photosensitive resin composition of the present embodiment is applied will be described with reference to FIG.
  • Such a color filter can be applied to a liquid crystal display device or a solid-state imaging device.
  • a color filter 100 shown in FIG. 1 is obtained by forming a black matrix 20 and a colored pattern 30 on a support 10. Further, a protective film 40 and a transparent electrode are formed on the black matrix 20 and the colored pattern 30. A layer 50 is provided.
  • the support 10 is usually made of a material that transmits light.
  • the support 10 is made of a polymer of polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin in addition to glass.
  • the support 10 may be subjected to corona discharge treatment, ozone treatment, chemical solution treatment, or the like as necessary.
  • the support 10 is preferably made of glass.
  • the black matrix 20 is composed of, for example, a cured product of a colored photosensitive resin composition in the case where a black pigment or a black dye is used as the colorant described above.
  • this black matrix 20 may be formed by another method.
  • the coloring pattern 30 in the color filter 100 usually has three colors of red, green, and blue.
  • the colored pattern 30 is composed of a cured product of the colored photosensitive resin composition when a pigment or dye corresponding to this color is used as the above-described colored photosensitive resin composition.
  • this colored pattern 20 may be formed by another method.
  • This protective film can be appropriately selected from known inorganic materials or organic materials used as protective films for color filters.
  • the color filter 100 shown in FIG. 1 includes a transparent electrode layer 50.
  • the transparent electrode layer 50 is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof.
  • ITO indium tin oxide
  • ZnO zinc oxide
  • SnO tin oxide
  • an alloy thereof As a specific forming method, a known method can be adopted. For example, a sputtering method, a vacuum deposition method, a CVD method, or the like can be adopted.
  • a method of manufacturing the color filter 100 is as follows.
  • the black matrix 20 and the coloring pattern 30 will be described by taking the case where the colored photosensitive resin composition of the present embodiment is applied as an example.
  • the colored photosensitive resin composition of this embodiment is apply
  • the colored photosensitive resin composition applied to the support 10 contains a black pigment or a black dye.
  • application methods such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, and the like can be used. Among these, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.
  • the support 10 is heated at an appropriate temperature and time to remove almost all of the solvent to form a coating film.
  • the heating temperature and time are, for example, 60 to 130 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes.
  • the thickness of the colored photosensitive resin composition layer (coating film) is preferably 1.0 to 5.0 ⁇ m.
  • Pattern formation on the coating film is performed by irradiating actinic rays or the like using a mask for forming a target pattern.
  • active light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; argon ion lasers, YAG Laser light sources such as lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers are used.
  • the target black matrix 20 can be obtained by further heating (see FIG. 2C).
  • Examples of the development method include a shower development method, a spray development method, and an immersion development method.
  • the development condition is usually about 1 to 10 minutes at 23 ° C.
  • alkali developer examples include alkaline aqueous solutions having a concentration of about 0.1 to 10% by mass such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide and the like.
  • the film can be further baked at 150 to 300 ° C. for 30 to 120 minutes and sufficiently cured to obtain a desired pattern.
  • the curing conditions are not limited to the above.
  • a colored photosensitive resin composition containing any one of red, green, and blue pigments or dyes is applied to the support 10 on which the black matrix 20 is formed, exposed, developed, and cured, so that a colored pattern 30 is obtained. Get. By repeating this operation, both the black matrix 20 and the colored pattern 30 can be formed on the support 10 (see FIG. 2D).
  • a protective film 40 is formed on the black matrix 20 and the colored pattern 30 (see FIG. 2E).
  • a known method can be adopted according to the material constituting the protective film 40.
  • a transparent electrolytic layer 50 is provided on the protective film 40 (see FIG. 2 (f)).
