WO2013031736A1 - Negative photosensitive resin composition, partition wall, black matrix and optical element - Google Patents

Negative photosensitive resin composition, partition wall, black matrix and optical element Download PDF

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Publication number
WO2013031736A1
WO2013031736A1 PCT/JP2012/071612 JP2012071612W WO2013031736A1 WO 2013031736 A1 WO2013031736 A1 WO 2013031736A1 JP 2012071612 W JP2012071612 W JP 2012071612W WO 2013031736 A1 WO2013031736 A1 WO 2013031736A1
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WIPO (PCT)
Prior art keywords
group
photosensitive resin
resin composition
negative photosensitive
solvent
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PCT/JP2012/071612
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French (fr)
Japanese (ja)
Inventor
光太郎 山田
高橋　秀幸
川島　正行
正樹 小尾
Original Assignee
旭硝子株式会社
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Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to CN201280042629.1A priority Critical patent/CN103782237B/en
Priority to KR1020147005071A priority patent/KR101940844B1/en
Priority to JP2013531308A priority patent/JP5994782B2/en
Publication of WO2013031736A1 publication Critical patent/WO2013031736A1/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/027—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
    • G03F7/038—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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • 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
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H10K59/8792—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. black layers

Definitions

  • the present invention relates to a negative photosensitive resin composition, a partition using the same, a black matrix, and an optical element having the partition.
  • a partition used in a pixel portion of a color filter or an organic EL (Electro-Luminescence) element is known to be formed by applying a photosensitive resin composition to a substrate and using a photolithography technique.
  • the photosensitive resin composition is applied by using a spin coating method. As the size of the substrate increases, coating by spin coating becomes difficult, and a coating method by slit coating has been proposed.
  • the viscosity of the photosensitive resin composition is preferably less than 3.5 mPa ⁇ s in order to obtain good film thickness uniformity, depending on the coating speed.
  • the viscosity of the photosensitive resin composition is high, the photosensitive resin composition supplied from the slit nozzle runs out of liquid, resulting in a portion that is not applied to the substrate surface.
  • High contrast is one of the required characteristics for color filters.
  • a photosensitive resin composition capable of producing a black matrix having high light shielding properties.
  • a photosensitive resin composition containing a pigment in a high concentration has been proposed (for example, Patent Document 4).
  • the photosensitive resin composition capable of producing a black matrix having a high light-shielding property needs to contain a pigment at a high concentration as proposed in Patent Document 4, but as the pigment concentration increases, the photosensitive resin composition The re-solubility of becomes worse. According to the knowledge of the present inventor, in a photosensitive resin composition containing a pigment at a high concentration for high contrast, re-solubility is satisfied even when a solvent proposed in the prior art is used. However, in the coating film obtained by applying the photosensitive resin composition described in Patent Document 4 by the slit coating method, defects due to the dried solidified product are likely to occur.
  • the present invention makes it possible to produce a black matrix having a high concentration of pigment and a high light-shielding property, and has a high re-dissolvability to dissolve its own dried solidified product, resulting in defects in the coating film obtained by the slit coating method.
  • An object of the present invention is to provide a negative photosensitive resin composition having a viscosity capable of being applied by a slit coating method, and a partition and a black matrix using the same.
  • an object of this invention is to provide the optical element which has a partition with high light-shielding property formed by hardening
  • the present invention provides a negative photosensitive resin composition, partition walls, a black matrix and an optical element having the following configurations [1] to [12].
  • a negative photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerization initiator (B), a black colorant (C), and a solvent (D), the total solid content of the composition
  • the content of the black colorant (C) is more than 20% by mass
  • the solvent (D1) is a compound represented by the following formula (1) with respect to the total amount of the solvent (D).
  • a negative photosensitive resin composition characterized by comprising 20 to 100% by mass.
  • R 1 represents a methyl group
  • R 2 represents an alkyl group having 2 or 3 carbon atoms.
  • R 3 represents a hydrogen atom
  • R 61 or OR 62 each of R 61 and R 62 independently represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom in a cycloalkane ring Is a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group A 6-30 phenyl group or a phenylalkyl group having 7-30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group is shown.
  • R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 30 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
  • a phenoxycarbonyl group or a cyano group A phenoxycarbonyl group or a cyano group.
  • R 5 represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group.
  • An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
  • R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R 61 , OR 62 , an alkanoyl group having 2 to 20 carbon atoms, or a hydrogen atom in the benzene ring.
  • a benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom
  • R 0 represents R 61 , OR 62 , a cyano group or a halogen atom.
  • a is 0 or an integer of 1 to 3.
  • a partition formed so as to partition the substrate surface into a plurality of sections for pixel formation, and comprising a cured film of the negative photosensitive resin composition according to any one of [1] to [9] Features a partition wall.
  • An optical element having a plurality of pixels and a partition located between adjacent pixels on the surface of the substrate, wherein the partition is formed of the partition of [10].
  • the present invention it is possible to produce a black matrix having a high concentration of pigment and a high light-shielding property, and having a high re-dissolvability for dissolving its own dried solidified product, and a coating film obtained by a slit coating method.
  • a negative photosensitive resin composition having a viscosity that can be applied by a slit coating method, a partition wall, and a black matrix. According to the present invention, an optical element using the negative photosensitive resin composition of the present invention can be obtained.
  • (meth) acryloyl ...” is a general term for “methacryloyl ...” and “acryloyl...”. The same applies to (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, and (meth) acrylic resin.
  • the compound represented by Formula (1) in this specification is called compound (1).
  • the “total solid content” in this specification refers to a partition-forming component among the components contained in the negative photosensitive resin composition, and the negative photosensitive resin composition is heated at 140 ° C. for 24 hours to remove the solvent. It is a removed residue. Specifically, all components other than the volatile component which volatilizes by heating etc. in the partition formation process such as the solvent (D) are shown. The total solid content can also be calculated from the charged amount.
  • a film coated with the negative photosensitive resin composition is referred to as a “coating film”, a dried state is referred to as a “film”, and a film obtained by curing the film is referred to as a “cured film”.
  • the negative photosensitive resin composition contains a black colorant, the substrate surface is partitioned into partitions by a “partition” made of a cured film formed so as to partition the substrate surface into a plurality of partitions. Black matrix ".
  • the “ink” in the present specification is a general term for liquid compositions having, for example, optical and electrical functions after being dried and cured, and is not limited to conventionally used coloring materials. .
  • “pixels” formed by injecting the ink are also used to indicate sections having optical and electrical functions, which are partitioned by partition walls. Embodiments of the present invention will be described below. In addition, unless otherwise indicated in this specification,% represents the mass%.
  • the alkali-soluble resin (A) in the present invention is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. Since the alkali-soluble resin (A) has an ethylenic double bond in the molecule, the exposed portion of the negative photosensitive resin composition is polymerized and cured by radicals generated from the photopolymerization initiator (B). The exposed portion thus cured is not removed with an alkaline developer. Moreover, when the alkali-soluble resin (A) has an acidic group in the molecule, an unexposed portion of the uncured negative photosensitive resin composition can be selectively removed with an alkali developer. As a result, a partition wall can be formed.
  • a carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, etc. are mentioned, These may be used individually by 1 type or may use 2 or more types together.
  • limit especially as said ethylenic double bond The double bond which has addition polymerizability, such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, and a vinyloxyalkyl group, is mentioned, These are 1 You may use a seed
  • some or all of the hydrogen atoms of the ethylenic double bond group may be substituted with an alkyl group, preferably a methyl group.
  • the alkali-soluble resin (A) is not particularly limited, but is a resin (A1-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy group having an acidic group and an ethylenic double chain. And a resin (A1-2) having a bond introduced therein, and a monomer (A1-3) having a side chain having an acidic group and a side chain having an ethylenic double bond. These may be used alone or in combination of two or more.
  • Resin (A1-1) can be synthesized, for example, by the following method (i) or (ii).
  • a monomer having a reactive group other than an acidic group in the side chain for example, a monomer having a reactive group such as a hydroxyl group or an epoxy group, and a monomer having an acidic group in the side chain are copolymerized and reactive.
  • a copolymer having a side chain having a group and a side chain having an acidic group is obtained.
  • this copolymer is reacted with a compound having a functional group capable of bonding to the reactive group and an ethylenic double bond.
  • the acidic group remains after the reaction with the functional group capable of bonding to the acidic group and the compound having an ethylenic double bond.
  • (Ii) having a monomer having a reactive group other than an acidic group in the side chain as in (i) above, a functional group capable of binding to this reactive group, and a protected ethylenic double bond The compound is reacted.
  • the protection of the ethylenic double bond is removed.
  • the protection of the ethylenic double bond is removed.
  • the method (i) is preferably used in the present invention.
  • the method (i) will be specifically described.
  • monomers having a hydroxyl group as a reactive group 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5 -Hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (Meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl Meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide.
  • the monomer having an acidic group to be copolymerized is not particularly limited.
  • examples of the monomer having a phosphate group include 2- (meth) acryloyloxyethyl phosphate.
  • Examples of the compound having an ethylenic double bond and a functional group capable of bonding to a hydroxyl group to be reacted with the obtained copolymer include an acid anhydride having an ethylenic double bond, an isocyanate group and an ethylenic double bond. And a compound having an acyl chloride group and an ethylenic double bond.
  • Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal And acid anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, and the like.
  • Examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
  • Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.
  • Examples of the monomer having an epoxy group as a reactive group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
  • a monomer having an acidic group to be copolymerized with a monomer having an epoxy group as a reactive group the same monomer as described in the monomer having a hydroxyl group as a reactive group can be used, Copolymerization of a monomer having an epoxy group as a reactive group and a monomer having an acidic group can also be performed by a conventionally known method.
  • Examples of the compound having an ethylenic double bond and a functional group capable of bonding to an epoxy group to be reacted with the obtained copolymer include compounds having a carboxy group and an ethylenic double bond.
  • Specific examples of the compound include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
  • a carboxy group may be introduced into the resin (A1-1) by reacting the generated hydroxyl group with an acid anhydride in which the dehydration condensation part of the carboxylic acid forms part of the cyclic structure.
  • Examples of the monomer having a carboxy group as a reactive group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
  • these monomers are used also as a monomer which has the acidic group mentioned above.
  • the monomer When using a monomer having a carboxy group as a reactive group, the monomer is polymerized as described above.
  • the compound having an ethylenic double bond and a functional group capable of bonding to a carboxy group to be reacted with the obtained polymer include compounds having an epoxy group and an ethylenic double bond.
  • the compound include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
  • the amount of the functional group capable of bonding to the carboxy group and the compound having an ethylenic double bond to be reacted with the copolymer having a carboxy group is such that the carboxy group is converted into an acidic group in the polymer after the reaction. The amount remaining in the side chain.
  • Resin (A1-2) is synthesized by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond, which will be described later, and then reacting with a polyvalent carboxylic acid or an anhydride thereof. Can do. Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond. Next, a carboxyl group can be introduced by reacting a polycarboxylic acid or an anhydride thereof with an epoxy resin into which an ethylenic double bond has been introduced.
  • the epoxy resin is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having naphthalene skeleton, And an epoxy resin having a biphenyl skeleton represented by (A1-2a), an epoxy resin represented by the following formula (A1-2b), an epoxy resin having a biphenyl skeleton represented by the following formula (A1-2c), and the like. It is done.
  • v is an integer of 1 to 50, preferably an integer of 2 to 10.
  • the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, halogen An atom or a part of hydrogen atoms may be substituted with a phenyl group which may be substituted with a substituent.
  • R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and w is 0 or (It is an integer from 1 to 10.)
  • the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which some of the hydrogen atoms may be substituted with a substituent.
  • u is an integer of 0 or 1 to 10.
  • Compounds having carboxy groups and ethylenic double bonds that are reacted with epoxy resins to introduce ethylenic double bonds include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid. Acid, cinnamic acid and salts thereof are preferable, and acrylic acid or methacrylic acid is particularly preferable. That is, the resin (A1-2) is preferably an epoxy (meth) acrylate resin into which an acidic group has been introduced.
  • Resin (A1-2) is obtained by reacting a polycarboxylic acid anhydride with an alcoholic hydroxyl group of a resin obtained by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond.
  • a polyvalent carboxylic acid anhydride a mixture of dicarboxylic acid anhydride and tetracarboxylic dianhydride is preferably used.
  • the molecular weight can be controlled.
  • the resin (A1-2) a commercially available product can be used.
  • commercial products all are trade names, such as KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR- 1535H, ZAR-2001H, ZAR-2002, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H (above, Nipponization) Yakusho), EX1010 (manufactured by Nagase ChemteX) and the like.
  • Examples of the monomer (A1-3) include 2,2,2-triacryloyloxymethylethylphthalic acid (NK ester CBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • alkali-soluble resin (A) As alkali-soluble resin (A), the peeling of the cured film during development is suppressed, a high-resolution pattern can be obtained, the line linearity is good, and the appearance after the post-baking process is maintained.
  • the resin (A1-2) is preferably used from the viewpoint that a smooth cured film surface can be easily obtained.
  • Examples of the resin (A1-2) include a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, phenol Resin with acid group and ethylenic double bond introduced into novolac type epoxy resin, resin with acid group and ethylenic double bond introduced into cresol novolac type epoxy resin, acid group and ethylene into trisphenol methane type epoxy resin A resin into which an acidic double bond is introduced, and a resin in which an acidic group and an ethylenic double bond are introduced into the epoxy resins represented by the formulas (A1-2a) to (A1-2c) are preferable. Furthermore, as the resin (A1-2), an epoxy (meth) acrylate resin having an acidic group introduced is particularly preferable.
  • the number of ethylenic double bonds of the alkali-soluble resin (A) in one molecule is preferably 3 or more on average, and particularly preferably 6 or more.
  • the number of ethylenic double bonds is at least the lower limit of the above range, the alkali solubility between the exposed and unexposed portions is likely to be different, and a fine pattern can be formed with a smaller exposure amount.
  • the mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1.5 ⁇ 10 3 to 30 ⁇ 10 3 , particularly preferably 2 ⁇ 10 3 to 20 ⁇ 10 3 .
  • the number average molecular weight (Mn) is preferably from 500 to 20 ⁇ 10 3 , particularly preferably from 1 ⁇ 10 3 to 10 ⁇ 10 3 .
  • the acid value of the alkali-soluble resin (A) is preferably 10 to 300 mgKOH / g, particularly preferably 30 to 150 mgKOH / g. When the acid value is in the above range, the developability of the negative photosensitive resin composition is improved.
  • the alkali-soluble resin (A) contained in the negative photosensitive resin composition may be used alone or in combination of two or more.
  • the content of the alkali-soluble resin (A) in the total solid content in the negative photosensitive resin composition is preferably 5 to 80% by mass, particularly preferably 10 to 60% by mass. When the content ratio is in the above range, the developability of the negative photosensitive resin composition is good.
  • Photopolymerization initiator (B) As the photopolymerization initiator (B) in the present invention, a compound that generates a radical by light is used without particular limitation.
  • Specific examples of such compounds include O-acyloxime compounds.
  • IRGACURE OXE01 corresponding to BASF Corporation: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)]
  • Adekaoptomer N-1919 Adeka Cruz NCI -831, NCI-930 (manufactured by ADEKA) and the like.
  • O-acyloxime compounds compounds represented by the following formula (3) that can produce partition walls having a good shape even with a small exposure amount are preferable.
  • a photoinitiator (B) contains 1 type, or 2 or more types of a photoinitiator (3), and it is especially preferable to be comprised only with a photoinitiator (3).
  • R 3 represents a hydrogen atom
  • R 61 or OR 62 each of R 61 and R 62 independently represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom in a cycloalkane ring Is a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group A 6-30 phenyl group or a phenylalkyl group having 7-30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group is shown.
  • R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 30 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
  • R 5 represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group.
  • An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
  • R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R 61 , OR 62 , an alkanoyl group having 2 to 20 carbon atoms, or a hydrogen atom in the benzene ring.
  • a benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom
  • R 0 represents R 61 , OR 62 , a cyano group or a halogen atom.
  • a is 0 or an integer of 1 to 3.
  • R 3 is preferably an alkyl group having 1 to 10 carbon atoms, or a phenyl group having 6 to 12 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, such as a methyl group, Examples include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a phenyl group.
  • R 4 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and the like.
  • An alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
  • the photopolymerization initiator (3) No. 1 described in International Publication No. 2008/078678. 1 to 71 can also be used.
  • R 5 is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Can be mentioned. An alkyl group having 2 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
  • R 6 , R 8 and R 9 are preferably a hydrogen atom or a nitro group.
  • R 7 represents a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
  • benzylcarbonyl groups or nitro groups are preferred, benzoyl group, 2-methylbenzoyl group, 2-methyl-4-tetrahydropyranylmethoxybenzoyl group, 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group, 2-methyl A -5-tetrahydropyranylmethoxybenzoyl group, benzylcarbonyl group, 1,3,5 trimethylbenzylcarbonyl group and nitro group are particularly preferred.
  • “A” indicating the number of R 0 is 0.
  • the photopolymerization initiator (3) include compounds (3-1) to (3) wherein R 3 to R 9 are the following groups, and a indicating the number of R 0 is 0: (3-10).
  • Compound (3-2) wherein R 3 is a methyl group, R 4 is an octyl group, R 5 is an ethyl group, R 6 , R 8 , R 9 is a hydrogen atom, and R 7 is a benzoyl group
  • photopolymerization initiator (3) a commercially available product can be used.
  • examples of commercially available products include IRGACURE OXE02 (manufactured by BASF: equivalent to the above compound (3-7)) under the trade name.
  • the proportion of the photopolymerization initiator (B) in the total solid content in the negative photosensitive resin composition is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and particularly preferably 3 to 6% by mass.
  • the ratio of the photopolymerization initiator (3) in the photopolymerization initiator (B) is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and particularly preferably 100% by mass.
  • the ratio of the photopolymerization initiator (B) in the total solid content and the ratio of the photopolymerization initiator (3) in the photopolymerization initiator (B) are in the above ranges, the curability of the negative photosensitive resin composition.
  • the line pattern and the line width can be formed in a shape close to the mask pattern at the time of exposure.
  • Examples of the photopolymerization initiator that the photopolymerization initiator (B) may contain together with the photopolymerization initiator (3) in the negative photosensitive resin composition of the present invention include the following photopolymerization initiators.
  • Photopolymerization initiators that may be used in combination with the photopolymerization initiator (3) include ⁇ -diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether Acylo ethers such as benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Thioxanthones such as 2,4-diisopropylthioxanthone and thioxanthone-4-sulfonic acid; benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (
  • the negative photosensitive resin composition in this invention contains a black coloring agent (C) in the ratio of more than 20 mass% with respect to the total solid.
  • the black colorant (C) include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, azomethine black pigment, specifically C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned.
  • the black colorant (C) a mixture of organic pigments and inorganic pigments such as a red pigment, a blue pigment, a green pigment, and a yellow pigment can also be used. Specific examples of organic pigments include C.I. I. Pigment Blue 15: 6, Pigment Red 254, Pigment Green 36, and Pigment Yellow 150.
  • an organic pigment is preferable from the viewpoint of electrical characteristics, and carbon black is preferable from the viewpoint of cost and light shielding properties.
  • the carbon black is preferably surface-treated with a resin or the like, and a blue pigment or a violet pigment can be used in combination to adjust the color tone.
  • an organic pigment is preferable from the point of a favorable electrical property and a contrast improvement.
  • the organic pigment preferably has a specific surface area of 50 to 200 m 2 / g by the BET method from the viewpoint of the shape of the black matrix.
  • the specific surface area is 50 m 2 / g or more, the black matrix shape is hardly deteriorated.
  • it is 200 m 2 / g or less, the dispersion aid is not excessively adsorbed on the organic pigment, and it is not necessary to add a large amount of dispersion aid in order to develop various physical properties.
  • the average primary particle diameter of the organic pigment observed with a transmission electron microscope is preferably 20 to 150 nm.
  • the average primary particle diameter is 20 nm or more, the negative photosensitive resin composition can be dispersed at a high concentration with the negative photosensitive resin composition, and a negative photosensitive resin composition with good temporal stability can be easily obtained.
  • the black matrix shape is hardly deteriorated.
  • the average secondary particle diameter by observation with a transmission electron microscope is preferably 80 to 200 nm.
  • the content ratio of the black colorant (C) in the total solid content in the negative photosensitive resin composition is more than 20% by mass as described above. By setting the content ratio to more than 20% by mass, a color produced using the partition walls and the black matrix is obtained by sufficiently securing the optical density (OD), which is a value indicating the light shielding properties of the partition walls and the black matrix obtained. A high contrast such as a filter can be achieved.
  • the content of the black colorant (C) is preferably 20 to 65% by mass, particularly preferably 25 to 65% by mass. When it is not more than the upper limit of the above range, the curability of the negative photosensitive resin composition becomes good, and a cured film having a good appearance can be obtained.
  • the polymer dispersant is preferably a compound having a basic functional group from the viewpoint of affinity for the black colorant (C).
  • the basic functional group has a primary, secondary or tertiary amino group, the dispersibility is particularly excellent.
  • Polymer dispersing agents include urethane, polyimide, alkyd, epoxy, unsaturated polyester, melamine, phenol, acrylic, vinyl chloride, vinyl chloride vinyl acetate copolymer, polyamide, polycarbonate And the like. Of these, urethane-based and polyester-based compounds are particularly preferable.
  • the amount of the polymer dispersant used is preferably 5 to 30% by mass, particularly preferably 10 to 25% by mass, based on the black colorant (C).
  • the amount used is not less than the lower limit of the above range, the dispersion of the black colorant (C) becomes good, and when it is not more than the upper limit of the above range, the developability becomes good.
  • the negative photosensitive resin composition in the present invention contains a solvent (D).
  • the solvent (D) contains the solvent (D1), which is a compound represented by the following formula (1), in a proportion of 20 to 100% by mass with respect to the total amount of the solvent (D).
  • R 1 represents a methyl group
  • R 2 represents an alkyl group having 2 or 3 carbon atoms.
  • the solvent (D) reacts with the alkali-soluble resin (A) contained in the negative photosensitive resin composition, the photopolymerization initiator (B), the black colorant (C), and optional components contained as necessary. It is composed of a compound having no properties.
  • the solvent (D) is suitably dissolved or dispersed evenly in the composition containing each of these solid components, particularly the black colorant (C) in a proportion of more than 20% by mass with respect to the total solid content. It has a function of making the negative photosensitive composition uniformly and efficiently applied to the base material on which the partition walls are formed. Further, the solvent (D) has a function of giving the negative photosensitive resin composition the property of dissolving its own dried solidified product with the same composition, that is, a re-solubility.
  • the content ratio of the solvent (D) in the negative photosensitive resin composition varies depending on the composition and use of the negative photosensitive resin composition, the coating method when using this to form partition walls on the substrate surface, and the like.
  • the negative photosensitive resin composition is preferably blended in an amount of 50 to 99% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass.
  • the re-solubility in the negative photosensitive resin composition is a property that is particularly required when the composition is applied to the substrate surface by the slit coating method.
  • the negative photosensitive resin composition that adheres to and remains on the slit nozzle during repeated use forms a protrusion by drying and solidifying, and streaks occur in the direction of nozzle movement in coating, There is a problem that the dried solid product falls and foreign matter is mixed into the coating film.
  • the negative photosensitive resin composition is required to have re-solubility.
  • the viscosity suitable for making the application of the negative photosensitive composition uniform and simple varies depending on the coating method used.
  • the viscosity of the negative photosensitive composition is preferably less than 3.5 mPa ⁇ s, particularly preferably less than 3 mPa ⁇ s, depending on the coating speed.
  • the lower limit is 1 mPa ⁇ s or more.