  • a method such as a sputtering method, a vacuum vapor deposition method, or a CVD method can be employed as the formation method.
  • ⁇ Synthesis Example 2 10.0 g of a copolymer of 2-norbornene and maleic anhydride synthesized in the same manner as in Synthesis Example 1 is dissolved in 30 g of methyl ethyl ketone, and further 40.0 g of 2-hydroxyethyl methacrylate, 0.5 g of hydroquinone, sodium acetate 0 Mixed with 0.5 g and reacted at 80 ° C. for 16 hours. After the reaction, 25 g of acetone and 1.0 g of formic acid were mixed and added dropwise to 750 g of pure water to reprecipitate and purify the polymer.
  • the polymer thus obtained had a weight average molecular weight (Mw) of 13,000 and a dispersity of 1.87.
  • the alkali dissolution rate was 22800 kg / sec.
  • the esterification rate determined by NMR was 90%.
  • Example 1 5.0 g of the polymer synthesized in Synthesis Example 1, 0.5 g of Irgacure OXE02 (manufactured by BASF) as a photopolymerization initiator, 7.5 g of a pigment dispersion (NX-501 manufactured by Dainichi Seika Co., Ltd .; pigment content 58%), 15.0 g of cyclohexanone was mixed.
  • the white photosensitive resin composition thus prepared was applied on soda glass (100 mm ⁇ 100 mm square, thickness 1.0 mm) by spin coating, and then heated on a hot plate at 100 ° C. for 2 minutes to give a film thickness of 10 ⁇ m. A coating film was obtained.
  • This coating film was exposed at 200 mJ / cm 2 with a g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. through a mask having L / S patterns of 10 ⁇ m, 20 ⁇ m and 50 ⁇ m. This was dip-developed with a 0.1N aqueous potassium hydroxide solution at 23 ° C. for 4 minutes and then rinsed with pure water. Then, the board
  • developability, adhesion, and pattern formability were evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
  • heat treatment was performed by heating at 230 ° C. for 60 minutes in an oven.
  • the pattern after processing was evaluated based on the following evaluation criteria for heat resistance and heat discoloration.
  • Example 2 Evaluation was performed in the same manner as in Example 1 except that the polymer was changed to that obtained in Synthesis Example 2. The evaluation results are summarized in Table 1.
  • Example 3 5.0 g of the polymer synthesized in Synthesis Example 2, 2.5 g of dipentaerythritol hexaacrylate (A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.5 g of Irgacure OXE02 (manufactured by BASF) as a photopolymerization initiator Then, 7.5 g of a pigment dispersion (NX-595 manufactured by Dainichi Seika Co., Ltd.) and 15.0 g of cyclohexanone were mixed.
  • A-DPH dipentaerythritol hexaacrylate
  • Irgacure OXE02 manufactured by BASF
  • the black photosensitive resin composition thus prepared was applied onto soda glass (100 mm ⁇ 100 mm square, thickness 1.0 mm) by spin coating, and then heated on a hot plate at 100 ° C. for 2 minutes to give a film thickness of 10 ⁇ m.
  • a coating film was obtained.
  • This coating film was exposed at 200 mJ / cm 2 with a g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. through a mask having L / S patterns of 10 ⁇ m, 20 ⁇ m and 50 ⁇ m.
  • PPA-501F g + h + i line mask aligner
  • This was dip-developed with a 0.1N aqueous potassium hydroxide solution at 23 ° C. for 4 minutes and then rinsed with pure water.
  • substrate was dried by high speed rotation and the L / S pattern was created.
  • the developability, adhesion, pattern formability, heat resistance, and heat discoloration here were evaluated based on the above evaluation criteria. The
  • Example 4 Evaluation was performed in the same manner as in Example 2 except that the pigment dispersion was changed to Dainichi Seika Co., Ltd .: NX-061 to obtain a green photosensitive resin composition.
  • Example 5 Evaluation was made in the same manner as in Example 2 except that the pigment dispersion was changed to NX-053 manufactured by Dainichi Seika Co., Ltd. and the blue photosensitive resin composition was used.
  • Example 6 Evaluation was performed in the same manner as in Example 2, except that the pigment dispersion was changed to NX-032 manufactured by Dainichi Seika Co., Ltd. and a red photosensitive resin composition was used.
  • ⁇ Comparative Example 1> 6 5.0 g of the polymer synthesized in Comparative Synthesis Example 1, 5.0 g of dipentaerythritol hexaacrylate (A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.), Irgacure OXE02 (manufactured by BASF) as a photopolymerization initiator 5 g and 15.0 g of cyclohexanone were mixed to obtain a white photosensitive resin composition. Evaluation was performed in the same manner as in Example 1. The evaluation results are summarized in Table 1.
  • a colored photosensitive resin composition having excellent developability, adhesion, and pattern moldability, and excellent heat resistance when cured is provided. can do.

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Abstract

L'invention concerne une composition de résine colorante photosensible qui contient : un polymère qui contient des unités de répétition représentées par la formule (1) et la formule (2a), et R5 dans la formule (2a) étant un groupe organique ayant un groupe polymérisable par voie radicalaire et 2 à 18 atomes de carbone; un initiateur de photopolymérisation radical; et un agent colorant. (Dans la formule (1), chacun de R1, R2, R3 et R4 représente indépendamment un atome d'hydrogène ou un groupe organique ayant 1 à 30 atomes de carbone; et n représente 0, 1 ou 2.)
PCT/JP2016/064828 2015-05-29 2016-05-19 Composition de résine colorante photosensible, motif coloré, matrice noire, filtre de couleur, dispositif d'affichage à cristaux liquides, élément d'imagerie à semi-conducteurs, et procédé de production de filtre de couleur WO2016194619A1 (fr)

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KR1020177037236A KR20180012313A (ko) 2015-05-29 2016-05-19 착색 감광성 수지 조성물, 착색 패턴 또는 블랙 매트릭스, 컬러 필터, 액정 표시 장치 또는 고체 촬상 소자 및 컬러 필터의 제조 방법
CN201680031343.1A CN107615167A (zh) 2015-05-29 2016-05-19 着色感光性树脂组合物、着色图案或黑矩阵、滤色器、液晶显示装置或固体摄像元件和滤色器的制造方法
JP2017521792A JPWO2016194619A1 (ja) 2015-05-29 2016-05-19 着色感光性樹脂組成物、着色パターンまたはブラックマトリクス、カラーフィルタ、液晶表示装置または固体撮像素子およびカラーフィルタの製造方法
HK18103523.0A HK1244066A1 (zh) 2015-05-29 2018-03-13 着色感光性樹脂組合物、着色圖案或黑矩陣、濾色器、液晶顯示裝置或固體攝像元件和濾色器的製造方法

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JP2020126117A (ja) * 2019-02-04 2020-08-20 三菱ケミカル株式会社 感光性着色樹脂組成物、硬化物、及び画像表示装置
WO2021060080A1 (fr) * 2019-09-26 2021-04-01 住友ベークライト株式会社 Polymère, composition de résine photosensible, film de résine et dispositif électronique
JP2021063933A (ja) * 2019-10-16 2021-04-22 住友ベークライト株式会社 樹脂組成物、感光性樹脂組成物、フィルム、カラーフィルタ、ブラックマトリクス、表示装置および撮像素子

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JP6332583B1 (ja) * 2017-01-10 2018-05-30 住友ベークライト株式会社 ネガ型感光性樹脂組成物、樹脂膜及び電子装置
WO2018131351A1 (fr) * 2017-01-10 2018-07-19 住友ベークライト株式会社 Composition de résine photosensible négative, film de résine et dispositif électronique
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CN110178085A (zh) * 2017-01-10 2019-08-27 住友电木株式会社 负型感光性树脂组合物、树脂膜和电子装置
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TWI759378B (zh) * 2017-01-10 2022-04-01 日商住友電木股份有限公司 負型感光性樹脂組成物、樹脂膜及電子裝置
CN110462512B (zh) * 2017-03-28 2021-07-06 住友电木株式会社 感光性组合物、彩色滤光片及由其衍生的微透镜
US10915019B2 (en) 2017-03-28 2021-02-09 Promerus, Llc Photosensitive compositions, color filter and microlens derived therefrom
JP2020515893A (ja) * 2017-03-28 2020-05-28 プロメラス， エルエルシー 感光性組成物、カラーフィルタ及びそれに由来するマイクロレンズ
CN110462512A (zh) * 2017-03-28 2019-11-15 普罗米鲁斯有限责任公司 感光性组合物、彩色滤光片及由其衍生的微透镜
JP7051893B2 (ja) 2017-03-28 2022-04-11 プロメラス， エルエルシー 感光性組成物、カラーフィルタ及びそれに由来するマイクロレンズ
WO2018183413A1 (fr) 2017-03-28 2018-10-04 Promerus, Llc Compositions photosensibles, filtre coloré et microlentille associés à celles-ci
US20180284609A1 (en) * 2017-03-28 2018-10-04 Promerus, Llc Photosensitive compositions, color filter and microlens derived therefrom
JP2020126117A (ja) * 2019-02-04 2020-08-20 三菱ケミカル株式会社 感光性着色樹脂組成物、硬化物、及び画像表示装置
JP7331371B2 (ja) 2019-02-04 2023-08-23 三菱ケミカル株式会社 感光性着色樹脂組成物、硬化物、及び画像表示装置
WO2021060080A1 (fr) * 2019-09-26 2021-04-01 住友ベークライト株式会社 Polymère, composition de résine photosensible, film de résine et dispositif électronique
JP2021063933A (ja) * 2019-10-16 2021-04-22 住友ベークライト株式会社 樹脂組成物、感光性樹脂組成物、フィルム、カラーフィルタ、ブラックマトリクス、表示装置および撮像素子

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