  • the solvent (D) contains the solvent (D1), which is the compound (1), in the above ratio, thereby containing the black colorant (C) at a high concentration.
  • the compound (1) has a hydrophilic structure in the structure of —O—C 2 H 4 —O—C 2 H 4 —O— in the formula (1), so that the compound (1) has a hydrophilic property. The solubility is good.
  • one (R 1 ) is a methyl group and the other (R 2 ) is an alkyl group having 2 or 3 carbon atoms, that is, an ethyl group or a propyl group. Or an isopropyl group.
  • the end groups represented by R 1 and R 2 have moderate lipophilicity.
  • the compound (1) is an amphiphilic compound by having both the structure having the lipophilic group and the hydrophilic structure.
  • Examples of the compound (1) include diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether, and diethylene glycol isopropyl methyl ether. Of these, diethylene glycol ethyl methyl ether and diethylene glycol isopropyl methyl ether are preferable, and diethylene glycol ethyl methyl ether is particularly preferable.
  • the boiling point of the compound (1) is in the range of 176 to 200 ° C.
  • the viscosity is in the range of 1 to 1.5 mPa ⁇ s.
  • the boiling point of the solvent used is preferably 150 ° C. or higher so that the composition does not dry and solidify with a slit nozzle during coating. Further, from the viewpoint of productivity, it is preferable that the drying rate of the coated film after application is fast, and the upper limit of the boiling point of the solvent used is preferably about 220 ° C.
  • the solvent used depends on the viscosity of the solid component used and the amount of the solvent relative to the solid component, but the solvent viscosity is 2.5 mPa ⁇ s or less. Preferably there is.
  • a compound (1) it is a compound which also satisfy
  • the solvent (D1) one kind selected from the compound (1) may be used, or two or more kinds may be used in combination.
  • the content of the solvent (D1) in the solvent (D) is 20 to 100% by mass, preferably 30 to 90% by mass, particularly preferably 30 to 80% by mass.
  • the negative photosensitive resin composition of the present invention contains, as a solvent (D), together with the solvent (D1), as a ring-constituting atom, one or more carbon atoms bonded to an oxygen atom via a double bond, and It is preferable to use together the solvent (D2) which is an aliphatic cyclic compound (D2-1) which may contain an oxygen atom.
  • the ratio of the solvent (D2) to the total amount of the solvent (D) is preferably 10 to 40% by mass, particularly preferably 15 to 30% by mass.
  • the number of members of the aliphatic cyclic compound (D2-1) is preferably 3 to 7, and particularly preferably a 5-membered or 6-membered ring from the viewpoints of boiling point and melting point.
  • the atoms constituting the ring in the aliphatic cyclic compound (D2-1) are carbon atoms or etheric oxygen atoms, but the number of etheric oxygen atoms may be zero. Further, the number of carbon atoms> the number of etheric oxygen atoms. At least one of the carbon atoms constituting the ring is bonded to one oxygen atom through a double bond. Of the carbon atoms constituting the ring, all those not bonded to the oxygen atom through a double bond are bonded to two hydrogen atoms.
  • the number of carbonyl groups constituting the ring may be one or more, and preferably one.
  • the re-solubility of the negative photosensitive resin composition is further improved. be able to. Since the aliphatic cyclic compound (D2-1) as the solvent (D2) has a carbonyl group that is a polar group and does not have a terminal alkyl group, the aliphatic cyclic compound (D2-1) has high hydrophilicity. The solubility with respect to (A) can be made favorable.
  • the aliphatic cyclic compound (D2-1) has a higher viscosity than the compound (1), in order to make the viscosity of the obtained negative photosensitive resin composition appropriate, In (D), it is preferable to use with the said compounding quantity.
  • Examples of the aliphatic cyclic compound (D2-1) include cyclic esters and cyclic ketones.
  • Examples of the cyclic ester include lactones such as ⁇ -acetolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
  • Examples of the cyclic ketone include cycloalkanones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, and cycloheptanone.
  • the solvent (D2) cyclohexanone, ⁇ -butyrolactone and the like are preferable from the viewpoint of availability and boiling point.
  • the solvent (D2) one kind selected from the above aliphatic cyclic compounds (D2-1) may be used, or two or more kinds may be used in combination.
  • the negative photosensitive resin composition of the present invention may contain a solvent (D3) other than the above-mentioned solvent (D1) and solvent (D2) as necessary, as the solvent (D).
  • a solvent (D3) the above-mentioned alkali-soluble resin (A), the solvent used for the synthesis of the following ink repellent agent (E), and the like, together with the alkali-soluble resin (A) and the ink repellent agent (E), negative photosensitivity.
  • blending with a resin composition are mentioned.
  • the solvent used for the synthesis of the alkali-soluble resin (A) or the ink repellent agent (E) the solvent (D1) or the solvent (D2) may be used.
  • the negative photosensitive resin composition contains the solvent (D1) or the solvent (D2) derived from these compounding components, it is calculated by the total amount of the solvent (D1) and the solvent (D2) containing them. What is necessary is just to adjust so that content of the solvent (D1) and the solvent (D2) in a solvent (D) may become said range, respectively.
  • the solvent (D3) is not particularly limited as long as it is used together with the solvent (D1) and the solvent (D2) used as necessary and does not inhibit the function as the solvent (D). Therefore, when the alkali-soluble resin (A) or the ink repellent agent (E) is blended in the negative photosensitive resin composition together with the solvent used for the synthesis, the above function as the solvent (D) is used as the solvent used in the synthesis. It is preferable to select a solvent that does not inhibit the reaction.
  • alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol; ketones such as acetone, 2-butanone and methyl isobutyl ketone; 2-methoxyethanol, 2-ethoxy Cellsolves such as ethanol and 2-butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; methyl acetate, ethyl Acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol
  • the content of the solvent (D3) in the solvent (D) is an amount obtained by subtracting the amount of the solvent (D1) and the solvent (D2) from the total amount of the solvent (D), specifically, the total amount of the solvent (D).
  • a ratio of 1 to 70% by mass is preferable, and 20 to 70% by mass is particularly preferable.
  • an aspect including the solvent (D1), the solvent (D2), and / or the solvent (D3), which includes only the solvent (D1) can be given.
  • a preferable blending ratio (mass ratio) when the solvent (D) is composed of the solvent (D1) and the solvent (D2) includes solvent (D1): solvent (D2) 85: 15 to 70:30.
  • a preferable blending ratio (mass ratio) when the solvent (D) is composed of the solvent (D1) and the solvent (D3) 30: 70 to 80:20.
  • solvent (D1): solvent (D2): solvent (D3) ) 30 to 80:10 to 30: 0 to 60.
  • the negative photosensitive resin composition in the present invention may further contain an ink repellent agent (E) as an optional component.
  • an ink repellent agent (E) for example, an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (provided that the alkyl group has an etheric oxygen atom between the carbon atoms).
  • R 11 and R 12 each independently represents a methyl group or a phenyl group.
  • N represents an integer of 1 to 200.
  • the ink repellent agent (E) one type of the polymer (E1) may be used alone, or two or more types may be used in combination. If an ink repellent agent (E) is mix
  • the number average molecular weight (Mn) of the polymer (E1) is preferably from 1,500 to 50,000, particularly preferably from 10,000 to 50,000. When the number average molecular weight (Mn) is in the above range, alkali solubility and developability are good.
  • the polymer (E1) contains a fluorine atom the fluorine atom content in the polymer (E1) is preferably 5 to 35% by mass from the viewpoint of ink repellency and partition wall moldability, and 10 to 30% by mass. % Is particularly preferred.
  • the silicon content in the polymer (E1) is preferably 0.1 to 25% by mass from the viewpoint of ink repellency and partition wall moldability. It is particularly preferably 5 to 10% by mass.
  • the polymer (E1) preferably has ethylenic double bonds in the side chain at a rate of 3 to 100 molecules / molecule.
  • the ratio is particularly preferably 6 to 30 / molecule.
  • the polymer (E1) preferably has an acidic group, for example, at least one acidic group selected from the group consisting of a carboxy group, a phenolic hydroxyl group and a sulfo group.
  • an acidic group for example, at least one acidic group selected from the group consisting of a carboxy group, a phenolic hydroxyl group and a sulfo group.
  • the polymer having the ink repellency (E1) hardly remains in the region (dots) divided by the partition walls or the black matrix on the base material because it has alkali solubility, and when the ink is injected. This is because the ink wettability is improved.
  • the acid value of the polymer (E1) is preferably 10 to 400 mgKOH / g, particularly preferably 20 to 300 mgKOH / g.
  • the content ratio of the ink repellent agent (E) in the total solid content in the negative photosensitive resin composition is preferably 0.01 to 30% by mass, particularly preferably 0.05 to 20% by mass.
  • the content ratio is not less than the lower limit of the above range, sufficient ink repellency is imparted to the partition walls and the upper surface of the black matrix formed by the negative photosensitive resin composition. Adhesiveness of a partition or a black matrix and a base material becomes it favorable that it is below the upper limit of the said range.
  • the negative photosensitive resin composition in the present invention may contain a crosslinking agent (F) as an optional component for promoting radical curing.
  • a crosslinking agent (F) the compound which has two or more ethylenic double bonds in 1 molecule, and does not have an acidic group is preferable.
  • crosslinking agent (F) examples include diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate, ⁇ -caprolactone modified tris- (2-acryloxyethyl) isocyanurate, ⁇ 4-
  • hept-5-ene-2,3-dicarboximide 1,3-dicarboximide
  • urethane acrylate 1,3-dicarboximide
  • photoreactivity it is preferable to have a large number of ethylenic double bonds.
  • these may be used individually by 1 type, or may use 2 or more types together.
  • crosslinking agent F
  • Commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9530 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., dipenta Erythritol pentaacrylate and dipentaerythritol hexaacrylate)), NK Este A-9300 (trade name, Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, new Nakamura Chemical Co., Ltd., ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name, manufactured by Maruzen Petrochemical Co., Ltd., Bis ⁇ 4-
  • urethane acrylate examples include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20. Etc.
  • the content of the crosslinking agent (F) in the total solid content in the negative photosensitive resin composition is preferably 3 to 50% by mass, particularly preferably 5 to 40% by mass. Within the above range, the alkali developability of the negative photosensitive resin composition is improved.
  • the negative photosensitive resin composition in the present invention may contain fine particles (G) as necessary.
  • the partition obtained from the negative photosensitive resin composition becomes a partition excellent in heat resistance in which thermal sagging is prevented.
  • the fine particles (G) various inorganic and organic fine particles can be used, and those in which the basic polymer dispersant is negatively charged from the viewpoint of adsorption ability are preferably used.
  • inorganic materials include silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO).
  • organic system examples include polyethylene and polymethyl methacrylate (PMMA).
  • PMMA polymethyl methacrylate
  • the fine particles (G) do not absorb the light irradiated at the time of exposure, i-line (365 nm) which is the main emission wavelength of the ultra-high pressure mercury lamp, It is particularly preferable not to absorb h-line (405 nm) and g-line (436 nm).
  • the particle diameter of the fine particles (G) is preferably 1 ⁇ m or less, and particularly preferably 200 nm or less, because the surface smoothness of the partition walls is improved.
  • Silica is preferable as the fine particles (G).
  • colloidal silica is preferable.
  • colloidal silica includes silica hydrosol dispersed in water and organosilica sol in which water is replaced with an organic solvent, and organosilica sol using an organic solvent as a dispersion medium is preferable.
  • Commercially available products can be used as such organosilica sols, all of which are trade names manufactured by Nissan Chemical Industries, Ltd., PMA-ST (silica particle diameter: 10 to 20 nm, silica solid content).
  • NPC-ST sica particle diameter: 10 to 20 nm, silica solid content: 30% by mass, n-propyl cellosolve: 70% by mass
  • IPA- ST sica particle diameter: 10 to 20 nm, silica solid content: 30% by mass, isopropyl alcohol (2-propanol): 70% by mass
  • the content of the fine particles (G) in the total solid content in the negative photosensitive resin composition is preferably 5 to 35% by mass, particularly preferably 10 to 30% by mass.
  • the content ratio is not less than the lower limit value of the above range, thermal sag of the partition due to post-baking is prevented, and when it is not more than the upper limit value of the above range, the storage stability of the negative photosensitive resin composition becomes good.
  • the negative photosensitive resin composition in the present invention may contain a silane coupling agent (H) as necessary.
  • a silane coupling agent (H) as necessary.
  • the substrate adhesion of the cured film formed from the negative photosensitive resin composition can be improved.
  • the silane coupling agent (H) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane.
  • a commercially available product can be used as the silane coupling agent (H).
  • Examples of commercially available products include KBM5013 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloyloxypropyltrimethoxysilane).
  • the content ratio of the silane coupling agent (H) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass.
  • the base material adhesiveness of the cured film formed from a negative photosensitive resin composition improves that it is more than the lower limit of the said range.
  • the negative photosensitive resin composition in the present invention may contain a thermosetting agent (I) as necessary.
  • the thermosetting agent (I) includes an amino resin, a compound having two or more epoxy groups, a compound having two or more hydrazino groups, a polycarbodiimide compound, a compound having two or more oxazoline groups, two or more Examples thereof include compounds having an aziridine group, polyvalent metals, compounds having two or more mercapto groups, and polyisocyanate compounds.
  • an amino resin, a compound having two or more epoxy groups, or a compound having two or more oxazoline groups is particularly preferable from the viewpoint of improving chemical resistance of the formed partition wall.
  • the content ratio of the thermosetting agent (I) in the total solid content in the negative photosensitive resin composition is preferably from 0.1 to 20% by mass, particularly preferably from 1 to 20% by mass. Within the above range, the developability of the obtained negative photosensitive resin composition becomes good.
  • the negative photosensitive resin composition in this invention may contain the phosphoric acid compound (J) as needed. Adhesiveness with a base material can be improved because a negative photosensitive resin composition contains a phosphoric acid compound (J).
  • the phosphoric acid compound include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.
  • the content of the phosphoric acid compound (J) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 10% by mass, particularly preferably 0.1 to 1% by mass. Adhesiveness with the base material of the cured film formed from the negative photosensitive resin composition obtained as it is the said range becomes favorable.
  • the negative photosensitive resin composition in the present invention may contain a surfactant (K) as necessary.
  • a surfactant (K) As the negative photosensitive resin composition contains the surfactant (K), the thickness of the cured film becomes uniform.
  • the ink repellent agent (E) described above also usually has an action as a surfactant.
  • a negative photosensitive resin composition for forming a partition for an optical element that forms a pixel by a method other than the ink jet method usually does not contain an ink repellent, and therefore, a surfactant is preferably used.
  • the surfactant (K) the same polymer as the ink repellent agent (E) may be used, and examples thereof include a fluorine-based surfactant, a silicone-based surfactant, and an acrylic surfactant.
  • Surfactant (K) may be a commercially available product. All are trade names of BYK-Japan Japan, BYK-306 (polyether-modified polydimethylsiloxane: 12% by mass, xylene: 68% by mass, monophenyl glycol: 20% by mass), BYK-307 (polyether-modified poly Dimethylsiloxane), BYK-323 (aralkyl-modified polymethylalkylsiloxane), BYK-320 (polyether-modified polymethylalkylsiloxane: 52 mass%, white spirit: 43 mass%, PGMEA: 5 mass%), BYK-350 ( Acrylic copolymer) and the like.
  • the content ratio of the surfactant (K) in the total solid content in the negative photosensitive resin composition is preferably 0.01 to 30% by mass, particularly preferably 0.05 to 20% by mass. When the thickness is in the above range, the film thickness of the obtained negative photosensitive resin composition becomes uniform.
  • the negative photosensitive resin composition in the present invention can further use a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a repellency inhibitor, an ultraviolet absorber, and the like, if necessary.
  • the negative photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a photopolymerization initiator (B), a black colorant (C) in a proportion of more than 20% by mass relative to the total solid content, and a solvent ( D). Further, as required, the ink repellent agent (E), the crosslinking agent (F), the fine particles (G), the silane coupling agent (H), the thermosetting agent (I), the phosphoric acid compound (J), and the surfactant. (K) and other additives may be contained. It does not restrict
  • the negative photosensitive resin composition of the present invention is used as a material such as photolithography in the same manner as an ordinary negative photosensitive resin composition, and the obtained cured film has a black colorant at a particularly high concentration as a partition.
  • a black matrix containing a high light-shielding property it can be used as a member of an optical element in which a cured film of a normal negative photosensitive resin composition is used.
  • the negative photosensitive resin composition of the present invention in which the solvent (D1) as the compound (1) is blended as the solvent (D) is resoluble while containing a black colorant at a high concentration. Furthermore, it has a viscosity capable of being applied by a slit coating method.
  • the negative photosensitive resin composition of the present invention has a suitable viscosity when the slit coating method is used in the application of the negative photosensitive resin composition when forming a cured film such as a partition wall on the substrate.
  • a suitable viscosity when the slit coating method is used in the application of the negative photosensitive resin composition when forming a cured film such as a partition wall on the substrate.
  • it is particularly suitable for forming a cured film from coating using the slit coating method.
  • Photopolymerization initiator (B) O-acyloxime compound, 3 to 6% by mass in the total solid content in the negative photosensitive resin composition
  • Black colorant (C) at least one colorant selected from carbon black and organic pigments, 25 to 65% by mass in the total solid content of the negative photosensitive resin composition
  • Solvent (D) The solvent (D) is a negative type containing 30 to 80% by mass of the solvent (D1) and 20 to 70% by mass of PGMEA as the solvent (D3) with respect to the total amount of the solvent (D).
  • Crosslinking agent (F) a compound having two or more ethylenic double bonds in the molecule and having no acidic group, and 5 to 40 mass in the total solid content in the negative photosensitive resin composition %
  • Surfactant (K) At least one surfactant selected from a fluorine-based surfactant, a silicone-based surfactant, and an acrylic-based surfactant, and in the total solid content in the negative photosensitive resin composition 0.05 to 20% by mass.
  • Solvent (D) 30 to 80% by mass of solvent (D1), 10 to 30% by mass of solvent (D2), and 0 to 60% by mass of PGMEA as solvent (D3) with respect to the total amount of the solvent (D) 65 to 90% by mass of the solvent (D) each contained in the negative photosensitive resin composition.
  • the partition of this invention is a partition formed in order to provide a division on the substrate surface, Comprising: It consists of a cured film of the said negative photosensitive resin composition of this invention.
  • the partition wall of the present invention is suitably used for an optical element, and since the negative photosensitive resin composition contains a black colorant (C), the resulting partition wall can be applied as a black matrix. is there.
  • the partition formed from the negative photosensitive resin composition contains the black colorant (C) in a high concentration
  • the partition formed from the negative photosensitive resin composition that is, the black matrix has high light-shielding properties, specifically Specifically, it has a high light shielding property with an optical density (OD) of 2.5 or more.
  • a black matrix having an optical density (OD) of 3 or more can be provided by further adjusting the conditions. If the black matrix has an optical density (OD) of 2.5 or more, particularly 3 or more, for example, it can sufficiently contribute to an increase in contrast of a color filter produced using the black matrix.
  • the partition of the present invention is applied to, for example, a partition for an optical element (black matrix) having a plurality of pixels and a partition located between adjacent pixels on the substrate surface.
  • Examples of the method for producing the barrier rib (black matrix) for the optical element of the present invention using the negative photosensitive resin composition of the present invention include the following methods.
  • the negative photosensitive resin composition of the present invention is applied to the substrate surface to form a coating film (coating film forming process), then the coating film is dried to form a film (drying process), and then the film Then, only the part to be the partition wall is exposed and photocured (exposure process), and then the film other than the photocured part is removed to form the partition wall made of the photocured part of the film (development process), and then
  • the partition walls (black matrix) for the optical element of the present invention can be produced by further thermally curing the formed partition walls and the like as necessary (post-baking step). Moreover, you may put further the photocuring (post exposure process) of the said formed partition etc. between a image development process and a post-baking process.
  • the material of the substrate is not particularly limited, but various glass plates; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin, etc.
  • Thermoplastic plastic sheet; Cured sheet of thermosetting resin such as epoxy resin and unsaturated polyester can be used.
  • a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance.
  • a post exposure may be performed from the back surface (board
  • the coating method is not particularly limited as long as a coating film having a uniform film thickness is formed. Usually, spin coating, spraying, slit coating, roll coating, spin coating, bar coating, etc. The method used for the coating film formation of this is mentioned. In particular, a slit coating method that can be applied at once to a large area is preferred.
  • the negative photosensitive resin composition of the present invention contains the black colorant (C) at a high concentration, while using the solvent (D) containing the solvent (D1) as the compound (1). It has excellent re-solubility and has a viscosity that can be applied by slit coating.
  • the film thickness of the coating film is determined in consideration of the height of the partition wall finally obtained and the solid content concentration of the negative photosensitive resin composition.
  • the film thickness of the coating film is preferably 500 to 2,000%, particularly preferably 550 to 1,000%, of the height of the partition wall (black matrix) finally obtained.
  • the thickness of the coating film is preferably from 0.3 to 100 ⁇ m, particularly preferably from 1 to 50 ⁇ m.
  • the coating film formed on the substrate surface in the coating film forming step is dried to obtain a film.
  • the volatile components including the solvent contained in the negative photosensitive resin composition constituting the coating film are volatilized and removed, and a non-sticky film is obtained.
  • vacuum drying or heat drying is preferable. Further, in order to efficiently dry the film without causing unevenness of the film appearance, it is more preferable to use vacuum drying and heat drying in combination.
  • the vacuum drying conditions vary depending on the type of each component, the blending ratio, and the like, but it is preferable to perform the drying at 10 to 500 Pa for 10 to 300 seconds. Heat drying is preferably performed at 50 to 120 ° C. for 10 to 2,000 seconds with a heating device such as a hot plate or oven together with the substrate.
  • the negative photosensitive resin composition in the exposed portion is cured, and the negative photosensitive resin composition in the unexposed portion is not cured.
  • the irradiation light is visible light; ultraviolet light; far ultraviolet light; excimer laser such as KrF excimer laser, ArF excimer laser, F 2 excimer laser, Kr 2 excimer laser, KrAr excimer laser, Ar 2 excimer laser; X-ray; Etc.
  • the irradiation light is preferably light having a wavelength of 100 to 600 nm, more preferably light having a distribution in the range of 300 to 500 nm, and particularly preferably i-line (365 nm), h-line (405 nm), and g-line (436 nm). .
  • a well-known super high pressure mercury lamp etc. can be used as an irradiation apparatus.
  • Exposure dose, i-line basis preferably 5 ⁇ 1,000mJ / cm 2, particularly preferably 10 ⁇ 200mJ / cm 2.
  • the exposure amount is at least the lower limit of the above range, the negative photosensitive resin composition serving as the partition is sufficiently cured, and subsequent development does not easily cause dissolution or peeling from the substrate.
  • a high resolution is obtained when it is not more than the upper limit of the above range.
  • the development process It develops with a developing solution and the negative photosensitive resin composition of an unexposed part is removed.
  • an aqueous alkali solution containing alkalis such as inorganic alkalis, amines, alkanolamines, and quaternary ammonium salts can be used.
  • an organic solvent such as a surfactant or alcohol can be added to the developer in order to improve solubility and remove residues.
  • the development time time for contact with the developer
  • Examples of the developing method include a liquid piling method, a dipping method, and a shower method. After the development, water on the substrate surface can be removed by washing with high pressure water or running water and drying with compressed air or compressed nitrogen.
  • the post-exposure may be performed from either the front surface where the partition walls are formed or the back surface (substrate side) where the partition walls are not formed. Moreover, you may expose from both front and back. Exposure is preferably 50 mJ / cm 2 or more, more preferably 200 mJ / cm 2 or more, more preferably 1,000 mJ / cm 2 or more, 2,000 mJ / cm 2 or more is particularly preferable.
  • the light to be irradiated is preferably ultraviolet light, and a known ultra-high pressure mercury lamp or high-pressure mercury lamp can be used as the light source. These light sources are preferably used because they emit light having a wavelength of 600 nm or less that contributes to the hardening of the barrier ribs, and emit less light having a wavelength of 200 nm or less that causes oxidative decomposition of the barrier ribs. Furthermore, it is preferable that the quartz tube glass used for the mercury lamp has an optical filter function for cutting light of 200 nm or less.
  • a low pressure mercury lamp can also be used as the light source.
  • a low-pressure mercury lamp has a high emission intensity at a wavelength of 200 nm or less, and oxidative decomposition of the partition walls is likely to occur due to the generation of ozone.
  • the exposure amount is preferably 500 mJ / cm 2 or less, particularly preferably 300 mJ / cm 2 or less.
  • the partition wall By performing heat treatment for 5 to 90 minutes with a heating device such as a hot plate or an oven, a pattern composed of partition walls and regions (dots) divided by the partition walls is formed.
  • the heating temperature is preferably 150 to 250 ° C, particularly preferably 180 to 250 ° C.
  • the partition walls are sufficiently cured, sufficient chemical resistance is obtained, and is included in the ink when the ink is applied during the subsequent pixel formation.
  • the partition wall does not swell or the ink does not ooze due to the solvent.
  • thermal decomposition of the partition wall is difficult to occur.
  • the pattern formed from the negative photosensitive resin composition of the present invention preferably has an average partition wall width of 100 ⁇ m or less, particularly preferably 20 ⁇ m or less.
  • the average distance between adjacent barrier ribs (dot width) is preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
  • the average height of the partition walls is preferably 0.05 to 50 ⁇ m, particularly preferably 0.2 to 10 ⁇ m.
  • Examples of the optical element to which the partition wall (black matrix) of the present invention is applied include a color filter and an organic EL element.
  • the ink used for the photolithography method mainly includes a coloring component, an initiator, a binder resin component, and a solvent.
  • a coloring component it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like.
  • the binder resin component a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin.
  • the water-based ink contains water and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary.
  • the oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
  • pixels can be formed by injecting ink into an area partitioned by a partition wall (black matrix) by an inkjet method using an inkjet apparatus.
  • an alkaline aqueous solution is applied to the surface of the substrate exposed in the dot before the ink is put into the region (dot) partitioned by the partition wall (black matrix).
  • the ink repellency treatment may be performed by a method such as cleaning by UV, UV cleaning, UV / ozone cleaning, excimer cleaning, corona discharge, oxygen plasma.
  • the ink jet device is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, a method in which ink is ejected intermittently using a piezoelectric element, and ink is heated to foam.
  • An apparatus using various methods such as a method of intermittent injection by use can be used.
  • the pixel shape may be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type.
  • the ink used for the ink jet method mainly includes a coloring component, a binder resin component, and a solvent.
  • a coloring component it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like.
  • the binder resin component a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin.
  • the water-based ink contains water and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary.
  • the oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
  • the ink jet method after ink is injected into the dots by the ink jet device, the ink layer formed in the dots is subjected to treatment such as drying, heat curing, and ultraviolet curing as necessary. Pixels are formed.
  • a protective film layer is formed as necessary.
  • the protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the elution from the partition wall (black matrix) or the pixel portion ink from reaching the liquid crystal layer.
  • the ink repellency of the partition wall (black matrix) is strong, it is preferable to remove the ink repellency of the partition wall (black matrix) in advance. In this case, unless the ink repellency is removed, the overcoat coating solution may be repelled and a uniform film thickness may not be obtained.
  • Examples of a method for removing the ink repellency of the partition walls (black matrix) include plasma ashing and light ashing.
  • the color filter of the present invention is a color filter having sufficiently high contrast performance because the partition wall having high light shielding properties according to the present invention is used as a black matrix.
  • a transparent electrode such as tin-doped indium tin oxide (ITO) is formed on a transparent substrate such as glass by sputtering or the like, and the transparent electrode is etched into a desired pattern as necessary.
  • a barrier rib is formed using the negative photosensitive resin composition of the present invention, and a hole transport material and a light emitting material solution are sequentially applied to the dots using a vapor deposition method and an ink jet method, and dried to form holes.
  • a transport layer and a light emitting layer are formed.
  • an electrode of aluminum or the like is formed by a vapor deposition method or the like, thereby obtaining a pixel of the organic EL element.
  • Examples 1 to 11 are examples, and examples 21 to 28 are comparative examples.
  • Alkali-soluble resin (A)) ZCR1642 Resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the above formula (A1-2a) (trade name: ZCR-1642H, manufactured by Nippon Kayaku Co., Ltd., mass average molecular weight) (Mw): 5,800, acid value: 100 mg KOH / g, solid content: 70% by mass, PGMEA: 30% by mass).
  • OXE02 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (in the compound represented by formula (3), R 3 : methyl group, R 4 : methyl group, R 5 : ethyl group, R 6 , R 8 , R 9 : hydrogen atom, R 7 : 2-methylbenzoyl group, manufactured by BASF, trade name: OXE02. ).
  • NCI831 Made by ADEKA, product name: Adeka Cruz NCI-831.
  • N1919 Made by ADEKA, trade name: Adeka optomer N-1919.
  • Black colorant (C) + polymer dispersion) CB carbon black dispersion (average secondary particle size: 120 nm, carbon black: 20% by mass, polyurethane polymer dispersant having an amine value of 18 mgKOH / g: 5% by mass, PGMEA: 75% by mass).
  • Mixed organic pigment C.I. I. Pigment blue 15: 6, C.I. I. Pigment red 254, C.I. I. Pigment Yellow 139 and a polymeric dispersant in a 10: 5: 5: 5 mixture (solid content: 25 mass%, PGMEA: 75 mass%).
  • Solvent (D) (I) Solvent (D1) EDM: Diethylene glycol ethyl methyl ether (boiling point: 176 ° C., viscosity: 1.2 mPa ⁇ s). IPDM: Diethylene glycol isopropyl methyl ether (boiling point: 179 ° C., viscosity: 1.3 mPa ⁇ s). (ii) Solvent (D2) CHN: cyclohexanone (boiling point: 155 ° C., viscosity: 2.1 mPa ⁇ s).
  • BDM Diethylene glycol butyl methyl ether (boiling point: 212 ° C., viscosity: 1.5 mPa ⁇ s).
  • DMM Dipropylene glycol dimethyl ether (boiling point: 171 ° C., viscosity: 1.0 mPa ⁇ s).
  • CHXA cyclohexyl acetate (cyclohexanol acetate, boiling point: 173 ° C., viscosity: 2.0 mPa ⁇ s).
  • DPMA dipropylene glycol monomethyl ether acetate (boiling point: 213 ° C., viscosity: 2.2 mPa ⁇ s).
  • IPA isopropyl alcohol (2-propanol, boiling point: 82 ° C., viscosity: 1.8 mPa ⁇ s).
  • BA Butyl acetate (n-butyl acetate, boiling point: 126 ° C., viscosity: 0.9 mPa ⁇ s).
  • thermosetting agent (I) XD1000: Multifunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: XD1000).
  • a negative photosensitive resin composition was applied to the surface of a glass substrate (75 ⁇ 75 mm) using a spinner to form a coating film (coating film forming step). Next, drying was performed on a hot plate at 100 ° C. for 2 minutes. For Examples 1, 2, and 21 to 27, the film thickness was 1.0 ⁇ m, for Examples 3 to 10, the film thickness was 2.0 ⁇ m, and for Example 11, Glass substrates (1) each having a film thickness of 3.0 ⁇ m were obtained (drying step).
  • the unexposed portion was developed by being immersed in an inorganic alkali type developer (Yokohama Yushi Kogyo Co., Ltd., trade name: Semi-clean DL-A4 10-fold diluted aqueous solution), and the unexposed portion was washed away with water and dried. (Development process). Subsequently, the glass substrate (2) in which the pattern (black matrix) was formed in the surface was obtained by heating on a hotplate at 220 degreeC for 1 hour (post-baking process).
  • an inorganic alkali type developer Yokohama Yushi Kogyo Co., Ltd., trade name: Semi-clean DL-A4 10-fold diluted aqueous solution
  • Viscosity The viscosity of the negative photosensitive resin composition is 25 ° C. using a TVE25L viscometer (manufactured by Toki Sangyo Co., Ltd.) calibrated with a standard solution JS2.5 for viscometer calibration (manufactured by Nippon Grease Co., Ltd.). Measured under conditions. The viscosity of each compound used as the solvent (D) was also measured in the same manner. The obtained measured values were evaluated according to the following criteria based on the viscosity characteristics obtained in the slit coating method.
  • the negative photosensitive resin composition used in Examples 1 and 22 was applied to the surface of a glass substrate (370 mm ⁇ 470 mm) by the slit coating method described below to form a coating film.
  • the coatability was evaluated.
  • As the slit coat die a die made of SUS304 having a width of 370 mm, a height of 100 mm, and a thickness of 60 mm was used.
  • the gap between the die and the glass substrate was 100 ⁇ m, and a gear pump was used as a method for supplying the negative photosensitive resin composition to the die. Under these conditions, the die was moved at a relative speed of 50 mm / second with respect to the glass substrate to form a coating film of the negative photosensitive resin composition on the glass substrate surface.
  • the coating film was dried to form a film having a thickness of 1.0 ⁇ m.
  • the slit coat die was allowed to stand for 5 minutes after coating, and a coating film was formed again by the slit coat method and dried to form a film. This was repeated 10 times. The obtained film was visually observed. The case where no defects due to the streaks or the dried solidified product of the photosensitive composition were observed was evaluated as ⁇ (good), and the case where defects were observed was evaluated as x (defective).
  • the optical density (OD) on the pattern (black matrix) of the glass substrate (2) was measured using a monochrome transmission densitometer Ihca-T5 (manufactured by Ihara Electronics Co., Ltd.). An optical density of 2.5 or higher was evaluated as ⁇ (good), and an optical density of less than 2.5 was evaluated as x (bad).
  • Example 22 using a negative photosensitive resin composition containing 47% by mass of the solvent in which R 1 and R 2 in formula (1) are both methyl groups in the total solvent (D) were poor. From these facts, it is presumed that when both R 1 and R 2 are methyl groups, the boiling point is low, and drying and solidification occurs at the slit nozzle, resulting in poor slit coat characteristics.
  • Example 23 The re-solubility of Example 23 using a negative photosensitive resin composition containing 47% by mass of the solvent in which R 1 and R 2 in the formula (1) are both ethyl groups in the total solvent (D) was poor. Therefore, it is presumed that when the number of carbon atoms in the alkyl chain is increased, the alkyl chain becomes hydrophobic and the re-solubility becomes poor. Further, in Example 24 using a negative photosensitive resin composition containing a solvent in which R 1 is a methyl group and the alkyl chain of R 2 has 4 carbon atoms, re-solubility was poor, so that Example 23 It is presumed that the re-solubility became poor for the same reason. Even in Examples 25 to 27 using a negative photosensitive resin composition containing 47% by mass of the solvent described in the prior art document in the total solvent (D), the re-solubility was poor.
  • the negative photosensitive resin composition of the present invention is a composition suitable for the production of a black matrix having a high concentration of pigment and a high light-shielding property. Using the resulting black matrix, a high-resolution color filter or organic EL An element is manufactured.

Abstract

Provided are: a negative photosensitive resin composition, which contains a pigment at high concentration and is capable of producing a black matrix that has high light shielding properties, which has high re-solubility, which is capable of providing a coating film by a slit coating method, said coating film being free from defects, and which has such a viscosity that enables coating by a slit coating method; a partition wall which is formed by curing the photosensitive resin composition and has high light shielding properties; and an optical element which has the partition wall. A negative photosensitive resin composition, which contains an alkali-soluble resin, a photopolymerization initiator, a black coloring agent and a solvent, and wherein the black coloring agent is contained in an amount of more than 20% by mass relative to the total solid content of the composition and the solvent contains a compound represented by R1O(C2H4O)2R2 (wherein R1 represents a methyl group and R2 represents an alkyl group having 2 or 3 carbon atoms) in an amount of 20-100% by mass relative to the total mass of the solvent; and a partition wall which is formed of a cured film of the negative photosensitive resin composition and which is formed to have such a shape that divides the surface of a substrate into a plurality of compartments for pixel formation.

Description

ネガ型感光性樹脂組成物、隔壁、ブラックマトリックスおよび光学素子Negative photosensitive resin composition, partition, black matrix and optical element
　本発明は、ネガ型感光性樹脂組成物、これを用いた隔壁、ブラックマトリックス、ならびに、該隔壁を有する光学素子に関する。 The present invention relates to a negative photosensitive resin composition, a partition using the same, a black matrix, and an optical element having the partition.
　カラーフィルタや有機ＥＬ（Ｅｌｅｃｔｒｏ－Ｌｕｍｉｎｅｓｃｅｎｃｅ）素子の画素部に用いられる隔壁は、感光性樹脂組成物を基板に塗布してフォトリソグラフィ技術により形成する方法が知られている。従来、感光性樹脂組成物の塗布はスピンコート法を用いて行われている。基板の大型化に伴い、スピンコート法による塗布が困難となり、スリットコート法による塗布方法が提案されている。 A partition used in a pixel portion of a color filter or an organic EL (Electro-Luminescence) element is known to be formed by applying a photosensitive resin composition to a substrate and using a photolithography technique. Conventionally, the photosensitive resin composition is applied by using a spin coating method. As the size of the substrate increases, coating by spin coating becomes difficult, and a coating method by slit coating has been proposed.
　感光性組成物をスリットコート法で基板表面に塗布する場合、塗布速度にもよるが、良好な膜厚均一性を得るために感光性樹脂組成物の粘度は３．５ｍＰａ・ｓ未満が好ましい。感光性樹脂組成物の粘度が高い場合、スリットノズルから供給される感光性樹脂組成物が液切れし、基板表面に塗布されない部分が生じる。 When the photosensitive composition is applied to the substrate surface by the slit coating method, the viscosity of the photosensitive resin composition is preferably less than 3.5 mPa · s in order to obtain good film thickness uniformity, depending on the coating speed. When the viscosity of the photosensitive resin composition is high, the photosensitive resin composition supplied from the slit nozzle runs out of liquid, resulting in a portion that is not applied to the substrate surface.
　また感光性樹脂組成物をスリットコート法で塗布する場合、繰り返し使用するうちにスリットノズルに付着、残留する感光性樹脂組成物の乾燥固化物を、塗布前に洗浄する工程が必要である。この乾燥固化物の感光性樹脂組成物への再溶解性が低い場合、ノズル部分に残留した乾燥固化物が突起となって残り、基板に感光性樹脂組成物を塗布した際にノズルの進行方向に対して筋が発生するといった問題や、感光性樹脂組成物の乾燥固化物が落下して基板に付着し、欠陥となって歩留まりを低下させるといった問題が生じる。したがって、感光性樹脂組成物においては再溶解性を有することが生産性の点で重要となる。感光性樹脂組成物の再溶解性の改善を目的として、特定の溶媒を用いた感光性樹脂組成物が提案されている（例えば、特許文献１、特許文献２および特許文献３） In addition, when the photosensitive resin composition is applied by the slit coating method, it is necessary to wash the dried solidified product of the photosensitive resin composition that adheres to and remains on the slit nozzle during repeated use before application. When the re-solubility of the dried solidified product in the photosensitive resin composition is low, the dried solidified product remaining in the nozzle portion remains as a protrusion, and the nozzle traveling direction when the photosensitive resin composition is applied to the substrate As a result, problems such as streaks occur, and the dried and solidified product of the photosensitive resin composition drops and adheres to the substrate, resulting in defects and a decrease in yield. Therefore, in the photosensitive resin composition, having re-solubility is important in terms of productivity. In order to improve the re-solubility of the photosensitive resin composition, photosensitive resin compositions using a specific solvent have been proposed (for example, Patent Document 1, Patent Document 2, and Patent Document 3).
　カラーフィルタに対する要求特性のひとつに高コントラスト化がある。遮光性が高いブラックマトリックスを製造可能な感光性樹脂組成物が求められている。遮光性が高いブラックマトリックスを製造するために、顔料を高濃度に含有する感光性樹脂組成物が提案されている（例えば特許文献４）。 High contrast is one of the required characteristics for color filters. There is a need for a photosensitive resin composition capable of producing a black matrix having high light shielding properties. In order to produce a black matrix having a high light-shielding property, a photosensitive resin composition containing a pigment in a high concentration has been proposed (for example, Patent Document 4).
特開２００８－５８５５１号公報JP 2008-58551 A 特開２００８－８９７４３号公報JP 2008-89743 A 特開２００８－８９７４４号公報JP 2008-89744 A 国際公開第２００８／１３３３１２号International Publication No. 2008/13312
　遮光性が高いブラックマトリックスを製造できる感光性樹脂組成物には、特許文献４で提案されるように、顔料を高濃度に含有させる必要があるが、顔料濃度の増加に伴い感光性樹脂組成物の再溶解性が悪化する。
　本発明者の知見によれば、高コントラスト化のために顔料を高濃度に含有させた感光性樹脂組成物においては、先行文献で提案されている溶媒を用いても、再溶解性は満足するものではなく、特許文献４に記載の感光性樹脂組成物をスリットコート法で塗布した塗膜において、乾燥固化物による欠陥が発生しやすい。 The photosensitive resin composition capable of producing a black matrix having a high light-shielding property needs to contain a pigment at a high concentration as proposed in Patent Document 4, but as the pigment concentration increases, the photosensitive resin composition The re-solubility of becomes worse.
According to the knowledge of the present inventor, in a photosensitive resin composition containing a pigment at a high concentration for high contrast, re-solubility is satisfied even when a solvent proposed in the prior art is used. However, in the coating film obtained by applying the photosensitive resin composition described in Patent Document 4 by the slit coating method, defects due to the dried solidified product are likely to occur.
　本発明は、顔料を高濃度に含有する遮光性が高いブラックマトリックスの製造が可能であり、かつそれ自体の乾燥固化物を溶解する再溶解性が高く、スリットコート法で得られる塗膜に欠陥が発生せず、さらにスリットコート法による塗布が可能な粘度を有するネガ型感光性樹脂組成物ならびにこれを用いた隔壁およびブラックマトリックスを提供することを目的とする。また本発明は、該感光性樹脂組成物を硬化することにより形成される、遮光性が高い隔壁を有する光学素子を提供することを目的とする。 The present invention makes it possible to produce a black matrix having a high concentration of pigment and a high light-shielding property, and has a high re-dissolvability to dissolve its own dried solidified product, resulting in defects in the coating film obtained by the slit coating method. An object of the present invention is to provide a negative photosensitive resin composition having a viscosity capable of being applied by a slit coating method, and a partition and a black matrix using the same. Moreover, an object of this invention is to provide the optical element which has a partition with high light-shielding property formed by hardening | curing this photosensitive resin composition.
　本発明は、以下［１］～［１２］の構成を有するネガ型感光性樹脂組成物、隔壁、ブラックマトリックスおよび光学素子を提供する。
［１］　アルカリ可溶性樹脂（Ａ）、光重合開始剤（Ｂ）、黒色着色剤（Ｃ）および溶媒（Ｄ）を含むネガ型感光性樹脂組成物であって、前記組成物の全固形分に対する前記黒色着色剤（Ｃ）の含有量が２０質量％超であり、前記溶媒（Ｄ）が下式（１）で表される化合物である溶媒（Ｄ１）を前記溶媒（Ｄ）の全量に対して、２０～１００質量％の割合で含むことを特徴とするネガ型感光性樹脂組成物。
　Ｒ１Ｏ（Ｃ２Ｈ４Ｏ）２Ｒ２　　　（１）
　式（１）中、Ｒ１はメチル基を示し、Ｒ２は炭素原子数２または３のアルキル基を示す。 The present invention provides a negative photosensitive resin composition, partition walls, a black matrix and an optical element having the following configurations [1] to [12].
[1] A negative photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerization initiator (B), a black colorant (C), and a solvent (D), the total solid content of the composition The content of the black colorant (C) is more than 20% by mass, and the solvent (D1) is a compound represented by the following formula (1) with respect to the total amount of the solvent (D). A negative photosensitive resin composition characterized by comprising 20 to 100% by mass.
R 1 O (C 2 H 4 O) 2 R 2 (1)
In formula (1), R 1 represents a methyl group, and R 2 represents an alkyl group having 2 or 3 carbon atoms.
［２］　前記溶媒（Ｄ１）が、ジエチレングリコールエチルメチルエーテルである、［１］のネガ型感光性樹脂組成物。
［３］　前記溶媒（Ｄ）が、さらに、環の構成原子として、二重結合を介して酸素原子と結合する炭素原子を１個以上含み、かつエーテル性酸素原子を含んでもよい、脂肪族環式化合物である溶媒（Ｄ２)を、前記溶媒（Ｄ）の全量に対して、１０～４０質量％の割合で含む、［１］または［２］のネガ型感光性樹脂組成物。
［４］　前記脂肪族環式化合物が環状エステルまたは環状ケトンである、［３］のネガ型感光性樹脂組成物。 [2] The negative photosensitive resin composition according to [1], wherein the solvent (D1) is diethylene glycol ethyl methyl ether.
[3] An aliphatic ring in which the solvent (D) further contains, as a ring constituent atom, one or more carbon atoms bonded to an oxygen atom via a double bond, and may contain an etheric oxygen atom. The negative photosensitive resin composition according to [1] or [2], wherein the solvent (D2), which is the formula compound, is contained in a proportion of 10 to 40% by mass with respect to the total amount of the solvent (D).
[4] The negative photosensitive resin composition according to [3], wherein the aliphatic cyclic compound is a cyclic ester or a cyclic ketone.
［５］　前記アルカリ可溶性樹脂（Ａ）が、１分子中に酸性基とエチレン性二重結合とを有する感光性樹脂である、［１］～［４］のいずれかのネガ型感光性樹脂組成物。
［６］　前記アルカリ可溶性樹脂（Ａ）が、酸性基が導入されたエポキシ(メタ）アクリレート樹脂である、［１］～［５］のいずれかのネガ型感光性樹脂組成物。 [5] The negative photosensitive resin composition according to any one of [1] to [4], wherein the alkali-soluble resin (A) is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. object.
[6] The negative photosensitive resin composition according to any one of [1] to [5], wherein the alkali-soluble resin (A) is an epoxy (meth) acrylate resin having an acidic group introduced.
［７］　前記光重合開始剤（Ｂ）がＯ－アシルオキシム化合物である、［１］～［６］のいずれかのネガ型感光性樹脂組成物。
［８］　前記光重合開始剤（Ｂ）が、下式（３）で表されるＯ－アシルオキシム化合物である、［１］～［７］のいずれかのネガ型感光性樹脂組成物。
Figure JPOXMLDOC01-appb-C000002
　式（３）中、Ｒ３は、水素原子、Ｒ６１またはＯＲ６２を示し、該Ｒ６１およびＲ６２は、それぞれ独立に、炭素原子数１～２０のアルキル基、シクロアルカン環中の水素原子がアルキル基に置換されていてもよい炭素原子数３～８のシクロアルキル基、炭素原子数２～５のアルケニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～３０のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～３０のフェニルアルキル基を示す。
　Ｒ４は、水素原子、炭素原子数１～２０のアルキル基、炭素原子数３～８のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～３０のフェニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～３０のフェニルアルキル基、炭素原子数２～２０のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンゾイル基、炭素原子数２～１２のアルコキシカルボニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のフェノキシカルボニル基、またはシアノ基を示す。
　Ｒ５は、炭素原子数１～２０のアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～３０のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～３０のフェニルアルキル基を示す。
　Ｒ６、Ｒ７、Ｒ８およびＲ９は、それぞれ独立に、水素原子、シアノ基、ハロゲン原子、ニトロ基、Ｒ６１、ＯＲ６２、炭素原子数２～２０のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンゾイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンジルカルボニル基、炭素原子数２～１２のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のフェノキシカルボニル基、炭素原子数１～２０のアミド基を示す。
　Ｒ０は、Ｒ６１、ＯＲ６２、シアノ基またはハロゲン原子を示す。ａは０または１～３の整数である。 [7] The negative photosensitive resin composition according to any one of [1] to [6], wherein the photopolymerization initiator (B) is an O-acyloxime compound.
[8] The negative photosensitive resin composition according to any one of [1] to [7], wherein the photopolymerization initiator (B) is an O-acyloxime compound represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000002
In formula (3), R 3 represents a hydrogen atom, R 61 or OR 62 , and each of R 61 and R 62 independently represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom in a cycloalkane ring Is a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group A 6-30 phenyl group or a phenylalkyl group having 7-30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group is shown.
R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 30 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. A phenyl group having 7 to 30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring being an alkyl group A benzoyl group having 7 to 20 carbon atoms which may be substituted, an alkoxycarbonyl group having 2 to 12 carbon atoms or a hydrogen atom in the benzene ring which may be substituted with an alkyl group having 7 to 20 carbon atoms A phenoxycarbonyl group or a cyano group.
R 5 represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group. An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R 61 , OR 62 , an alkanoyl group having 2 to 20 carbon atoms, or a hydrogen atom in the benzene ring. A benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an amide group having 1 to 20 carbon atoms.
R 0 represents R 61 , OR 62 , a cyano group or a halogen atom. a is 0 or an integer of 1 to 3.
［９］　前記黒色着色剤（Ｃ）がカーボンブラックまたは有機顔料である、［１］～［８］のいずれかのネガ型感光性樹脂組成物。
［１０］　基板表面を画素形成用の複数の区画に仕切る形に形成された隔壁であって、［１］～［９］のいずれかのネガ型感光性樹脂組成物の硬化膜からなることを特徴とする隔壁。
［１１］　［１０］の隔壁からなる基板表面を複数の区画に仕切ることを特徴とするブラックマトリックス。
［１２］　基板表面に複数の画素と隣接する画素間に位置する隔壁とを有する光学素子であって、前記隔壁が［１０］の隔壁で形成されていることを特徴とする光学素子。 [9] The negative photosensitive resin composition according to any one of [1] to [8], wherein the black colorant (C) is carbon black or an organic pigment.
[10] A partition formed so as to partition the substrate surface into a plurality of sections for pixel formation, and comprising a cured film of the negative photosensitive resin composition according to any one of [1] to [9] Features a partition wall.
[11] A black matrix characterized in that the substrate surface comprising the partition walls of [10] is partitioned into a plurality of sections.
[12] An optical element having a plurality of pixels and a partition located between adjacent pixels on the surface of the substrate, wherein the partition is formed of the partition of [10].
　本発明によれば、顔料を高濃度に含有する遮光性が高いブラックマトリックスの製造が可能であり、かつそれ自体の乾燥固化物を溶解する再溶解性が高く、スリットコート法で得られる塗膜に欠陥が発生せず、さらにスリットコート法による塗布が可能な粘度を有するネガ型感光性樹脂組成物ならびにこれを用いた隔壁およびブラックマトリックスの提供が可能である。本発明によれば、上記本発明のネガ型感光性樹脂組成物を用いた光学素子が得られる。 According to the present invention, it is possible to produce a black matrix having a high concentration of pigment and a high light-shielding property, and having a high re-dissolvability for dissolving its own dried solidified product, and a coating film obtained by a slit coating method. In addition, it is possible to provide a negative photosensitive resin composition having a viscosity that can be applied by a slit coating method, a partition wall, and a black matrix. According to the present invention, an optical element using the negative photosensitive resin composition of the present invention can be obtained.
　本明細書における「（メタ）アクリロイル…」とは、「メタクリロイル…」と「アクリロイル…」の総称である。（メタ）アクリル酸、（メタ）アクリレート、（メタ）アクリルアミド、（メタ）アクリル樹脂もこれと同様である。 In this specification, “(meth) acryloyl ...” is a general term for “methacryloyl ...” and “acryloyl…”. The same applies to (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, and (meth) acrylic resin.
　本明細書における式（１）で表される化合物を、化合物（１）という。他の化合物も同様である。
　本明細書における「全固形分」とは、ネガ型感光性樹脂組成物が含有する成分のうち、隔壁形成成分をいい、ネガ型感光性樹脂組成物を１４０℃で２４時間加熱して溶媒を除去した、残存物である。具体的には、溶媒（Ｄ）等の隔壁形成過程における加熱等により揮発する揮発性成分以外の全成分を示す。なお、全固形分の量は仕込み量からも計算できる。
　本明細書においては、ネガ型感光性樹脂組成物を塗布した膜を「塗膜」、それを乾燥させた状態を「膜」、さらに、それを硬化させて得られる膜を「硬化膜」という。ネガ型感光性樹脂組成物が黒色着色剤を含有することから、基板表面を複数の区画に仕切るように形成された硬化膜からなる「隔壁」によって基板表面が区画に仕切られたものを、「ブラックマトリックス」とする。 The compound represented by Formula (1) in this specification is called compound (1). The same applies to other compounds.
The “total solid content” in this specification refers to a partition-forming component among the components contained in the negative photosensitive resin composition, and the negative photosensitive resin composition is heated at 140 ° C. for 24 hours to remove the solvent. It is a removed residue. Specifically, all components other than the volatile component which volatilizes by heating etc. in the partition formation process such as the solvent (D) are shown. The total solid content can also be calculated from the charged amount.
In the present specification, a film coated with the negative photosensitive resin composition is referred to as a “coating film”, a dried state is referred to as a “film”, and a film obtained by curing the film is referred to as a “cured film”. . Since the negative photosensitive resin composition contains a black colorant, the substrate surface is partitioned into partitions by a “partition” made of a cured film formed so as to partition the substrate surface into a plurality of partitions. Black matrix ".
　本明細書における「インク」とは、乾燥硬化した後に、例えば光学的、電気的に機能を有する液状組成物を総称するものであり、従来から用いられている着色材料に限定されるものではない。また、上記インクを注入して形成される「画素」についても同様に、隔壁で仕切られた、光学的、電気的な機能を有する区分を表すものとして用いられる。
　以下、本発明の実施の形態を説明する。なお、本明細書において特に説明のない場合、％は質量％を表す。 The “ink” in the present specification is a general term for liquid compositions having, for example, optical and electrical functions after being dried and cured, and is not limited to conventionally used coloring materials. . Similarly, “pixels” formed by injecting the ink are also used to indicate sections having optical and electrical functions, which are partitioned by partition walls.
Embodiments of the present invention will be described below. In addition, unless otherwise indicated in this specification,% represents the mass%.
［アルカリ可溶性樹脂（Ａ）］
　本発明におけるアルカリ可溶性樹脂（Ａ）は、１分子中に酸性基とエチレン性二重結合とを有する感光性樹脂である。アルカリ可溶性樹脂（Ａ）が分子中にエチレン性二重結合を有することで、ネガ型感光性樹脂組成物の露光部は、光重合開始剤（Ｂ）から発生したラジカルにより重合して硬化する。このように硬化した露光部分はアルカリ現像液にて除去されない。また、アルカリ可溶性樹脂（Ａ）が分子中に酸性基を有することで、アルカリ現像液にて、硬化していないネガ型感光性樹脂組成物の未露光部を選択的に除去することができる。その結果、隔壁を形成することができる。 [Alkali-soluble resin (A)]
The alkali-soluble resin (A) in the present invention is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. Since the alkali-soluble resin (A) has an ethylenic double bond in the molecule, the exposed portion of the negative photosensitive resin composition is polymerized and cured by radicals generated from the photopolymerization initiator (B). The exposed portion thus cured is not removed with an alkaline developer. Moreover, when the alkali-soluble resin (A) has an acidic group in the molecule, an unexposed portion of the uncured negative photosensitive resin composition can be selectively removed with an alkali developer. As a result, a partition wall can be formed.
　前記酸性基としては、特に制限されないが、カルボキシ基、フェノール性水酸基、スルホ基およびリン酸基等が挙げられ、これらは１種を単独で用いても２種以上を併用してもよい。
　前記エチレン性二重結合としては、特に制限されないが、（メタ）アクリロイル基、アリル基、ビニル基、ビニルオキシ基およびビニルオキシアルキル基等の付加重合性を有する二重結合が挙げられ、これらは１種を単独で用いても２種以上を併用してもよい。なお、該エチレン性二重結合基が有する水素原子の一部または全てが、アルキル基、好ましくはメチル基で置換されていてもよい。 Although it does not restrict | limit especially as said acidic group, A carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, etc. are mentioned, These may be used individually by 1 type or may use 2 or more types together.
Although it does not restrict | limit especially as said ethylenic double bond, The double bond which has addition polymerizability, such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, and a vinyloxyalkyl group, is mentioned, These are 1 You may use a seed | species independently or may use 2 or more types together. In addition, some or all of the hydrogen atoms of the ethylenic double bond group may be substituted with an alkyl group, preferably a methyl group.
　アルカリ可溶性樹脂（Ａ）としては、特に限定されないが、酸性基を有する側鎖とエチレン性二重結合を有する側鎖とを有する樹脂（Ａ１－１）、エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂（Ａ１－２）、酸性基を有する側鎖とエチレン性二重結合を有する側鎖とを有する単量体（Ａ１－３）等が挙げられる。これらは１種を単独で用いても２種以上を併用してもよい。 The alkali-soluble resin (A) is not particularly limited, but is a resin (A1-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy group having an acidic group and an ethylenic double chain. And a resin (A1-2) having a bond introduced therein, and a monomer (A1-3) having a side chain having an acidic group and a side chain having an ethylenic double bond. These may be used alone or in combination of two or more.
　樹脂（Ａ１－１）は、例えば、以下の（ｉ）または(ii）の方法で合成できる。
（ｉ）側鎖に酸性基以外の反応性基、例えば、水酸基、エポキシ基等の反応性基を有する単量体と、側鎖に酸性基を有する単量体とを共重合させ、反応性基を有する側鎖と、酸性基を有する側鎖を有する共重合体を得る。次いで、この共重合体と、上記反応性基に対して結合し得る官能基およびエチレン性二重結合を有する化合物を反応させる。または、側鎖に酸性基、例えばカルボキシ基等を有する単量体を共重合させた後、酸性基に対して結合し得る官能基およびエチレン性二重結合を有する化合物を反応後に酸性基が残る量、反応させる。
（ii）上記（ｉ）と同様の酸性基以外の反応性基を側鎖に有する単量体と、この反応性基に対して結合し得る官能基および保護されたエチレン性二重結合を有する化合物を反応させる。次いで、この単量体と側鎖に酸性基を有する単量体とを共重合させた後、エチレン性二重結合の保護を外す。または、側鎖に酸性基を有する単量体と、側鎖に保護されたエチレン性二重結合を有する単量体とを共重合させた後、エチレン性二重結合の保護を外す。
　なお、（ｉ）または(ii）は溶媒中で実施することが好ましい。
　これらのうちでも、本発明においては（ｉ）の方法が好ましく用いられる。以下、（ｉ）の方法について具体的に説明する。 Resin (A1-1) can be synthesized, for example, by the following method (i) or (ii).
(I) A monomer having a reactive group other than an acidic group in the side chain, for example, a monomer having a reactive group such as a hydroxyl group or an epoxy group, and a monomer having an acidic group in the side chain are copolymerized and reactive. A copolymer having a side chain having a group and a side chain having an acidic group is obtained. Next, this copolymer is reacted with a compound having a functional group capable of bonding to the reactive group and an ethylenic double bond. Alternatively, after copolymerization of a monomer having an acidic group such as a carboxy group in the side chain, the acidic group remains after the reaction with the functional group capable of bonding to the acidic group and the compound having an ethylenic double bond. Let react.
(Ii) having a monomer having a reactive group other than an acidic group in the side chain as in (i) above, a functional group capable of binding to this reactive group, and a protected ethylenic double bond The compound is reacted. Next, after the monomer and a monomer having an acidic group in the side chain are copolymerized, the protection of the ethylenic double bond is removed. Alternatively, after the monomer having an acidic group in the side chain is copolymerized with the monomer having an ethylenic double bond protected in the side chain, the protection of the ethylenic double bond is removed.
In addition, it is preferable to implement (i) or (ii) in a solvent.
Among these, the method (i) is preferably used in the present invention. Hereinafter, the method (i) will be specifically described.
　反応性基として水酸基を有する単量体としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、５－ヒドロキシペンチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、４－ヒドロキシシクロヘキシル（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、シクロヘキサンジオールモノビニルエーテル、２－ヒドロキシエチルアリルエーテル、Ｎ－ヒドロキシメチル（メタ）アクリルアミド、Ｎ，Ｎ－ビス（ヒドロキシメチル）（メタ）アクリルアミド等が挙げられる。 As monomers having a hydroxyl group as a reactive group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5 -Hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (Meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl Meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide.
　上述の（ｉ）において、反応性基として水酸基を有する単量体を用いる場合、共重合させる酸性基を有する単量体は、特に限定されない。後述のカルボキシ基を有する単量体の他に、リン酸基を有する単量体として、２－（メタ）アクリロイルオキシエチルフォスフェート等が挙げられる。水酸基を反応性基として有する単量体と、酸性基を有する単量体との共重合は、従来公知の方法で行うことができる。 In the above (i), when a monomer having a hydroxyl group as a reactive group is used, the monomer having an acidic group to be copolymerized is not particularly limited. In addition to the monomer having a carboxy group described below, examples of the monomer having a phosphate group include 2- (meth) acryloyloxyethyl phosphate. Copolymerization of a monomer having a hydroxyl group as a reactive group and a monomer having an acidic group can be carried out by a conventionally known method.
　得られた共重合体と反応させる、水酸基に対して結合し得る官能基およびエチレン性二重結合を有する化合物としては、エチレン性二重結合を有する酸無水物、イソシアネート基とエチレン性二重結合とを有する化合物、塩化アシル基とエチレン性二重結合とを有する化合物等が挙げられる。
　エチレン性二重結合を有する酸無水物としては、無水マレイン酸、無水イタコン酸、無水シトラコン酸、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物、３，４，５，６－テトラヒドロフタル酸無水物、ｃｉｓ－１，２，３，６－テトラヒドロフタル酸無水物、２－ブテン－１－イルサクシニックアンハイドライド等が挙げられる。
　イソシアネート基とエチレン性二重結合とを有する化合物としては、２－（メタ）アクリロイルオキシエチルイソシアネート、１，１－ビス（（メタ）アクリロイルオキシメチル）エチルイソシアネート等が挙げられる。
　塩化アシル基とエチレン性二重結合とを有する化合物としては、（メタ）アクリロイルクロライド等が挙げられる。 Examples of the compound having an ethylenic double bond and a functional group capable of bonding to a hydroxyl group to be reacted with the obtained copolymer include an acid anhydride having an ethylenic double bond, an isocyanate group and an ethylenic double bond. And a compound having an acyl chloride group and an ethylenic double bond.
Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal And acid anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, and the like.
Examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.
　反応性基としてエポキシ基を有する単量体としては、グリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチルアクリレート等が挙げられる。
　反応性基としてエポキシ基を有する単量体と共重合させる酸性基を有する単量体としては、上記水酸基を反応性基として有する単量体で説明したのと同様の単量体が使用でき、エポキシ基を反応性基として有する単量体と酸性基を有する単量体の共重合についても、従来公知の方法で行うことができる。 Examples of the monomer having an epoxy group as a reactive group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
As a monomer having an acidic group to be copolymerized with a monomer having an epoxy group as a reactive group, the same monomer as described in the monomer having a hydroxyl group as a reactive group can be used, Copolymerization of a monomer having an epoxy group as a reactive group and a monomer having an acidic group can also be performed by a conventionally known method.
　得られた共重合体と反応させる、エポキシ基に対して結合し得る官能基およびエチレン性二重結合を有する化合物として、カルボキシ基とエチレン性二重結合を有する化合物が挙げられる。該化合物の具体例としては、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、ケイ皮酸およびこれらの塩等が挙げられる。なお、ここで生じた水酸基とカルボン酸の脱水縮合部分が環状構造の一部をなす酸無水物とを反応させ、樹脂（Ａ１－１）中にカルボキシ基を導入してもよい。 Examples of the compound having an ethylenic double bond and a functional group capable of bonding to an epoxy group to be reacted with the obtained copolymer include compounds having a carboxy group and an ethylenic double bond. Specific examples of the compound include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. In addition, a carboxy group may be introduced into the resin (A1-1) by reacting the generated hydroxyl group with an acid anhydride in which the dehydration condensation part of the carboxylic acid forms part of the cyclic structure.
　反応性基としてカルボキシ基を有する単量体としては、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、ケイ皮酸およびこれらの塩等が挙げられる。なお、これらの単量体は上述した酸性基を有する単量体としても用いられる。 Examples of the monomer having a carboxy group as a reactive group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. In addition, these monomers are used also as a monomer which has the acidic group mentioned above.
　反応性基としてカルボキシ基を有する単量体を用いる場合、上記の通り該単量体を重合させる。得られた重合体と反応させる、カルボキシ基に対して結合し得る官能基およびエチレン性二重結合を有する化合物として、エポキシ基とエチレン性二重結合を有する化合物が挙げられる。該化合物としては、グリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチルアクリレート等が挙げられる。なお、この場合、カルボキシ基を有する共重合体と反応させる、カルボキシ基に対して結合し得る官能基およびエチレン性二重結合を有する化合物の量は、反応後に重合体においてカルボキシ基が酸性基として側鎖に残る量とする。 When using a monomer having a carboxy group as a reactive group, the monomer is polymerized as described above. Examples of the compound having an ethylenic double bond and a functional group capable of bonding to a carboxy group to be reacted with the obtained polymer include compounds having an epoxy group and an ethylenic double bond. Examples of the compound include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate. In this case, the amount of the functional group capable of bonding to the carboxy group and the compound having an ethylenic double bond to be reacted with the copolymer having a carboxy group is such that the carboxy group is converted into an acidic group in the polymer after the reaction. The amount remaining in the side chain.
　樹脂（Ａ１－２）は、エポキシ樹脂と、後述するカルボキシ基とエチレン性二重結合とを有する化合物とを反応させた後に、多価カルボン酸またはその無水物とを反応させることにより合成することができる。
　具体的には、エポキシ樹脂と、カルボキシ基とエチレン性二重結合を有する化合物とを反応させることにより、エポキシ樹脂にエチレン性二重結合が導入される。次に、エチレン性二重結合が導入されたエポキシ樹脂に多価カルボン酸またはその無水物を反応させることにより、カルボキシ基を導入することができる。 Resin (A1-2) is synthesized by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond, which will be described later, and then reacting with a polyvalent carboxylic acid or an anhydride thereof. Can do.
Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond. Next, a carboxyl group can be introduced by reacting a polycarboxylic acid or an anhydride thereof with an epoxy resin into which an ethylenic double bond has been introduced.
　エポキシ樹脂としては、特に限定されないが、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ナフタレン骨格を有するエポキシ樹脂、下式（Ａ１－２ａ）で表されるビフェニル骨格を有するエポキシ樹脂、下式（Ａ１－２ｂ）で表されるエポキシ樹脂、下式（Ａ１－２ｃ）で表されるビフェニル骨格を有するエポキシ樹脂等が挙げられる。 The epoxy resin is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having naphthalene skeleton, And an epoxy resin having a biphenyl skeleton represented by (A1-2a), an epoxy resin represented by the following formula (A1-2b), an epoxy resin having a biphenyl skeleton represented by the following formula (A1-2c), and the like. It is done.
Figure JPOXMLDOC01-appb-C000003
 　（式（Ａ１－２ａ）中、ｖは、１～５０の整数であり、２～１０の整数が好ましい。またベンゼン環の水素原子はそれぞれ独立に、炭素原子数１～１２のアルキル基、ハロゲン原子、または、一部の水素原子が置換基で置換されていてもよいフェニル基、で置換されていてもよい。）
Figure JPOXMLDOC01-appb-C000003
 (In the formula (A1-2a), v is an integer of 1 to 50, preferably an integer of 2 to 10. The hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, halogen An atom or a part of hydrogen atoms may be substituted with a phenyl group which may be substituted with a substituent.)
Figure JPOXMLDOC01-appb-C000004
　（式（Ａ１－２ｂ）中、Ｒ３１、Ｒ３２、Ｒ３３およびＲ３４は、それぞれ独立に、水素原子、塩素原子または炭素原子数が１～５のアルキル基であり、ｗは、０または１～１０の整数である。）
Figure JPOXMLDOC01-appb-C000004
(In the formula (A1-2b), R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and w is 0 or (It is an integer from 1 to 10.)
Figure JPOXMLDOC01-appb-C000005
　（式（Ａ１－２ｃ）中、ベンゼン環の水素原子はそれぞれ独立に炭素原子数１～１２のアルキル基、ハロゲン原子、または、一部の水素原子が置換基で置換されていてもよいフェニル基、で置換されていてもよい。ｕは、０または１～１０の整数である。）
Figure JPOXMLDOC01-appb-C000005
(In the formula (A1-2c), the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which some of the hydrogen atoms may be substituted with a substituent. And u is an integer of 0 or 1 to 10.)
　エチレン性二重結合を導入するためにエポキシ樹脂と反応させる、カルボキシ基とエチレン性二重結合とを有する化合物としては、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、ケイ皮酸およびこれらの塩等が好ましく、アクリル酸またはメタクリル酸が特に好ましい。すなわち、樹脂（Ａ１－２）としては、酸性基が導入されたエポキシ(メタ）アクリレート樹脂が好ましい。
　エポキシ樹脂と、カルボキシ基とエチレン性二重結合を有する化合物とを反応させて得られる樹脂のアルコール性水酸基に、多価カルボン酸無水物を反応させることで樹脂（Ａ１－２）が得られる。多価カルボン酸無水物としては、ジカルボン酸無水物およびテトラカルボン酸二無水物の混合物を用いることが好ましい。ジカルボン酸無水物とテトラカルボン酸二無水物の比率を変化させることにより、分子量を制御することができる。 Compounds having carboxy groups and ethylenic double bonds that are reacted with epoxy resins to introduce ethylenic double bonds include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid. Acid, cinnamic acid and salts thereof are preferable, and acrylic acid or methacrylic acid is particularly preferable. That is, the resin (A1-2) is preferably an epoxy (meth) acrylate resin into which an acidic group has been introduced.
Resin (A1-2) is obtained by reacting a polycarboxylic acid anhydride with an alcoholic hydroxyl group of a resin obtained by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond. As the polyvalent carboxylic acid anhydride, a mixture of dicarboxylic acid anhydride and tetracarboxylic dianhydride is preferably used. By changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride, the molecular weight can be controlled.
　樹脂（Ａ１－２）は、市販品を使用することができる。市販品としては、いずれも商品名で、ＫＡＹＡＲＡＤ　ＰＣＲ－１０６９、Ｋ－４８Ｃ、ＣＣＲ－１１０５、ＣＣＲ－１１１５、ＣＣＲ－１１５９Ｈ、ＣＣＲ－１２３５、ＴＣＲ－１０２５、ＴＣＲ－１０６４Ｈ、ＴＣＲ－１２８６Ｈ、ＺＡＲ－１５３５Ｈ、ＺＡＲ－２００１Ｈ、ＺＡＲ－２００２、ＺＦＲ－１４９１Ｈ、ＺＦＲ－１４９２Ｈ、ＺＣＲ－１５７１Ｈ、ＺＣＲ－１５６９Ｈ、ＺＣＲ－１５８０Ｈ、ＺＣＲ－１５８１Ｈ、ＺＣＲ－１５８８Ｈ、ＺＣＲ－１６４２Ｈ、ＺＣＲ－１６６４Ｈ（以上、日本化薬社製）、ＥＸ１０１０（ナガセケムテックス社製）等が挙げられる。 As the resin (A1-2), a commercially available product can be used. As commercial products, all are trade names, such as KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR- 1535H, ZAR-2001H, ZAR-2002, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H (above, Nipponization) Yakusho), EX1010 (manufactured by Nagase ChemteX) and the like.
　単量体（Ａ１－３）としては、２，２，２－トリアクリロイルオキシメチルエチルフタル酸（ＮＫエステル　ＣＢＸ－１　新中村化学工業社製）等が挙げられる。 Examples of the monomer (A1-3) include 2,2,2-triacryloyloxymethylethylphthalic acid (NK ester CBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.).
　アルカリ可溶性樹脂（Ａ）としては、現像時の硬化膜の剥離が抑制されて、高解像度のパターンを得ることができる点、ラインの直線性が良好である点、ポストベーク工程後の外観が維持され、平滑な硬化膜の表面が得られやすい点で、樹脂（Ａ１－２）を用いることが好ましい。 As alkali-soluble resin (A), the peeling of the cured film during development is suppressed, a high-resolution pattern can be obtained, the line linearity is good, and the appearance after the post-baking process is maintained. The resin (A1-2) is preferably used from the viewpoint that a smooth cured film surface can be easily obtained.
　樹脂（Ａ１－２）としては、ビスフェノールＡ型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、ビスフェノールＦ型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、フェノールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、クレゾールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、トリスフェノールメタン型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、式（Ａ１－２ａ）～（Ａ１－２ｃ）で表されるエポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂が好ましい。さらに、樹脂（Ａ１－２）としては、酸性基が導入されたエポキシ(メタ）アクリレート樹脂が特に好ましい。 Examples of the resin (A1-2) include a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, phenol Resin with acid group and ethylenic double bond introduced into novolac type epoxy resin, resin with acid group and ethylenic double bond introduced into cresol novolac type epoxy resin, acid group and ethylene into trisphenol methane type epoxy resin A resin into which an acidic double bond is introduced, and a resin in which an acidic group and an ethylenic double bond are introduced into the epoxy resins represented by the formulas (A1-2a) to (A1-2c) are preferable. Furthermore, as the resin (A1-2), an epoxy (meth) acrylate resin having an acidic group introduced is particularly preferable.
　アルカリ可溶性樹脂（Ａ）が１分子中に有するエチレン性二重結合の数は、平均３個以上が好ましく、６個以上が特に好ましい。エチレン性二重結合の数が上記範囲の下限値以上であると、露光部分と未露光部分とのアルカリ溶解度に差がつきやすく、より少ない露光量での微細なパターン形成が可能となる。 The number of ethylenic double bonds of the alkali-soluble resin (A) in one molecule is preferably 3 or more on average, and particularly preferably 6 or more. When the number of ethylenic double bonds is at least the lower limit of the above range, the alkali solubility between the exposed and unexposed portions is likely to be different, and a fine pattern can be formed with a smaller exposure amount.
　アルカリ可溶性樹脂（Ａ）の質量平均分子量（Ｍｗ）は、１．５×１０３～３０×１０３が好ましく、２×１０３～２０×１０３が特に好ましい。また、数平均分子量（Ｍｎ）は、５００～２０×１０３が好ましく、１×１０３～１０×１０３が特に好ましい。質量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）が上記範囲の下限値以上であると、露光時の硬化性に優れ、上記範囲の上限値以下であると、現像性が良好である。
　アルカリ可溶性樹脂（Ａ）の酸価は、１０～３００ｍｇＫＯＨ／ｇが好ましく、３０～１５０ｍｇＫＯＨ／ｇが特に好ましい。酸価が上記範囲であると、ネガ型感光性樹脂組成物の現像性が良好になる。 The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1.5 × 10 3 to 30 × 10 3 , particularly preferably 2 × 10 3 to 20 × 10 3 . The number average molecular weight (Mn) is preferably from 500 to 20 × 10 3 , particularly preferably from 1 × 10 3 to 10 × 10 3 . When the mass average molecular weight (Mw) and the number average molecular weight (Mn) are not less than the lower limit of the above range, the curability at the time of exposure is excellent, and when it is not more than the upper limit of the above range, the developability is good.
The acid value of the alkali-soluble resin (A) is preferably 10 to 300 mgKOH / g, particularly preferably 30 to 150 mgKOH / g. When the acid value is in the above range, the developability of the negative photosensitive resin composition is improved.
　ネガ型感光性樹脂組成物に含まれるアルカリ可溶性樹脂（Ａ）は、１種を単独で用いても２種以上を併用してもよい。
　ネガ型感光性樹脂組成物における全固形分中のアルカリ可溶性樹脂（Ａ）の含有割合は、５～８０質量％が好ましく、１０～６０質量％が特に好ましい。含有割合が上記範囲であると、ネガ型感光性樹脂組成物の現像性が良好である。 The alkali-soluble resin (A) contained in the negative photosensitive resin composition may be used alone or in combination of two or more.
The content of the alkali-soluble resin (A) in the total solid content in the negative photosensitive resin composition is preferably 5 to 80% by mass, particularly preferably 10 to 60% by mass. When the content ratio is in the above range, the developability of the negative photosensitive resin composition is good.
［光重合開始剤（Ｂ）］
　本発明における光重合開始剤（Ｂ）としては、光によりラジカルを発生する化合物が特に制限なく用いられる。このような化合物として、具体的には、Ｏ－アシルオキシム化合物が挙げられる。例えば、ＩＲＧＡＣＵＲＥ　ＯＸＥ０１（ＢＡＳＦ社製：１，２－オクタンジオン，１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］に相当する。）、アデカオプトマー　Ｎ－１９１９、アデカクルーズ　ＮＣＩ－８３１、ＮＣＩ－９３０（以上、ＡＤＥＫＡ社製）等が挙げられる。該Ｏ－アシルオキシム化合物のなかでも、少ない露光量においても良好な形状の隔壁を製造できる下式（３）で表される化合物が好ましい。以下、式（３）で表される化合物を光重合開始剤（３）という。光重合開始剤（Ｂ）は、光重合開始剤（３）の１種または２種以上を含むことが好ましく、光重合開始剤（３）のみで構成されることが特に好ましい。 [Photoinitiator (B)]
As the photopolymerization initiator (B) in the present invention, a compound that generates a radical by light is used without particular limitation. Specific examples of such compounds include O-acyloxime compounds. For example, IRGACURE OXE01 (corresponding to BASF Corporation: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)]), Adekaoptomer N-1919, Adeka Cruz NCI -831, NCI-930 (manufactured by ADEKA) and the like. Among the O-acyloxime compounds, compounds represented by the following formula (3) that can produce partition walls having a good shape even with a small exposure amount are preferable. Hereinafter, the compound represented by the formula (3) is referred to as a photopolymerization initiator (3). It is preferable that a photoinitiator (B) contains 1 type, or 2 or more types of a photoinitiator (3), and it is especially preferable to be comprised only with a photoinitiator (3).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（３）中、Ｒ３は、水素原子、Ｒ６１またはＯＲ６２を示し、該Ｒ６１およびＲ６２は、それぞれ独立に、炭素原子数１～２０のアルキル基、シクロアルカン環中の水素原子がアルキル基に置換されていてもよい炭素原子数３～８のシクロアルキル基、炭素原子数２～５のアルケニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～３０のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～３０のフェニルアルキル基を示す。 In formula (3), R 3 represents a hydrogen atom, R 61 or OR 62 , and each of R 61 and R 62 independently represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom in a cycloalkane ring Is a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group A 6-30 phenyl group or a phenylalkyl group having 7-30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group is shown.
　Ｒ４は、水素原子、炭素原子数１～２０のアルキル基、炭素原子数３～８のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～３０のフェニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～３０のフェニルアルキル基、炭素原子数２～２０のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンゾイル基、炭素原子数２～１２のアルコキシカルボニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のフェノキシカルボニル基、またはシアノ基を示す。 R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 30 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. A phenyl group having 7 to 30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring being an alkyl group A benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a hydrogen atom in the benzene ring which may be substituted with an alkyl group. A phenoxycarbonyl group or a cyano group.
　Ｒ５は、炭素原子数１～２０のアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～３０のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～３０のフェニルアルキル基を示す。
　Ｒ６、Ｒ７、Ｒ８およびＲ９は、それぞれ独立に、水素原子、シアノ基、ハロゲン原子、ニトロ基、Ｒ６１、ＯＲ６２、炭素原子数２～２０のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンゾイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンジルカルボニル基、炭素原子数２～１２のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のフェノキシカルボニル基、炭素原子数１～２０のアミド基を示す。
　Ｒ０は、Ｒ６１、ＯＲ６２、シアノ基またはハロゲン原子を示す。ａは０または１～３の整数である。 R 5 represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group. An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R 61 , OR 62 , an alkanoyl group having 2 to 20 carbon atoms, or a hydrogen atom in the benzene ring. A benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an amide group having 1 to 20 carbon atoms.
R 0 represents R 61 , OR 62 , a cyano group or a halogen atom. a is 0 or an integer of 1 to 3.
　光重合開始剤（３）のなかでも、以下の態様である化合物が特に好ましい。
　Ｒ３としては、炭素原子数１～１０のアルキル基、または、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～１２のフェニル基が好ましく、例えば、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、ノニル基、デシル基、フェニル基等が挙げられる。炭素原子数１～４のアルキル基がより好ましく、炭素原子数１～２のアルキル基がさらに好ましく、メチル基が特に好ましい。
　Ｒ４としては、炭素原子数１～１０のアルキル基、または、炭素原子数２～５のアルコキシカルボニル基が好ましく、例えば、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、ノニル基、デシル基、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基等が挙げられる。炭素原子数１～６のアルキル基がより好ましく、炭素原子数１～３のアルキル基がさらに好ましく、メチル基が特に好ましい。
　光重合開始剤（３）として、国際公開第２００８／０７８６７８号に記載のＮｏ．１～７１も使用できる。 Among the photopolymerization initiators (3), compounds having the following modes are particularly preferable.
R 3 is preferably an alkyl group having 1 to 10 carbon atoms, or a phenyl group having 6 to 12 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, such as a methyl group, Examples include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a phenyl group. An alkyl group having 1 to 4 carbon atoms is more preferred, an alkyl group having 1 to 2 carbon atoms is more preferred, and a methyl group is particularly preferred.
R 4 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and the like. An alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
As the photopolymerization initiator (3), No. 1 described in International Publication No. 2008/078678. 1 to 71 can also be used.
　光重合開始剤（３）のなかでも、以下の態様である化合物が好ましい。
　式（３）中、Ｒ５としては、炭素原子数１～８のアルキル基が好ましく、例えばメチル基、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、等が挙げられる。炭素原子数２～６のアルキル基がより好ましく、エチル基が特に好ましい。
　Ｒ６、Ｒ８およびＲ９としては、水素原子またはニトロ基が好ましい。
　Ｒ７としては、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンゾイル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンジルカルボニル基またはニトロ基が好ましく、ベンゾイル基、２－メチルベンゾイル基、２－メチル－４－テトラヒドロピラニルメトキシベンゾイル基、２－メチル－５－テトラヒドロフラニルメトキシベンゾイル基、２－メチル－５－テトラヒドロピラニルメトキシベンゾイル基、ベンジルカルボニル基、１，３，５トリメチルベンジルカルボニル基、ニトロ基が特に好ましい。
　Ｒ０の個数を示すａは０である。 Among the photopolymerization initiators (3), compounds having the following modes are preferred.
In formula (3), R 5 is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Can be mentioned. An alkyl group having 2 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
R 6 , R 8 and R 9 are preferably a hydrogen atom or a nitro group.
R 7 represents a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. 7-20 benzylcarbonyl groups or nitro groups are preferred, benzoyl group, 2-methylbenzoyl group, 2-methyl-4-tetrahydropyranylmethoxybenzoyl group, 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group, 2-methyl A -5-tetrahydropyranylmethoxybenzoyl group, benzylcarbonyl group, 1,3,5 trimethylbenzylcarbonyl group and nitro group are particularly preferred.
“A” indicating the number of R 0 is 0.
　光重合開始剤（３）の具体例としては、式（３）において、Ｒ３～Ｒ９がそれぞれ以下の基であり、Ｒ０の個数を示すａは０である化合物（３－１）～（３－１０）等を挙げることができる。
Ｒ３：フェニル基、Ｒ４：オクチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：ベンゾイル基である化合物（３－１）、
Ｒ３：メチル基、Ｒ４：オクチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：ベンゾイル基である化合物（３－２）、
Ｒ３：メチル基、Ｒ４：ブチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：ベンゾイル基である化合物（３－３）、
Ｒ３：メチル基、Ｒ４：ヘプチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：ベンゾイル基である化合物（３－４）、
Ｒ３：フェニル基、Ｒ４：オクチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：２－メチルベンゾイル基である化合物（３－５）、
Ｒ３：メチル基、Ｒ４：オクチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：２－メチルベンゾイル基である化合物（３－６）、
Ｒ３：メチル基、Ｒ４：メチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：２－メチルベンゾイル基である化合物（３－７）、
Ｒ３：メチル基、Ｒ４：メチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：２－メチル－４－テトラヒドロピラニルメトキシベンゾイル基である化合物（３－８）、
Ｒ３：メチル基、Ｒ４：メチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：２－メチル－５－テトラヒドロフラニルメトキシベンゾイル基である化合物（３－９）、
Ｒ３：メチル基、Ｒ４：メチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：２－メチル－５－テトラヒドロピラニルメトキシベンゾイル基である化合物（３－１０） Specific examples of the photopolymerization initiator (3) include compounds (3-1) to (3) wherein R 3 to R 9 are the following groups, and a indicating the number of R 0 is 0: (3-10).
A compound (3-1) wherein R 3 is a phenyl group, R 4 is an octyl group, R 5 is an ethyl group, R 6 , R 8 , R 9 is a hydrogen atom, and R 7 is a benzoyl group;
Compound (3-2), wherein R 3 is a methyl group, R 4 is an octyl group, R 5 is an ethyl group, R 6 , R 8 , R 9 is a hydrogen atom, and R 7 is a benzoyl group,
Compound (3-3) wherein R 3 is a methyl group, R 4 is a butyl group, R 5 is an ethyl group, R 6 , R 8 , R 9 is a hydrogen atom, and R 7 is a benzoyl group,
Compound (3-4), wherein R 3 is a methyl group, R 4 is a heptyl group, R 5 is an ethyl group, R 6 , R 8 , R 9 is a hydrogen atom, and R 7 is a benzoyl group,
Compound (3-5) wherein R 3 is a phenyl group, R 4 is an octyl group, R 5 is an ethyl group, R 6 , R 8 , R 9 is a hydrogen atom, and R 7 is a 2-methylbenzoyl group,
Compound (3-6), wherein R 3 is a methyl group, R 4 is an octyl group, R 5 is an ethyl group, R 6 , R 8 , R 9 is a hydrogen atom, and R 7 is a 2-methylbenzoyl group,
Compound (3-7), wherein R 3 : methyl group, R 4 : methyl group, R 5 : ethyl group, R 6 , R 8 , R 9 : hydrogen atom, R 7 : 2-methylbenzoyl group,
R 3 : methyl group, R 4 : methyl group, R 5 : ethyl group, R 6 , R 8 , R 9 : hydrogen atom, R 7 : 2-methyl-4-tetrahydropyranylmethoxybenzoyl group (3 -8),
R 3 : methyl group, R 4 : methyl group, R 5 : ethyl group, R 6 , R 8 , R 9 : hydrogen atom, R 7 : 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group (3- 9),
R 3 : methyl group, R 4 : methyl group, R 5 : ethyl group, R 6 , R 8 , R 9 : hydrogen atom, R 7 : 2-methyl-5-tetrahydropyranylmethoxybenzoyl group (3 -10)
　光重合開始剤（３）は市販品を使用することができる。市販品としては、いずれも商品名で、ＩＲＧＡＣＵＲＥ　ＯＸＥ０２（ＢＡＳＦ社製：上記化合物（３－７）に相当する。）等が挙げられる。 As the photopolymerization initiator (3), a commercially available product can be used. Examples of commercially available products include IRGACURE OXE02 (manufactured by BASF: equivalent to the above compound (3-7)) under the trade name.
　ネガ型感光性樹脂組成物における全固形分中の光重合開始剤（Ｂ）の割合は１～１５質量％が好ましく、２～１０質量％がより好ましく、３～６質量％が特に好ましい。また、光重合開始剤（Ｂ）における光重合開始剤（３）の割合は、５０～１００質量％が好ましく、７５～１００質量％がより好ましく、１００質量％が特に好ましい。全固形分中の光重合開始剤（Ｂ）の割合および光重合開始剤（Ｂ）中の光重合開始剤（３）の割合が上記範囲であると、ネガ型感光性樹脂組成物の硬化性が良好で、塗膜形成後、露光工程および現像工程を経て得られる隔壁やブラックマトリックスにおいてラインパターンや線幅を露光時のマスクパターンに近い形状に形成することができる。 The proportion of the photopolymerization initiator (B) in the total solid content in the negative photosensitive resin composition is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and particularly preferably 3 to 6% by mass. The ratio of the photopolymerization initiator (3) in the photopolymerization initiator (B) is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and particularly preferably 100% by mass. When the ratio of the photopolymerization initiator (B) in the total solid content and the ratio of the photopolymerization initiator (3) in the photopolymerization initiator (B) are in the above ranges, the curability of the negative photosensitive resin composition. In the partition walls and black matrix obtained through the exposure process and the development process after forming the coating film, the line pattern and the line width can be formed in a shape close to the mask pattern at the time of exposure.
　本発明のネガ型感光性樹脂組成物において光重合開始剤（Ｂ）が、光重合開始剤（３）とともに含有してもよい光重合開始剤としては、以下の光重合開始剤が挙げられる。 Examples of the photopolymerization initiator that the photopolymerization initiator (B) may contain together with the photopolymerization initiator (3) in the negative photosensitive resin composition of the present invention include the following photopolymerization initiators.
　光重合開始剤（３）と併用してもよい光重合開始剤としては、メチルフェニルグリオキシレート、９，１０－フェナンスレンキノン等のα－ジケトン類；ベンゾイン等のアシロイン類；ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のアシロインエーテル類；チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン、２，４－ジイソプロピルチオキサントン、チオキサントン－４－スルホン酸等のチオキサントン類；ベンゾフェノン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン等のベンゾフェノン類；アセトフェノン、２－（４－トルエンスルホニルオキシ）－２－フェニルアセトフェノン、ｐ－ジメチルアミノアセトフェノン、２，２’－ジメトキシ－２－フェニルアセトフェノン、ｐ－メトキシアセトフェノン、２－メチル－［４－（メチルチオ）フェニル］－２－モルフォリノ－１－プロパノン、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－オン等のアセトフェノン類；アントラキノン、２－エチルアントラキノン、カンファーキノン、１，４－ナフトキノン等のキノン類；２－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸（ｎ－ブトキシ）エチル、４－ジメチルアミノ安息香酸イソアミル、４－ジメチルアミノ安息香酸２－エチルヘキシル等のアミノ安息香酸類；フェナシルクロライド、トリハロメチルフェニルスルホン等のハロゲン化合物；アシルホスフィンオキシド類；ジ－ｔ－ブチルパーオキサイド等の過酸化物；トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、ｎ－ブチルアミン、Ｎ－メチルジエタノールアミン、ジエチルアミノエチルメタクリレート等の脂肪族アミン類；２－メルカプトベンズイミダゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾチアゾール、１，４－ブタノールビス（３－メルカプトブチレート）、トリス（２－メルカプトプロパノイルオキシエチル）イソシアヌレート、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）等のチオール化合物等が挙げられる。 Photopolymerization initiators that may be used in combination with the photopolymerization initiator (3) include α-diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether Acylo ethers such as benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Thioxanthones such as 2,4-diisopropylthioxanthone and thioxanthone-4-sulfonic acid; benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzopheno Benzophenones such as acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [ Acetophenones such as 4- (methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; anthraquinone, 2-ethyl Quinones such as anthraquinone, camphorquinone, 1,4-naphthoquinone; ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), 4-dimethylaminobenzoic acid Isoamyl, 4-dimethylamino Aminobenzoic acids such as 2-ethylhexyl benzoate; halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone; peroxides such as di-t-butyl peroxide; triethanolamine, methyldiethanolamine, Aliphatic amines such as triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanol bis (3- Thiol compounds such as mercaptobutyrate), tris (2-mercaptopropanoyloxyethyl) isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), etc. And the like.
［黒色着色剤（Ｃ）］
　本発明におけるネガ型感光性樹脂組成物は、その全固形分に対して２０質量％超の割合で黒色着色剤（Ｃ）を含有する。
　黒色着色剤（Ｃ）としては、カーボンブラック、アニリンブラック、アントラキノン系黒色顔料、ペリレン系黒色顔料、アゾメチン系黒色顔料、具体的には、Ｃ．Ｉ．ピグメントブラック１、６、７、１２、２０、３１等が挙げられる。黒色着色剤（Ｃ）としては、赤色顔料、青色顔料、緑色顔料、黄色顔料等の有機顔料や無機顔料の混合物を用いることもできる。有機顔料の具体例としては、Ｃ．Ｉ．ピグメントブルー１５：６、ピグメントレッド２５４、ピグメントグリーン３６およびピグメントイエロー１５０が挙げられる。黒色着色剤（Ｃ）としては、電気特性の点から有機顔料が好ましく、価格および遮光性の点からはカーボンブラックが好ましい。カーボンブラックは樹脂等で表面処理されているのが好ましく、また、色調を調整するため、青色顔料や紫色顔料を併用することができる。なお、有機ＥＬ素子の画素部に用いられる隔壁においては、良好な電気特性とコントラスト向上の点から有機顔料が好ましい。 [Black colorant (C)]
The negative photosensitive resin composition in this invention contains a black coloring agent (C) in the ratio of more than 20 mass% with respect to the total solid.
Examples of the black colorant (C) include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, azomethine black pigment, specifically C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned. As the black colorant (C), a mixture of organic pigments and inorganic pigments such as a red pigment, a blue pigment, a green pigment, and a yellow pigment can also be used. Specific examples of organic pigments include C.I. I. Pigment Blue 15: 6, Pigment Red 254, Pigment Green 36, and Pigment Yellow 150. As the black colorant (C), an organic pigment is preferable from the viewpoint of electrical characteristics, and carbon black is preferable from the viewpoint of cost and light shielding properties. The carbon black is preferably surface-treated with a resin or the like, and a blue pigment or a violet pigment can be used in combination to adjust the color tone. In addition, in the partition used for the pixel part of an organic EL element, an organic pigment is preferable from the point of a favorable electrical property and a contrast improvement.
　有機顔料としては、ブラックマトリックスの形状の観点から、ＢＥＴ法による比表面積が５０～２００ｍ２／ｇであるものが好ましい。比表面積が５０ｍ２／ｇ以上であると、ブラックマトリックス形状が劣化しにくい。２００ｍ２／ｇ以下であると、有機顔料に分散助剤が過度に吸着することなく、諸物性を発現させるために多量の分散助剤を配合する必要がなくなる。 The organic pigment preferably has a specific surface area of 50 to 200 m 2 / g by the BET method from the viewpoint of the shape of the black matrix. When the specific surface area is 50 m 2 / g or more, the black matrix shape is hardly deteriorated. When it is 200 m 2 / g or less, the dispersion aid is not excessively adsorbed on the organic pigment, and it is not necessary to add a large amount of dispersion aid in order to develop various physical properties.
　また、有機顔料の透過型電子顕微鏡観察による平均１次粒子径は、２０～１５０ｎｍであることが好ましい。平均１次粒子径が２０ｎｍ以上であると、ネガ型感光性樹脂組成物で高濃度に分散でき、経時安定性の良好なネガ型感光性樹脂組成物が得られやすい。１５０ｎｍ以下であると、ブラックマトリックス形状が劣化しにくい。また、透過型電子顕微鏡観察による平均２次粒子径としては、８０～２００ｎｍが好ましい。 The average primary particle diameter of the organic pigment observed with a transmission electron microscope is preferably 20 to 150 nm. When the average primary particle diameter is 20 nm or more, the negative photosensitive resin composition can be dispersed at a high concentration with the negative photosensitive resin composition, and a negative photosensitive resin composition with good temporal stability can be easily obtained. When it is 150 nm or less, the black matrix shape is hardly deteriorated. Further, the average secondary particle diameter by observation with a transmission electron microscope is preferably 80 to 200 nm.
　ネガ型感光性樹脂組成物における全固形分中の黒色着色剤（Ｃ）の含有割合は、上記の通り２０質量％超である。含有割合を２０質量％超とすることで、得られる隔壁およびブラックマトリックスの光の遮光性を示す値である光学濃度（ＯＤ）を充分に確保し、隔壁およびブラックマトリックスを用いて作製されるカラーフィルタ等の高コントラスト化が可能となる。黒色着色剤（Ｃ）の含有割合は、２０～６５質量％が好ましく、２５～６５質量％が特に好ましい。上記範囲の上限値以下であると、ネガ型感光性樹脂組成物の硬化性が良好になり、良好な外観の硬化膜が得られる。 The content ratio of the black colorant (C) in the total solid content in the negative photosensitive resin composition is more than 20% by mass as described above. By setting the content ratio to more than 20% by mass, a color produced using the partition walls and the black matrix is obtained by sufficiently securing the optical density (OD), which is a value indicating the light shielding properties of the partition walls and the black matrix obtained. A high contrast such as a filter can be achieved. The content of the black colorant (C) is preferably 20 to 65% by mass, particularly preferably 25 to 65% by mass. When it is not more than the upper limit of the above range, the curability of the negative photosensitive resin composition becomes good, and a cured film having a good appearance can be obtained.
　黒色着色剤（Ｃ）のネガ型感光性樹脂組成物における分散性を向上するためには、高分子分散剤を含有させることが好ましい。該高分子分散剤は、黒色着色剤（Ｃ）への親和性の点から、塩基性官能基を有する化合物が好ましい。該塩基性官能基として、１級、２級もしくは３級アミノ基を有すると、特に分散性に優れる。
　高分子分散剤としては、ウレタン系、ポリイミド系、アルキッド系、エポキシ系、不飽和ポリエステル系、メラミン系、フェノール系、アクリル系、塩化ビニル系、塩化ビニル酢酸ビニル系共重合体系、ポリアミド系、ポリカーボネート系等の化合物が挙げられる。中でも特にウレタン系、ポリエステル系の化合物が好ましい。
　高分子分散剤の使用量は、黒色着色剤（Ｃ）に対して５～３０質量％が好ましく、１０～２５質量％が特に好ましい。使用量が上記範囲の下限値以上であると、黒色着色剤（Ｃ）の分散が良好になり、上記範囲の上限値以下であると、現像性が良好になる。 In order to improve the dispersibility of the black colorant (C) in the negative photosensitive resin composition, it is preferable to contain a polymer dispersant. The polymer dispersant is preferably a compound having a basic functional group from the viewpoint of affinity for the black colorant (C). When the basic functional group has a primary, secondary or tertiary amino group, the dispersibility is particularly excellent.
Polymer dispersing agents include urethane, polyimide, alkyd, epoxy, unsaturated polyester, melamine, phenol, acrylic, vinyl chloride, vinyl chloride vinyl acetate copolymer, polyamide, polycarbonate And the like. Of these, urethane-based and polyester-based compounds are particularly preferable.
The amount of the polymer dispersant used is preferably 5 to 30% by mass, particularly preferably 10 to 25% by mass, based on the black colorant (C). When the amount used is not less than the lower limit of the above range, the dispersion of the black colorant (C) becomes good, and when it is not more than the upper limit of the above range, the developability becomes good.
［溶媒（Ｄ）］
　本発明におけるネガ型感光性樹脂組成物は、溶媒（Ｄ）を含有する。また、溶媒（Ｄ）は、下式（１）で表される化合物である溶媒（Ｄ１）を前記溶媒（Ｄ）の全量に対して、２０～１００質量％の割合で含有する。
　Ｒ１Ｏ（Ｃ２Ｈ４Ｏ）２Ｒ２　　（１）
　式（１）中、Ｒ１はメチル基を示し、Ｒ２は炭素原子数が２または３のアルキル基を示す。 [Solvent (D)]
The negative photosensitive resin composition in the present invention contains a solvent (D). The solvent (D) contains the solvent (D1), which is a compound represented by the following formula (1), in a proportion of 20 to 100% by mass with respect to the total amount of the solvent (D).
R 1 O (C 2 H 4 O) 2 R 2 (1)
In formula (1), R 1 represents a methyl group, and R 2 represents an alkyl group having 2 or 3 carbon atoms.
　溶媒（Ｄ）は、ネガ型感光性樹脂組成物が含有する上記アルカリ可溶性樹脂（Ａ）、光重合開始剤（Ｂ）、黒色着色剤（Ｃ）および必要に応じて含有する任意成分と、反応性を有しない化合物で構成される。かつ、溶媒（Ｄ）は、これらの各固形成分を、特に黒色着色剤（Ｃ）を全固形分に対して２０質量％超の割合で含有する組成においても、均一に溶解または分散させて適度な粘度とし、隔壁が形成される基材へのネガ型感光性組成物の塗布を均一かつ効率的にする機能を有する。さらに、溶媒（Ｄ）は、ネガ型感光性樹脂組成物に、それ自体の乾燥固化物を同じ組成物で溶解させる性質、すなわち再溶解性を付与する機能を有する。 The solvent (D) reacts with the alkali-soluble resin (A) contained in the negative photosensitive resin composition, the photopolymerization initiator (B), the black colorant (C), and optional components contained as necessary. It is composed of a compound having no properties. In addition, the solvent (D) is suitably dissolved or dispersed evenly in the composition containing each of these solid components, particularly the black colorant (C) in a proportion of more than 20% by mass with respect to the total solid content. It has a function of making the negative photosensitive composition uniformly and efficiently applied to the base material on which the partition walls are formed. Further, the solvent (D) has a function of giving the negative photosensitive resin composition the property of dissolving its own dried solidified product with the same composition, that is, a re-solubility.
　ネガ型感光性樹脂組成物における溶媒（Ｄ）の含有割合は、ネガ型感光性樹脂組成物の組成や用途、これを用いて基板表面に隔壁等を形成する際の塗工方法等により異なるが、ネガ型感光性樹脂組成物中に５０～９９質量％の割合で配合されるのが好ましく、６０～９５質量％がより好ましく、６５～９０質量％が特に好ましい。 The content ratio of the solvent (D) in the negative photosensitive resin composition varies depending on the composition and use of the negative photosensitive resin composition, the coating method when using this to form partition walls on the substrate surface, and the like. The negative photosensitive resin composition is preferably blended in an amount of 50 to 99% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass.
　ネガ型感光性樹脂組成物における再溶解性は、特に、該組成物の基板表面への塗布をスリットコート法で行う場合に有することが求められる性質である。スリットコート法では、繰り返し使用するうちにスリットノズルに付着、残留したネガ型感光性樹脂組成物が乾燥固化して突起を形成し、塗工においてノズルの進行方向に対して筋が発生したり、乾燥固化物が落下して塗膜に異物が混入したりする問題があり、これらを防止するためにネガ型感光性樹脂組成物が再溶解性を有することが求められている。
　また、ネガ型感光性組成物の塗布を均一かつ簡便にするために好適な粘度としては、用いる塗工方法により異なる。塗工方法としてスリットコート法を用いる場合、塗布速度にもよるが、ネガ型感光性組成物の粘度は３．５ｍＰａ・ｓ未満が好ましく、特に好ましくは３ｍＰａ・ｓ未満である。下限値は１ｍＰａ・ｓ以上である。 The re-solubility in the negative photosensitive resin composition is a property that is particularly required when the composition is applied to the substrate surface by the slit coating method. In the slit coating method, the negative photosensitive resin composition that adheres to and remains on the slit nozzle during repeated use forms a protrusion by drying and solidifying, and streaks occur in the direction of nozzle movement in coating, There is a problem that the dried solid product falls and foreign matter is mixed into the coating film. In order to prevent these problems, the negative photosensitive resin composition is required to have re-solubility.
In addition, the viscosity suitable for making the application of the negative photosensitive composition uniform and simple varies depending on the coating method used. When the slit coating method is used as the coating method, the viscosity of the negative photosensitive composition is preferably less than 3.5 mPa · s, particularly preferably less than 3 mPa · s, depending on the coating speed. The lower limit is 1 mPa · s or more.
　本発明のネガ型感光性樹脂組成物においては、溶媒（Ｄ）が、上記化合物（１）である溶媒（Ｄ１）を上記割合で含有することで、黒色着色剤（Ｃ）を高濃度に含有しながら、スリットコート法において必要とされるネガ型感光性樹脂組成物の粘度と再溶解性を確保することを可能としている。
　化合物（１）は、式（１）中の－Ｏ－Ｃ２Ｈ４－Ｏ－Ｃ２Ｈ４－Ｏ－の構造が親水性を有することで、親水性を有するアルカリ可溶性樹脂（Ａ）に対する溶解性を良好なものとしている。また、Ｒ１、Ｒ２で示される末端基は、一方（Ｒ１）がメチル基であり、他方（Ｒ２）が、炭素原子数が２または３のアルキル基、すなわち、エチル基、プロピル基、イソプロピル基のいずれかである。Ｒ１、Ｒ２で示される末端基は適度な親油性を有する。化合物（１）は上記親油性基を有する構造と上記親水性の構造とを併せ持つことで、両親媒性を有する化合物である。 In the negative photosensitive resin composition of the present invention, the solvent (D) contains the solvent (D1), which is the compound (1), in the above ratio, thereby containing the black colorant (C) at a high concentration. However, it is possible to ensure the viscosity and re-solubility of the negative photosensitive resin composition required in the slit coating method.
The compound (1) has a hydrophilic structure in the structure of —O—C 2 H 4 —O—C 2 H 4 —O— in the formula (1), so that the compound (1) has a hydrophilic property. The solubility is good. In the terminal groups represented by R 1 and R 2 , one (R 1 ) is a methyl group and the other (R 2 ) is an alkyl group having 2 or 3 carbon atoms, that is, an ethyl group or a propyl group. Or an isopropyl group. The end groups represented by R 1 and R 2 have moderate lipophilicity. The compound (1) is an amphiphilic compound by having both the structure having the lipophilic group and the hydrophilic structure.
　化合物（１）としては、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プロピルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテルが挙げられる。なかでも、ジエチレングリコールエチルメチルエーテルおよびジエチレングリコールイソプロピルメチルエーテルが好ましく、ジエチレングリコールエチルメチルエーテルが特に好ましい。 Examples of the compound (1) include diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether, and diethylene glycol isopropyl methyl ether. Of these, diethylene glycol ethyl methyl ether and diethylene glycol isopropyl methyl ether are preferable, and diethylene glycol ethyl methyl ether is particularly preferable.
　ここで、化合物（１）の沸点は１７６～２００℃の範囲にあり、粘度は１～１．５ｍＰａ・ｓの範囲にある。ネガ型感光性樹脂組成物をスリットコート法で塗工する際には、塗工時にスリットノズルで該組成物が乾燥固化しないように、用いる溶媒の沸点は１５０℃以上が好ましい。また、生産性から塗布後の塗膜の乾燥速度は速い方が好ましく、用いる溶媒の沸点の上限は２２０℃程度が好ましい。また、スリットコート法に用いるネガ型感光性樹脂組成物について、用いる溶媒としては、用いる固形成分の粘度や固形成分に対する溶媒の量にもよるが、溶媒の粘度としては２．５ｍＰａ・ｓ以下であることが好ましい。化合物（１）については、このようなスリットコート法に用いるネガ型感光性樹脂組成物において溶媒に求められる沸点および粘度の特性についても満たす化合物である。 Here, the boiling point of the compound (1) is in the range of 176 to 200 ° C., and the viscosity is in the range of 1 to 1.5 mPa · s. When the negative photosensitive resin composition is applied by the slit coating method, the boiling point of the solvent used is preferably 150 ° C. or higher so that the composition does not dry and solidify with a slit nozzle during coating. Further, from the viewpoint of productivity, it is preferable that the drying rate of the coated film after application is fast, and the upper limit of the boiling point of the solvent used is preferably about 220 ° C. In addition, regarding the negative photosensitive resin composition used in the slit coating method, the solvent used depends on the viscosity of the solid component used and the amount of the solvent relative to the solid component, but the solvent viscosity is 2.5 mPa · s or less. Preferably there is. About a compound (1), it is a compound which also satisfy | fills about the characteristic of the boiling point and viscosity calculated | required by the solvent in the negative photosensitive resin composition used for such a slit coat method.
　溶媒（Ｄ１）としては、化合物（１）から選ばれる１種を用いても２種以上を併用してもよい。溶媒（Ｄ１）の溶媒（Ｄ）中の含有量は２０～１００質量％であり、３０～９０質量％が好ましく、３０～８０質量％が特に好ましい。ネガ型感光性樹脂組成物における溶媒（Ｄ）の含有量を上記範囲とし、溶媒（Ｄ）の全量に対する溶媒（Ｄ１）の含有量を上記範囲にすることで、上記アルカリ可溶性樹脂（Ａ）、光重合開始剤（Ｂ）等とともに全固形分に対して２０質量％超という高濃度に黒色着色剤（Ｃ）を含有するネガ型感光性樹脂組成物において、再溶解性に優れ、スリットコート法で塗布した塗膜において欠陥の発生が抑制され、さらにスリットコート法による塗布が可能な粘度を有するネガ型感光性樹脂組成物が得られる。 As the solvent (D1), one kind selected from the compound (1) may be used, or two or more kinds may be used in combination. The content of the solvent (D1) in the solvent (D) is 20 to 100% by mass, preferably 30 to 90% by mass, particularly preferably 30 to 80% by mass. By making content of the solvent (D) in a negative photosensitive resin composition into the said range, and making content of the solvent (D1) with respect to the whole quantity of solvent (D) into the said range, the said alkali-soluble resin (A), A negative photosensitive resin composition containing a black colorant (C) at a high concentration of more than 20% by mass with respect to the total solid content together with a photopolymerization initiator (B), etc. The negative photosensitive resin composition having a viscosity in which the occurrence of defects in the coating film applied in step 1 is suppressed and can be applied by the slit coating method is obtained.
　本発明のネガ型感光性樹脂組成物は、溶媒（Ｄ）として、溶媒（Ｄ１）と共に、環の構成原子として、二重結合を介して酸素原子と結合する炭素原子を１個以上含み、かつ酸素原子を含んでもよい、脂肪族環式化合物（Ｄ２－１）である溶媒（Ｄ２）を併用することが好ましい。溶媒（Ｄ）の全量に対する溶媒（Ｄ２）の割合は、１０～４０質量％が好ましく、１５～３０質量％が特に好ましい。 The negative photosensitive resin composition of the present invention contains, as a solvent (D), together with the solvent (D1), as a ring-constituting atom, one or more carbon atoms bonded to an oxygen atom via a double bond, and It is preferable to use together the solvent (D2) which is an aliphatic cyclic compound (D2-1) which may contain an oxygen atom. The ratio of the solvent (D2) to the total amount of the solvent (D) is preferably 10 to 40% by mass, particularly preferably 15 to 30% by mass.
　脂肪族環式化合物（Ｄ２－１）の環の員数は、沸点および融点の観点から、３～７が好ましく、５員環または６員環が特に好ましい。脂肪族環式化合物（Ｄ２－１）における環を構成する原子は炭素原子またはエーテル性酸素原子であるが、エーテル性酸素原子の数は０であってもよい。また、炭素原子数＞エーテル性酸素原子数の関係にある。環を構成する炭素原子のうち少なくとも１個は、二重結合を介して１個の酸素原子と結合する。環を構成する炭素原子のうち、二重結合を介して酸素原子と結合していないものは全て２個の水素原子と結合する。 The number of members of the aliphatic cyclic compound (D2-1) is preferably 3 to 7, and particularly preferably a 5-membered or 6-membered ring from the viewpoints of boiling point and melting point. The atoms constituting the ring in the aliphatic cyclic compound (D2-1) are carbon atoms or etheric oxygen atoms, but the number of etheric oxygen atoms may be zero. Further, the number of carbon atoms> the number of etheric oxygen atoms. At least one of the carbon atoms constituting the ring is bonded to one oxygen atom through a double bond. Of the carbon atoms constituting the ring, all those not bonded to the oxygen atom through a double bond are bonded to two hydrogen atoms.
　以下、環を構成する炭素原子とこれに二重結合で結合する酸素原子とからなる基を、「環を構成するカルボニル基」という。脂肪族環式化合物（Ｄ２－１）において、環を構成するカルボニル基の数としては、１個以上であればよく、１個が好ましい。 Hereinafter, a group composed of a carbon atom constituting a ring and an oxygen atom bonded to this by a double bond is referred to as a “carbonyl group constituting the ring”. In the aliphatic cyclic compound (D2-1), the number of carbonyl groups constituting the ring may be one or more, and preferably one.
　本発明のネガ型感光性樹脂組成物においては、溶媒（Ｄ）として、溶媒（Ｄ１）と併せて溶媒（Ｄ２)を用いることで、ネガ型感光性樹脂組成物の再溶解性をさらに向上させることができる。溶媒（Ｄ２)である脂肪族環式化合物（Ｄ２－１）は、極性基であるカルボニル基を有し、末端アルキル基を有さないため親水性が高いことから、親水性であるアルカリ可溶性樹脂（Ａ）に対する溶解性を良好にできる。ただし、脂肪族環式化合物（Ｄ２－１）は、上記化合物（１）に比べて高粘度であることから、得られるネガ型感光性樹脂組成物の粘度を適正なものとするために、溶媒（Ｄ）において上記配合量で用いることが好ましい。 In the negative photosensitive resin composition of the present invention, by using the solvent (D2) together with the solvent (D1) as the solvent (D), the re-solubility of the negative photosensitive resin composition is further improved. be able to. Since the aliphatic cyclic compound (D2-1) as the solvent (D2) has a carbonyl group that is a polar group and does not have a terminal alkyl group, the aliphatic cyclic compound (D2-1) has high hydrophilicity. The solubility with respect to (A) can be made favorable. However, since the aliphatic cyclic compound (D2-1) has a higher viscosity than the compound (1), in order to make the viscosity of the obtained negative photosensitive resin composition appropriate, In (D), it is preferable to use with the said compounding quantity.
　脂肪族環式化合物（Ｄ２－１）としては、環状エステル、環状ケトン等が挙げられる。
　環状エステルとしては、α－アセトラクトン、β－プロピオラクトン、γ－ブチロラクトン、δ－バレロラクトン、ε－カプロラクトン等のラクトン類が挙げられる。環状ケトンとしては、シクロプロパノン、シクロブタノン、シクロペンタノン、シクロヘキサノン、シクロヘプタノン等のシクロアルカノンが挙げられる。 Examples of the aliphatic cyclic compound (D2-1) include cyclic esters and cyclic ketones.
Examples of the cyclic ester include lactones such as α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Examples of the cyclic ketone include cycloalkanones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, and cycloheptanone.
　なかでも、溶媒（Ｄ２）としては、入手容易性と沸点の点からシクロヘキサノン、γ－ブチロラクトン等が好ましい。
　溶媒（Ｄ２）としては、上記脂肪族環式化合物（Ｄ２－１）から選ばれる１種を用いても２種以上を併用してもよい。 Among these, as the solvent (D2), cyclohexanone, γ-butyrolactone and the like are preferable from the viewpoint of availability and boiling point.
As the solvent (D2), one kind selected from the above aliphatic cyclic compounds (D2-1) may be used, or two or more kinds may be used in combination.
　本発明のネガ型感光性樹脂組成物は、溶媒（Ｄ）として、上述の溶媒（Ｄ１）および溶媒（Ｄ２）以外の溶媒（Ｄ３）を必要に応じて含有してもよい。溶媒（Ｄ３）としては、上記アルカリ可溶性樹脂（Ａ）や以下の撥インク剤（Ｅ）の合成に使用した溶媒等が、アルカリ可溶性樹脂（Ａ）や撥インク剤（Ｅ）とともにネガ型感光性樹脂組成物に配合される場合の溶媒等が挙げられる。 The negative photosensitive resin composition of the present invention may contain a solvent (D3) other than the above-mentioned solvent (D1) and solvent (D2) as necessary, as the solvent (D). As the solvent (D3), the above-mentioned alkali-soluble resin (A), the solvent used for the synthesis of the following ink repellent agent (E), and the like, together with the alkali-soluble resin (A) and the ink repellent agent (E), negative photosensitivity. The solvent etc. in the case of mix | blending with a resin composition are mentioned.
　なお、上記アルカリ可溶性樹脂（Ａ）や撥インク剤（Ｅ）の合成に使用する溶媒としては、上記溶媒（Ｄ１)や溶媒（Ｄ２）を用いる場合もある。ネガ型感光性樹脂組成物がこれら配合成分由来の溶媒（Ｄ１）や溶媒（Ｄ２)を含有する場合には、それぞれについて、これらを含む溶媒（Ｄ１）および溶媒（Ｄ２)の各総量により算出される、溶媒（Ｄ）における溶媒（Ｄ１）および溶媒（Ｄ２）の含有量がそれぞれ上記範囲となるように調整すればよい。 In addition, as the solvent used for the synthesis of the alkali-soluble resin (A) or the ink repellent agent (E), the solvent (D1) or the solvent (D2) may be used. When the negative photosensitive resin composition contains the solvent (D1) or the solvent (D2) derived from these compounding components, it is calculated by the total amount of the solvent (D1) and the solvent (D2) containing them. What is necessary is just to adjust so that content of the solvent (D1) and the solvent (D2) in a solvent (D) may become said range, respectively.
　溶媒（Ｄ３）としては、上記溶媒（Ｄ１)および必要に応じて用いられる溶媒（Ｄ２）とともに用いて、溶媒（Ｄ）としての上記機能を阻害しないものであれば特に制限されない。したがって、アルカリ可溶性樹脂（Ａ）や撥インク剤（Ｅ）をその合成に用いた溶媒と共にネガ型感光性樹脂組成物に配合する場合には、合成時に用いる溶媒として溶媒（Ｄ）としての上記機能を阻害しない溶媒を選択することが好ましい。 The solvent (D3) is not particularly limited as long as it is used together with the solvent (D1) and the solvent (D2) used as necessary and does not inhibit the function as the solvent (D). Therefore, when the alkali-soluble resin (A) or the ink repellent agent (E) is blended in the negative photosensitive resin composition together with the solvent used for the synthesis, the above function as the solvent (D) is used as the solvent used in the synthesis. It is preferable to select a solvent that does not inhibit the reaction.
　溶媒（Ｄ３）としては、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、エチレングリコール等のアルコール類；アセトン、２－ブタノン、メチルイソブチルケトン等のケトン類；２－メトキシエタノール、２－エトキシエタノール、２－ブトキシエタノール等のセルソルブ類；２－（２－メトキシエトキシ）エタノール、２－（２－エトキシエトキシ）エタノール、２－（２－ブトキシエトキシ）エタノール等のカルビトール類；メチルアセテート、エチルアセテート、ｎ－ブチルアセテート、エチルラクテート、ｎ－ブチルラクテート、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ブチルエーテルアセテート、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、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、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、エチル－３－エトキシプロピオネート、シクロヘキサノールアセテート、３－メチル－３－メトキシブチルアセテート、グリセリントリアセテート等のエステル類；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ジエチルエーテル、ジエチレングリコールブチルメチルエーテル、ジエチレングリコールジブチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、ジブチルエーテル等が挙げられる。 As the solvent (D3), alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol; ketones such as acetone, 2-butanone and methyl isobutyl ketone; 2-methoxyethanol, 2-ethoxy Cellsolves such as ethanol and 2-butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; methyl acetate, ethyl Acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclo Esters such as hexanol acetate, 3-methyl-3-methoxybutyl acetate, glycerin triacetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol Lumpur dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutyl ether and the like.
　溶媒（Ｄ）における溶媒（Ｄ３）の含有量は、溶媒（Ｄ）の全量から溶媒（Ｄ１）および溶媒（Ｄ２)の量を引いた量であり、具体的には、溶媒（Ｄ）の全量に対して１～７０質量％の割合が好ましく、２０～７０質量％が特に好ましい。 The content of the solvent (D3) in the solvent (D) is an amount obtained by subtracting the amount of the solvent (D1) and the solvent (D2) from the total amount of the solvent (D), specifically, the total amount of the solvent (D). A ratio of 1 to 70% by mass is preferable, and 20 to 70% by mass is particularly preferable.
　なお、溶媒（Ｄ）の具体的な態様として、溶媒（Ｄ１)のみで構成される、溶媒（Ｄ１）と溶媒（Ｄ２）および／または溶媒（Ｄ３）で構成される態様が挙げられる。溶媒（Ｄ）が溶媒（Ｄ１）と溶媒（Ｄ２）で構成される場合の好ましい配合割合（質量比）として、溶媒（Ｄ１）：溶媒（Ｄ２）＝８５：１５～７０：３０が挙げられる。溶媒（Ｄ）が溶媒（Ｄ１）と溶媒（Ｄ３）で構成される場合の好ましい配合割合（質量比）として、溶媒（Ｄ１）：溶媒（Ｄ３）＝３０：７０～８０：２０が挙げられる。また、溶媒（Ｄ）が溶媒（Ｄ１）、溶媒（Ｄ２)、および溶媒（Ｄ３）で構成される場合の好ましい配合割合（質量比）として、溶媒（Ｄ１）：溶媒（Ｄ２）：溶媒（Ｄ３）＝３０～８０：１０～３０：０～６０が挙げられる。 In addition, as a specific aspect of the solvent (D), an aspect including the solvent (D1), the solvent (D2), and / or the solvent (D3), which includes only the solvent (D1), can be given. A preferable blending ratio (mass ratio) when the solvent (D) is composed of the solvent (D1) and the solvent (D2) includes solvent (D1): solvent (D2) = 85: 15 to 70:30. A preferable blending ratio (mass ratio) when the solvent (D) is composed of the solvent (D1) and the solvent (D3) includes solvent (D1): solvent (D3) = 30: 70 to 80:20. Moreover, as a preferable mixture ratio (mass ratio) when the solvent (D) is composed of the solvent (D1), the solvent (D2), and the solvent (D3), solvent (D1): solvent (D2): solvent (D3) ) = 30 to 80:10 to 30: 0 to 60.
［撥インク剤（Ｅ）］
　本発明におけるネガ型感光性樹脂組成物は、さらに、任意成分として、撥インク剤（Ｅ）を含有してもよい。撥インク剤（Ｅ）としては、例えば、水素原子の少なくとも１つがフッ素原子に置換された炭素原子数１～２０のアルキル基（ただし、該アルキル基は炭素原子間にエーテル性酸素原子を有していてもよい。）および／または下式（４）で表される基を含む重合体（Ｅ１）等が挙げられる。 [Ink repellent (E)]
The negative photosensitive resin composition in the present invention may further contain an ink repellent agent (E) as an optional component. As the ink repellent agent (E), for example, an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (provided that the alkyl group has an etheric oxygen atom between the carbon atoms). And / or a polymer (E1) containing a group represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（式（４）中、Ｒ１１およびＲ１２は、それぞれ独立してメチル基またはフェニル基を表す。ｎは１～２００の整数を示す。） (In formula (4), R 11 and R 12 each independently represents a methyl group or a phenyl group. N represents an integer of 1 to 200.)
　撥インク剤（Ｅ）としては、重合体（Ｅ１)の１種を単独で用いてもよく、２種以上を併用してもよい。ネガ型感光性樹脂組成物に撥インク剤（Ｅ）を配合すれば、これを用いて作製される隔壁やブラックマトリックスの上部表面に撥インク性を付与することができる。隔壁やブラックマトリックスで区分された領域（ドット）にインクジェット法でインクを注入し画素を形成する際の、隣り合うドット間でのインクの混色を防ぐことができる。 As the ink repellent agent (E), one type of the polymer (E1) may be used alone, or two or more types may be used in combination. If an ink repellent agent (E) is mix | blended with a negative photosensitive resin composition, ink repellency can be provided to the partition surface produced using this, or the upper surface of a black matrix. It is possible to prevent ink color mixing between adjacent dots when ink is injected into an area (dot) divided by a partition wall or a black matrix by an ink jet method to form a pixel.
　重合体（Ｅ１）の数平均分子量（Ｍｎ）は、１,５００～５０，０００が好ましく、１０,０００～５０，０００が特に好ましい。数平均分子量（Ｍｎ）が上記範囲であると、アルカリ溶解性、現像性が良好である。重合体（Ｅ１）がフッ素原子を含有する場合の、重合体（Ｅ１）におけるフッ素原子の含有率は、撥インク性と隔壁成形性の点から、５～３５質量％が好ましく、１０～３０質量％が特に好ましい。また、重合体（Ｅ１）がケイ素原子を含有する場合の、重合体（Ｅ１）におけるケイ素の含有率は、撥インク性と隔壁成形性の点から、０．１～２５質量％が好ましく、０．５～１０質量％が特に好ましい。 The number average molecular weight (Mn) of the polymer (E1) is preferably from 1,500 to 50,000, particularly preferably from 10,000 to 50,000. When the number average molecular weight (Mn) is in the above range, alkali solubility and developability are good. When the polymer (E1) contains a fluorine atom, the fluorine atom content in the polymer (E1) is preferably 5 to 35% by mass from the viewpoint of ink repellency and partition wall moldability, and 10 to 30% by mass. % Is particularly preferred. In the case where the polymer (E1) contains a silicon atom, the silicon content in the polymer (E1) is preferably 0.1 to 25% by mass from the viewpoint of ink repellency and partition wall moldability. It is particularly preferably 5 to 10% by mass.
　重合体（Ｅ１）は側鎖に、３～１００個／分子の割合で、エチレン性二重結合を有することが好ましい。重合体（Ｅ１）が側鎖にエチレン性二重結合を有する場合、その割合は６～３０個／分子が特に好ましい。エチレン性二重結合を有することにより重合体（Ｅ１）は、ネガ型感光性樹脂組成物中のアルカリ可溶性樹脂（Ａ）にラジカル重合して隔壁上部に固定化されることが可能となる。 The polymer (E1) preferably has ethylenic double bonds in the side chain at a rate of 3 to 100 molecules / molecule. When the polymer (E1) has an ethylenic double bond in the side chain, the ratio is particularly preferably 6 to 30 / molecule. By having an ethylenic double bond, the polymer (E1) can be radically polymerized to the alkali-soluble resin (A) in the negative photosensitive resin composition and fixed to the upper part of the partition wall.
　さらに重合体（Ｅ１）は、酸性基、例えば、カルボキシ基、フェノール性水酸基およびスルホ基の群から選ばれる少なくとも１つの酸性基を有することが好ましい。その理由は、アルカリ可溶性を有することで、基材上の隔壁やブラックマトリックスで区分された領域（ドット）内に上記撥インク性を有する重合体（Ｅ１）が残りにくく、インクを注入した際のインクの濡れ拡がり性が良好となるからである。このような観点から、重合体（Ｅ１）の酸価は１０～４００ｍｇＫＯＨ／ｇであることが好ましく、２０～３００ｍｇＫＯＨ／ｇが特に好ましい。 Furthermore, the polymer (E1) preferably has an acidic group, for example, at least one acidic group selected from the group consisting of a carboxy group, a phenolic hydroxyl group and a sulfo group. The reason is that the polymer having the ink repellency (E1) hardly remains in the region (dots) divided by the partition walls or the black matrix on the base material because it has alkali solubility, and when the ink is injected. This is because the ink wettability is improved. From such a viewpoint, the acid value of the polymer (E1) is preferably 10 to 400 mgKOH / g, particularly preferably 20 to 300 mgKOH / g.
　ネガ型感光性樹脂組成物における全固形分中の撥インク剤（Ｅ）の含有割合は、０．０１～３０質量％が好ましく、０．０５～２０質量％が特に好ましい。含有割合が上記範囲の下限値以上であると、ネガ型感光性樹脂組成物により形成される隔壁やブラックマトリックスの上部表面に充分な撥インク性が付与される。上記範囲の上限値以下であると、隔壁やブラックマトリックスと基材との密着性が良好になる。 The content ratio of the ink repellent agent (E) in the total solid content in the negative photosensitive resin composition is preferably 0.01 to 30% by mass, particularly preferably 0.05 to 20% by mass. When the content ratio is not less than the lower limit of the above range, sufficient ink repellency is imparted to the partition walls and the upper surface of the black matrix formed by the negative photosensitive resin composition. Adhesiveness of a partition or a black matrix and a base material becomes it favorable that it is below the upper limit of the said range.
［架橋剤（Ｆ）］
　本発明におけるネガ型感光性樹脂組成物は、ラジカル硬化を促進する任意成分として、架橋剤（Ｆ）を含んでもよい。架橋剤（Ｆ）としては、１分子中に２つ以上のエチレン性二重結合を有し、酸性基を有しない化合物が好ましい。ネガ型感光性樹脂組成物が架橋剤（Ｆ）を含むことにより、露光時におけるネガ型感光性樹脂組成物の硬化性が向上し、少ない露光量でも隔壁を形成することができる。 [Crosslinking agent (F)]
The negative photosensitive resin composition in the present invention may contain a crosslinking agent (F) as an optional component for promoting radical curing. As a crosslinking agent (F), the compound which has two or more ethylenic double bonds in 1 molecule, and does not have an acidic group is preferable. When the negative photosensitive resin composition contains the crosslinking agent (F), the curability of the negative photosensitive resin composition at the time of exposure is improved, and the partition can be formed even with a small exposure amount.
　架橋剤（Ｆ）としては、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（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、ジペンタエリスリトールヘキサ（メタ）アクリレート、エトキシ化イソシアヌル酸トリアクリレート、ε－カプロラクトン変性トリス－（２－アクリロキシエチル）イソシアヌレート、ビス｛４－（アリルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド）フェニル｝メタン、Ｎ，Ｎ’－ｍ－キシリレン－ビス（アリルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド）、ウレタンアクリレート等が挙げられる。光反応性の点から多数のエチレン性二重結合を有することが好ましい。なお、これらは１種を単独で用いても２種以上を併用してもよい。 Examples of the crosslinking agent (F) include diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2. 1] hept-5-ene-2,3-dicarboximide), urethane acrylate and the like. From the viewpoint of photoreactivity, it is preferable to have a large number of ethylenic double bonds. In addition, these may be used individually by 1 type, or may use 2 or more types together.
　架橋剤（Ｆ）としては、市販品を使用することができる。市販品としては、ＫＡＹＡＲＡＤ　ＤＰＨＡ（商品名、日本化薬社製、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物）、ＮＫエステル　Ａ－９５３０（商品名、新中村化学工業社製、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物））、ＮＫエステ　Ａ－９３００（商品名、新中村化学工業社製、エトキシ化イソシアヌル酸トリアクリレート）、ＮＫエステル　Ａ－９３００－１ＣＬ（商品名、新中村化学工業社製、ε－カプロラクトン変性トリス－（２－アクリロキシエチル）イソシアヌレート）、ＢＡＮＩ－Ｍ（商品名、丸善石油化学社製、ビス｛４－（アリルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド）フェニル｝メタン）、ＢＡＮＩ－Ｘ（商品名、丸善石油化学社製、Ｎ，Ｎ’－ｍ－キシリレン－ビス（アリルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド））等が挙げられる。ウレタンアクリレートとしては、日本化薬社製のＫＡＹＡＲＡＤ　ＵＸシリーズが挙げられ、具体的商品名としては、ＵＸ－３２０４、ＵＸ－６１０１、ＵＸ－０９３７、ＤＰＨＡ－４０Ｈ、ＵＸ－５０００、ＵＸ－５００２Ｄ－Ｐ２０等が挙げられる。 Commercial products can be used as the crosslinking agent (F). Commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9530 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., dipenta Erythritol pentaacrylate and dipentaerythritol hexaacrylate)), NK Este A-9300 (trade name, Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, new Nakamura Chemical Co., Ltd., ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name, manufactured by Maruzen Petrochemical Co., Ltd., Bis {4- (allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboxy (Mid) phenyl} methane), BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd., N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide)) and the like. Examples of urethane acrylate include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20. Etc.
　ネガ型感光性樹脂組成物における全固形分中の架橋剤（Ｆ）の含有割合は、３～５０質量％が好ましく、５～４０質量％が特に好ましい。上記範囲であると、ネガ型感光性樹脂組成物のアルカリ現像性が良好となる。 The content of the crosslinking agent (F) in the total solid content in the negative photosensitive resin composition is preferably 3 to 50% by mass, particularly preferably 5 to 40% by mass. Within the above range, the alkali developability of the negative photosensitive resin composition is improved.
［微粒子（Ｇ）］
　本発明におけるネガ型感光性樹脂組成物は、必要に応じて、微粒子（Ｇ）を含んでいてもよい。ネガ型感光性樹脂組成物が微粒子（Ｇ）を含むことにより、ネガ型感光性樹脂組成物から得られる隔壁は熱垂れが防止された耐熱性に優れる隔壁となる。
　微粒子（Ｇ）としては、各種無機系、有機系の微粒子が使用可能であるが、塩基性高分子分散剤を吸着能の点から、マイナスに帯電しているものが好ましく用いられる。 [Fine particles (G)]
The negative photosensitive resin composition in the present invention may contain fine particles (G) as necessary. When the negative photosensitive resin composition contains the fine particles (G), the partition obtained from the negative photosensitive resin composition becomes a partition excellent in heat resistance in which thermal sagging is prevented.
As the fine particles (G), various inorganic and organic fine particles can be used, and those in which the basic polymer dispersant is negatively charged from the viewpoint of adsorption ability are preferably used.
　無機系としては、シリカ、ジルコニア、フッ化マグネシウム、スズドープ酸化インジウム（ＩＴＯ）、アンチモンドープ酸化スズ（ＡＴＯ）等が挙げられる。有機系としては、ポリエチレン、ポリメチルメタクリレート（ＰＭＭＡ）等が挙げられる。耐熱性を考慮すると、無機系微粒子が好ましく、入手容易性や分散安定性を考慮すると、シリカ、またはジルコニアが特に好ましい。さらに、ネガ型感光性樹脂組成物の露光感度を考慮すると、微粒子（Ｇ）は、露光時に照射される光を吸収しないことが好ましく、超高圧水銀灯の主発光波長であるｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）、ｇ線（４３６ｎｍ）を吸収しないことが特に好ましい。
　微粒子（Ｇ）の粒子径は、隔壁の表面平滑性が良好となることから、平均粒子径が１μｍ以下であることが好ましく、２００ｎｍ以下が特に好ましい。 Examples of inorganic materials include silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO). Examples of the organic system include polyethylene and polymethyl methacrylate (PMMA). In consideration of heat resistance, inorganic fine particles are preferable, and in view of availability and dispersion stability, silica or zirconia is particularly preferable. Furthermore, considering the exposure sensitivity of the negative photosensitive resin composition, it is preferable that the fine particles (G) do not absorb the light irradiated at the time of exposure, i-line (365 nm) which is the main emission wavelength of the ultra-high pressure mercury lamp, It is particularly preferable not to absorb h-line (405 nm) and g-line (436 nm).
The particle diameter of the fine particles (G) is preferably 1 μm or less, and particularly preferably 200 nm or less, because the surface smoothness of the partition walls is improved.
　微粒子（Ｇ）としてはシリカが好ましい。シリカとしては、コロイダルシリカが好ましい。一般にコロイダルシリカとしては、水に分散されたシリカヒドロゾル、水が有機溶媒に置換されたオルガノシリカゾルがあるが、有機溶媒を分散媒として用いたオルガノシリカゾルが好ましい。
　このようなオルガノシリカゾルとしては、市販品を用いることが可能であり、市販品としては、いずれも日産化学工業社製の商品名で、ＰＭＡ－ＳＴ（シリカ粒子径：１０～２０ｎｍ、シリカ固形分：３０質量％、プロピレングリコールモノメチルエーテルアセテート：７０質量％。）、ＮＰＣ－ＳＴ（シリカ粒子径：１０～２０ｎｍ、シリカ固形分：３０質量％、ｎ－プロピルセロソルブ：７０質量％。）、ＩＰＡ－ＳＴ（シリカ粒子径：１０～２０ｎｍ、シリカ固形分：３０質量％、イソプロピルアルコール（２－プロパノール）：７０質量％。）等を挙げることができる。 Silica is preferable as the fine particles (G). As silica, colloidal silica is preferable. In general, colloidal silica includes silica hydrosol dispersed in water and organosilica sol in which water is replaced with an organic solvent, and organosilica sol using an organic solvent as a dispersion medium is preferable.
Commercially available products can be used as such organosilica sols, all of which are trade names manufactured by Nissan Chemical Industries, Ltd., PMA-ST (silica particle diameter: 10 to 20 nm, silica solid content). : 30% by mass, propylene glycol monomethyl ether acetate: 70% by mass), NPC-ST (silica particle diameter: 10 to 20 nm, silica solid content: 30% by mass, n-propyl cellosolve: 70% by mass), IPA- ST (silica particle diameter: 10 to 20 nm, silica solid content: 30% by mass, isopropyl alcohol (2-propanol): 70% by mass) and the like.
　ネガ型感光性樹脂組成物における全固形分中の微粒子（Ｇ）の含有割合は、５～３５質量％が好ましく、１０～３０質量％が特に好ましい。含有割合が上記範囲の下限値以上であると、ポストベークによる隔壁の熱垂れが防止され、上記範囲の上限値以下であると、ネガ型感光性樹脂組成物の貯蔵安定性が良好になる。 The content of the fine particles (G) in the total solid content in the negative photosensitive resin composition is preferably 5 to 35% by mass, particularly preferably 10 to 30% by mass. When the content ratio is not less than the lower limit value of the above range, thermal sag of the partition due to post-baking is prevented, and when it is not more than the upper limit value of the above range, the storage stability of the negative photosensitive resin composition becomes good.
［シランカップリング剤（Ｈ）］
　本発明におけるネガ型感光性樹脂組成物は、必要に応じて、シランカップリング剤（Ｈ）を含んでいてもよい。ネガ型感光性樹脂組成物がシランカップリング剤（Ｈ）を含むことで、ネガ型感光性樹脂組成物から形成される硬化膜の基材密着性を向上させることができる。
　シランカップリング剤（Ｈ）としては、テトラエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、メチルトリメトキシシラン、ビニルトリメトキシシラン、３－メタクリロイルオキシプロピルトリメトキシシラン、３－クロロプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、ヘプタデカフルオロオクチルエチルトリメトキシシラン、ポリオキシアルキレン鎖含有トリエトキシシラン、イミダゾールシラン等が挙げられる。これらは１種を用いても２種以上を併用してもよい。 [Silane coupling agent (H)]
The negative photosensitive resin composition in the present invention may contain a silane coupling agent (H) as necessary. When the negative photosensitive resin composition contains the silane coupling agent (H), the substrate adhesion of the cured film formed from the negative photosensitive resin composition can be improved.
Examples of the silane coupling agent (H) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane. , 3-mercaptopropyltrimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, imidazolesilane and the like. These may be used alone or in combination of two or more.
　シランカップリング剤（Ｈ）としては、市販品を使用することができる。市販品としては、ＫＢＭ５０１３（商品名、信越化学社製、３－アクリロイルオキシプロピルトリメトキシシラン）等が挙げられる。 A commercially available product can be used as the silane coupling agent (H). Examples of commercially available products include KBM5013 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloyloxypropyltrimethoxysilane).
　ネガ型感光性樹脂組成物における全固形分中のシランカップリング剤（Ｈ）の含有割合は、０．１～２０質量％が好ましく、１～１０質量％が特に好ましい。上記範囲の下限値以上であると、ネガ型感光性樹脂組成物から形成される硬化膜の基材密着性が向上する。 The content ratio of the silane coupling agent (H) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass. The base material adhesiveness of the cured film formed from a negative photosensitive resin composition improves that it is more than the lower limit of the said range.
［熱硬化剤（Ｉ）］
　本発明におけるネガ型感光性樹脂組成物は、必要に応じて、熱硬化剤（Ｉ）を含んでいてもよい。ネガ型感光性樹脂組成物が熱硬化剤（Ｉ）を含むことで、隔壁の耐熱性および耐透水性を向上させることができる。
　熱硬化剤（Ｉ）としては、アミノ樹脂、２個以上のエポキシ基を有する化合物、２個以上のヒドラジノ基を有する化合物、ポリカルボジイミド化合物、２個以上のオキサゾリン基を有する化合物、２個以上のアジリジン基を有する化合物、多価金属類、２個以上のメルカプト基を有する化合物、ポリイソシアネート化合物等が挙げられる。中でも、形成された隔壁の耐薬品性が向上する点から、アミノ樹脂、２個以上のエポキシ基を有する化合物または２個以上のオキサゾリン基を有する化合物が特に好ましい。 [Thermosetting agent (I)]
The negative photosensitive resin composition in the present invention may contain a thermosetting agent (I) as necessary. When the negative photosensitive resin composition contains the thermosetting agent (I), the heat resistance and water permeability of the partition walls can be improved.
The thermosetting agent (I) includes an amino resin, a compound having two or more epoxy groups, a compound having two or more hydrazino groups, a polycarbodiimide compound, a compound having two or more oxazoline groups, two or more Examples thereof include compounds having an aziridine group, polyvalent metals, compounds having two or more mercapto groups, and polyisocyanate compounds. Among these, an amino resin, a compound having two or more epoxy groups, or a compound having two or more oxazoline groups is particularly preferable from the viewpoint of improving chemical resistance of the formed partition wall.
　ネガ型感光性樹脂組成物における全固形分中の熱硬化剤（Ｉ）の含有割合は、０．１～２０質量％が好ましく、１～２０質量％が特に好ましい。上記範囲であると、得られるネガ型感光性樹脂組成物の現像性が良好となる。 The content ratio of the thermosetting agent (I) in the total solid content in the negative photosensitive resin composition is preferably from 0.1 to 20% by mass, particularly preferably from 1 to 20% by mass. Within the above range, the developability of the obtained negative photosensitive resin composition becomes good.
［リン酸化合物（Ｊ）］
　本発明におけるネガ型感光性樹脂組成物は、必要に応じて、リン酸化合物（Ｊ）を含んでいてもよい。ネガ型感光性樹脂組成物がリン酸化合物（Ｊ）を含むことで、基材との密着性を向上させることができる。
　リン酸化合物しては、モノ（メタ）アクリロイルオキシエチルフォスフェート、ジ（メタ）アクリロイルオキシエチルフォスフェート、トリス（メタ）アクリロイルオキシエチルフォスフェート等が挙げられる。 [Phosphate compound (J)]
The negative photosensitive resin composition in this invention may contain the phosphoric acid compound (J) as needed. Adhesiveness with a base material can be improved because a negative photosensitive resin composition contains a phosphoric acid compound (J).
Examples of the phosphoric acid compound include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.
　ネガ型感光性樹脂組成物における全固形分中のリン酸化合物（Ｊ）の含有割合は、０．１～１０質量％が好ましく、０．１～１質量％が特に好ましい。上記範囲であると、得られるネガ型感光性樹脂組成物から形成される硬化膜の基材との密着性が良好となる。 The content of the phosphoric acid compound (J) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 10% by mass, particularly preferably 0.1 to 1% by mass. Adhesiveness with the base material of the cured film formed from the negative photosensitive resin composition obtained as it is the said range becomes favorable.
［界面活性剤（Ｋ）］
　本発明におけるネガ型感光性樹脂組成物は、必要に応じて、界面活性剤（Ｋ）を含んでいてもよい。ネガ型感光性樹脂組成物が界面活性剤（Ｋ）を含むことで、硬化膜の厚さが均一になる。
　上述した撥インク剤（Ｅ）は、通常、界面活性剤としての作用も有する。インクジェット法以外の方法で画素形成を行うような光学素子用の隔壁を形成するネガ型感光性樹脂組成物は、通常、撥インク剤を含有しないため、界面活性剤を使用することが好ましい。界面活性剤（Ｋ）としては、撥インク剤（Ｅ）と同様な重合体を用いてもよく、フッ素系界面活性剤、シリコーン系界面活性剤、アクリル系界面活性剤等が挙げられる。 [Surfactant (K)]
The negative photosensitive resin composition in the present invention may contain a surfactant (K) as necessary. When the negative photosensitive resin composition contains the surfactant (K), the thickness of the cured film becomes uniform.
The ink repellent agent (E) described above also usually has an action as a surfactant. A negative photosensitive resin composition for forming a partition for an optical element that forms a pixel by a method other than the ink jet method usually does not contain an ink repellent, and therefore, a surfactant is preferably used. As the surfactant (K), the same polymer as the ink repellent agent (E) may be used, and examples thereof include a fluorine-based surfactant, a silicone-based surfactant, and an acrylic surfactant.
　界面活性剤（Ｋ）は市販品を用いてもよい。いずれもビックケミー・ジャパン社製の商品名で、ＢＹＫ－３０６（ポリエーテル変性ポリジメチルシロキサン：１２質量％、キシレン：６８質量％、モノフェニルグリコール：２０質量％）、ＢＹＫ－３０７（ポリエーテル変性ポリジメチルシロキサン）、ＢＹＫ－３２３（アラルキル変性ポリメチルアルキルシロキサン）、ＢＹＫ－３２０（ポリエーテル変性ポリメチルアルキルシロキサン：５２質量％、ホワイトスピリット：４３質量％、ＰＧＭＥＡ：５質量％）、ＢＹＫ－３５０（アクリル系共重合物）等が挙げられる。 Surfactant (K) may be a commercially available product. All are trade names of BYK-Japan Japan, BYK-306 (polyether-modified polydimethylsiloxane: 12% by mass, xylene: 68% by mass, monophenyl glycol: 20% by mass), BYK-307 (polyether-modified poly Dimethylsiloxane), BYK-323 (aralkyl-modified polymethylalkylsiloxane), BYK-320 (polyether-modified polymethylalkylsiloxane: 52 mass%, white spirit: 43 mass%, PGMEA: 5 mass%), BYK-350 ( Acrylic copolymer) and the like.
　ネガ型感光性樹脂組成物における全固形分中の界面活性剤（Ｋ）の含有割合は、０．０１～３０質量％が好ましく、０．０５～２０質量％が特に好ましい。上記範囲であると、得られるネガ型感光性樹脂組成物の膜の厚さの均一性が良好となる。 The content ratio of the surfactant (K) in the total solid content in the negative photosensitive resin composition is preferably 0.01 to 30% by mass, particularly preferably 0.05 to 20% by mass. When the thickness is in the above range, the film thickness of the obtained negative photosensitive resin composition becomes uniform.
［その他の添加剤］
　本発明におけるネガ型感光性樹脂組成物は、さらに必要に応じて、硬化促進剤、増粘剤、可塑剤、消泡剤、ハジキ防止剤、紫外線吸収剤等を使用することができる。 [Other additives]
The negative photosensitive resin composition in the present invention can further use a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a repellency inhibitor, an ultraviolet absorber, and the like, if necessary.
［ネガ型感光性樹脂組成物］
　本発明のネガ型感光性樹脂組成物は、アルカリ可溶性樹脂（Ａ）、光重合開始剤（Ｂ）、全固形分に対して２０質量％超の割合の黒色着色剤（Ｃ）、および溶媒（Ｄ）を含有する。さらに、必要に応じて、撥インク剤（Ｅ）、架橋剤（Ｆ）、微粒子（Ｇ）、シランカップリング剤（Ｈ）、熱硬化剤（Ｉ）、リン酸化合物（Ｊ）、界面活性剤（Ｋ）およびその他の添加剤を含有してもよい。
　本発明のネガ型感光性樹脂組成物を製造する方法としては、特に制限されず、上記各成分の所定量を秤量し一般的な方法により混合することで製造できる。 [Negative photosensitive resin composition]
The negative photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a photopolymerization initiator (B), a black colorant (C) in a proportion of more than 20% by mass relative to the total solid content, and a solvent ( D). Further, as required, the ink repellent agent (E), the crosslinking agent (F), the fine particles (G), the silane coupling agent (H), the thermosetting agent (I), the phosphoric acid compound (J), and the surfactant. (K) and other additives may be contained.
It does not restrict | limit especially as a method of manufacturing the negative photosensitive resin composition of this invention, It can manufacture by measuring predetermined amount of said each component and mixing by a general method.
　本発明のネガ型感光性樹脂組成物は、通常のネガ型感光性樹脂組成物と同様にフォトリソグラフィ等の材料として用いられ、得られた硬化膜は隔壁として、特に高濃度で黒色着色剤を含有する遮光性が高いブラックマトリックスとして、通常のネガ型感光性樹脂組成物の硬化膜が用いられる光学素子の部材として、使用することが可能である。上記固形成分に加えて、溶媒（Ｄ）として化合物（１）である溶媒（Ｄ１）を配合した本発明のネガ型感光性樹脂組成物は、高濃度に黒色着色剤を含有しながら再溶解性に優れ、さらにスリットコート法による塗布が可能な粘度を有するものである。
　したがって、本発明のネガ型感光性樹脂組成物は、基材上に隔壁等の硬化膜を形成する際のネガ型感光性樹脂組成物の塗工においてスリットコート法を用いる場合に、好適な粘度を有し、さらにスリットノズル周辺の乾燥固化物に起因する不具合等を解消できることから、特にスリットコート法を用いた塗工から硬化膜を形成するのに好適である。 The negative photosensitive resin composition of the present invention is used as a material such as photolithography in the same manner as an ordinary negative photosensitive resin composition, and the obtained cured film has a black colorant at a particularly high concentration as a partition. As a black matrix containing a high light-shielding property, it can be used as a member of an optical element in which a cured film of a normal negative photosensitive resin composition is used. In addition to the solid component, the negative photosensitive resin composition of the present invention in which the solvent (D1) as the compound (1) is blended as the solvent (D) is resoluble while containing a black colorant at a high concentration. Furthermore, it has a viscosity capable of being applied by a slit coating method.
Therefore, the negative photosensitive resin composition of the present invention has a suitable viscosity when the slit coating method is used in the application of the negative photosensitive resin composition when forming a cured film such as a partition wall on the substrate. In addition, since it is possible to eliminate problems caused by the dried and solidified material around the slit nozzle, it is particularly suitable for forming a cured film from coating using the slit coating method.
（ネガ型感光性樹脂組成物の好ましい組み合わせ）
　本発明のネガ型感光性樹脂組成物は、用途や要求特性に合わせて組成と配合比を適宜選択することが好ましい。
　本発明のネガ型感光性樹脂組成物における各種配合成分の好ましい組成を以下に示す。 (Preferred combination of negative photosensitive resin composition)
In the negative photosensitive resin composition of the present invention, it is preferable to appropriately select the composition and the mixing ratio in accordance with the application and required characteristics.
The preferable composition of the various compounding components in the negative photosensitive resin composition of the present invention is shown below.
＜組み合わせ１＞
　アルカリ可溶性樹脂（Ａ）：ビスフェノールＡ型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、ビスフェノールＦ型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、フェノールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、クレゾールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、トリスフェノールメタン型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、上記式（Ａ１－２ａ）～（Ａ１－２ｃ）で表されるエポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂から選ばれる少なくとも１つの樹脂であって、ネガ型感光性樹脂組成物における全固形分中に１０～６０質量％、 <Combination 1>
Alkali-soluble resin (A): a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol A type epoxy resin, a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol F type epoxy resin, phenol novolac type Resin with an acidic group and ethylenic double bond introduced into an epoxy resin, a resin with an acidic group and ethylenic double bond introduced into a cresol novolac type epoxy resin, an acidic group and an ethylenic double group into a trisphenolmethane type epoxy resin A resin having a double bond introduced therein, or at least one resin selected from resins having an acidic group and an ethylenic double bond introduced into the epoxy resins represented by the formulas (A1-2a) to (A1-2c). 10 to 60% by mass in the total solid content of the negative photosensitive resin composition,
　光重合開始剤（Ｂ）：Ｏ－アシルオキシム系化合物であって、ネガ型感光性樹脂組成物における全固形分中に３～６質量％、
　黒色着色剤（Ｃ）：カーボンブラック、有機顔料から選ばれる少なくとも１つの着色剤であって、ネガ型感光性樹脂組成物における全固形分中に２５～６５質量％、
　溶媒（Ｄ）：該溶媒（Ｄ）の全量に対して、溶媒（Ｄ１)を３０～８０質量％、溶媒（Ｄ３）としてＰＧＭＥＡを２０～７０質量％それぞれ含有する、溶媒（Ｄ）をネガ型感光性樹脂組成物中に６５～９０質量％、
　架橋剤（Ｆ）：１分子中に２つ以上のエチレン性二重結合を有し、酸性基を有しない化合物であって、ネガ型感光性樹脂組成物における全固形分中に５～４０質量％、
　界面活性剤（Ｋ）：フッ素系界面活性剤、シリコーン系界面活性剤およびアクリル系界面活性剤から選ばれる少なくとも１つの界面活性剤であって、ネガ型感光性樹脂組成物における全固形分中に０．０５～２０質量％。 Photopolymerization initiator (B): O-acyloxime compound, 3 to 6% by mass in the total solid content in the negative photosensitive resin composition,
Black colorant (C): at least one colorant selected from carbon black and organic pigments, 25 to 65% by mass in the total solid content of the negative photosensitive resin composition,
Solvent (D): The solvent (D) is a negative type containing 30 to 80% by mass of the solvent (D1) and 20 to 70% by mass of PGMEA as the solvent (D3) with respect to the total amount of the solvent (D). 65 to 90% by mass in the photosensitive resin composition,
Crosslinking agent (F): a compound having two or more ethylenic double bonds in the molecule and having no acidic group, and 5 to 40 mass in the total solid content in the negative photosensitive resin composition %,
Surfactant (K): At least one surfactant selected from a fluorine-based surfactant, a silicone-based surfactant, and an acrylic-based surfactant, and in the total solid content in the negative photosensitive resin composition 0.05 to 20% by mass.
＜組み合わせ２＞
　アルカリ可溶性樹脂（Ａ）、光重合開始剤（Ｂ）、黒色着色剤（Ｃ）、架橋剤（Ｆ）および界面活性剤（Ｋ）は組み合わせ１と同様であり、溶媒（Ｄ）が以下である。
　溶媒（Ｄ）：該溶媒（Ｄ）の全量に対して、溶媒（Ｄ１)を３０～８０質量％、溶媒（Ｄ２）を１０～３０質量％、溶媒（Ｄ３）としてＰＧＭＥＡを０～６０質量％それぞれ含有する、溶媒（Ｄ）をネガ型感光性樹脂組成物中に６５～９０質量％。 <Combination 2>
Alkali-soluble resin (A), photopolymerization initiator (B), black colorant (C), cross-linking agent (F) and surfactant (K) are the same as in combination 1, and solvent (D) is as follows. .
Solvent (D): 30 to 80% by mass of solvent (D1), 10 to 30% by mass of solvent (D2), and 0 to 60% by mass of PGMEA as solvent (D3) with respect to the total amount of the solvent (D) 65 to 90% by mass of the solvent (D) each contained in the negative photosensitive resin composition.
［隔壁およびその製造方法］
　本発明の隔壁は、基板表面に区画を設けるために形成される隔壁であって、上記本発明のネガ型感光性樹脂組成物の硬化膜からなる。本発明の隔壁は、光学素子の用途に好適に用いられ、上記ネガ型感光性樹脂組成物が黒色着色剤（Ｃ）を含有することから、得られる隔壁は、ブラックマトリックスとしての適用が可能である。 [Partition and manufacturing method thereof]
The partition of this invention is a partition formed in order to provide a division on the substrate surface, Comprising: It consists of a cured film of the said negative photosensitive resin composition of this invention. The partition wall of the present invention is suitably used for an optical element, and since the negative photosensitive resin composition contains a black colorant (C), the resulting partition wall can be applied as a black matrix. is there.
　本発明のネガ型感光性樹脂組成物は、黒色着色剤（Ｃ）を高濃度に含有することから、該ネガ型感光性樹脂組成物から形成される隔壁すなわちブラックマトリックスは、高い遮光性、具体的には、光学濃度（ＯＤ）が２．５以上となる高い遮光性を有する。本発明においては、さらに条件を調整することにより光学濃度（ＯＤ）が３以上のブラックマトリックスの提供も可能である。光学濃度（ＯＤ）が２．５以上、特に３以上のブラックマトリックスであれば、例えば、これを用いて製造されるカラーフィルタの高コントラスト化に充分寄与できる。
　本発明の隔壁は、例えば、基板表面に複数の画素と隣接する画素間に位置する隔壁とを有する光学素子用の隔壁（ブラックマトリックス）に適用される。 Since the negative photosensitive resin composition of the present invention contains the black colorant (C) in a high concentration, the partition formed from the negative photosensitive resin composition, that is, the black matrix has high light-shielding properties, specifically Specifically, it has a high light shielding property with an optical density (OD) of 2.5 or more. In the present invention, a black matrix having an optical density (OD) of 3 or more can be provided by further adjusting the conditions. If the black matrix has an optical density (OD) of 2.5 or more, particularly 3 or more, for example, it can sufficiently contribute to an increase in contrast of a color filter produced using the black matrix.
The partition of the present invention is applied to, for example, a partition for an optical element (black matrix) having a plurality of pixels and a partition located between adjacent pixels on the substrate surface.
　本発明のネガ型感光性樹脂組成物を用いて本発明の光学素子用の隔壁（ブラックマトリックス）を製造する方法としては、例えば、以下の方法が挙げられる。 Examples of the method for producing the barrier rib (black matrix) for the optical element of the present invention using the negative photosensitive resin composition of the present invention include the following methods.
　本発明のネガ型感光性樹脂組成物を上記基板表面に塗布して塗膜を形成し（塗膜形成工程）、次いで、上記塗膜を乾燥して膜とし（乾燥工程）、次いで、上記膜の隔壁となる部分のみを露光して光硬化させ（露光工程）、次いで、上記光硬化した部分以外の膜を除去して上記膜の光硬化部分からなる隔壁を形成させ（現像工程）、次いで、必要に応じて上記形成された隔壁等をさらに熱硬化させる（ポストベーク工程）ことにより、本発明の光学素子用の隔壁（ブラックマトリックス）が製造できる。また、現像工程とポストベーク工程の間に、上記形成された隔壁等をさらに光硬化させる（ポスト露光工程）を入れてもよい。 The negative photosensitive resin composition of the present invention is applied to the substrate surface to form a coating film (coating film forming process), then the coating film is dried to form a film (drying process), and then the film Then, only the part to be the partition wall is exposed and photocured (exposure process), and then the film other than the photocured part is removed to form the partition wall made of the photocured part of the film (development process), and then The partition walls (black matrix) for the optical element of the present invention can be produced by further thermally curing the formed partition walls and the like as necessary (post-baking step). Moreover, you may put further the photocuring (post exposure process) of the said formed partition etc. between a image development process and a post-baking process.
　基板の材質は特に限定されるものではないが、各種ガラス板；ポリエステル（ポリエチレンテレフタレート等）、ポリオレフィン（ポリエチレン、ポリプロピレン等）、ポリカーボネート、ポリメチルメタクリレート、ポリスルホン、ポリイミド、ポリ（メタ）アクリル樹脂等の熱可塑性プラスチックシート；エポキシ樹脂、不飽和ポリエステル等の熱硬化性樹脂の硬化シート等を使用できる。特に、耐熱性の点からガラス板、ポリイミド等の耐熱性プラスチックが好ましい。また、ポスト露光を、隔壁が形成されていない裏面（基板側）から行うこともあるため、透明基板であることが好ましい。
　基板のネガ型感光性樹脂組成物の塗布面は、塗布前に予めアルコール洗浄、紫外線／オゾン洗浄等で洗浄することが好ましい。 The material of the substrate is not particularly limited, but various glass plates; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin, etc. Thermoplastic plastic sheet; Cured sheet of thermosetting resin such as epoxy resin and unsaturated polyester can be used. In particular, a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance. Moreover, since a post exposure may be performed from the back surface (board | substrate side) in which the partition is not formed, it is preferable that it is a transparent substrate.
It is preferable to clean the application surface of the negative photosensitive resin composition on the substrate by alcohol cleaning, ultraviolet / ozone cleaning or the like before application.
（塗膜形成工程）
　塗布方法としては、膜厚が均一な塗膜が形成される方法であれば特に制限されず、スピンコート法、スプレー法、スリットコート法、ロールコート法、回転塗布法、バー塗布法等、通常の塗膜形成に用いられる方法が挙げられる。特に大面積に一度に塗布できるスリットコート法が好ましい。
　上記の通り、本発明のネガ型感光性樹脂組成物は高濃度に黒色着色剤（Ｃ）を含有しながら、化合物（１）である溶媒（Ｄ１)を含む溶媒（Ｄ）を用いることで、再溶解性に優れ、さらにスリットコート法による塗布が可能な粘度を有するものである。よって、スリットノズル周辺の乾燥固化物に起因する不具合等を解消でき、さらに、適度な粘度により塗工自体も負荷なく行えることから、生産性のよい塗工が可能であり、特にスリットコート法を用いた塗工から硬化膜を形成するのに好適である。
　塗膜の膜厚は最終的に得られる隔壁の高さとネガ型感光性樹脂組成物の固形分濃度を勘案して決められる。塗膜の膜厚は、最終的に得られる隔壁（ブラックマトリックス）の高さの５００～２，０００％が好ましく、５５０～１，０００％が特に好ましい。塗膜の膜厚は０.３～１００μｍが好ましく、１～５０μｍが特に好ましい。 (Coating film formation process)
The coating method is not particularly limited as long as a coating film having a uniform film thickness is formed. Usually, spin coating, spraying, slit coating, roll coating, spin coating, bar coating, etc. The method used for the coating film formation of this is mentioned. In particular, a slit coating method that can be applied at once to a large area is preferred.
As described above, the negative photosensitive resin composition of the present invention contains the black colorant (C) at a high concentration, while using the solvent (D) containing the solvent (D1) as the compound (1). It has excellent re-solubility and has a viscosity that can be applied by slit coating. Therefore, it is possible to eliminate problems caused by the dried solidified material around the slit nozzle, and furthermore, since the coating itself can be carried out with no load due to an appropriate viscosity, it is possible to perform coating with good productivity. It is suitable for forming a cured film from the coating used.
The film thickness of the coating film is determined in consideration of the height of the partition wall finally obtained and the solid content concentration of the negative photosensitive resin composition. The film thickness of the coating film is preferably 500 to 2,000%, particularly preferably 550 to 1,000%, of the height of the partition wall (black matrix) finally obtained. The thickness of the coating film is preferably from 0.3 to 100 μm, particularly preferably from 1 to 50 μm.
（乾燥工程）
　上記塗膜形成工程で基板表面に形成された塗膜を乾燥し、膜を得る。乾燥によって、塗膜を構成するネガ型感光性樹脂組成物に含まれる溶媒を含む揮発成分が揮発、除去され、粘着性のない膜が得られる。 (Drying process)
The coating film formed on the substrate surface in the coating film forming step is dried to obtain a film. By drying, the volatile components including the solvent contained in the negative photosensitive resin composition constituting the coating film are volatilized and removed, and a non-sticky film is obtained.
　乾燥の方法としては、真空乾燥や加熱乾燥（プリベーク）が好ましい。また、膜外観のムラを発生させず、効率よく乾燥させるために、真空乾燥と加熱乾燥を併用することがより好ましい。
　真空乾燥の条件は、各成分の種類、配合割合等によっても異なるが、１０～５００Ｐａで１０～３００秒間行うことが好ましい。
　加熱乾燥は、基板とともに塗膜をホットプレート、オーブン等の加熱装置により、５０～１２０℃で１０～２，０００秒間行うことが好ましい。 As a drying method, vacuum drying or heat drying (pre-baking) is preferable. Further, in order to efficiently dry the film without causing unevenness of the film appearance, it is more preferable to use vacuum drying and heat drying in combination.
The vacuum drying conditions vary depending on the type of each component, the blending ratio, and the like, but it is preferable to perform the drying at 10 to 500 Pa for 10 to 300 seconds.
Heat drying is preferably performed at 50 to 120 ° C. for 10 to 2,000 seconds with a heating device such as a hot plate or oven together with the substrate.
（露光工程）
　得られた膜の一部に所定パターンのマスクを介して露光を行う。露光部のネガ型感光性樹脂組成物は硬化し、未露光部のネガ型感光性樹脂組成物は硬化しない。
　照射する光としては、可視光；紫外線；遠紫外線；ＫｒＦエキシマレーザ、ＡｒＦエキシマレーザ、Ｆ２エキシマレーザ、Ｋｒ２エキシマレーザ、ＫｒＡｒエキシマレーザ、Ａｒ２エキシマレーザ等のエキシマレーザ；Ｘ線；電子線等が挙げられる。また、照射光としては、波長１００～６００ｎｍの光が好ましく、３００～５００ｎｍの範囲に分布を有する光がより好ましく、ｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）およびｇ線（４３６ｎｍ）が特に好ましい。 (Exposure process)
A part of the obtained film is exposed through a mask having a predetermined pattern. The negative photosensitive resin composition in the exposed portion is cured, and the negative photosensitive resin composition in the unexposed portion is not cured.
The irradiation light is visible light; ultraviolet light; far ultraviolet light; excimer laser such as KrF excimer laser, ArF excimer laser, F 2 excimer laser, Kr 2 excimer laser, KrAr excimer laser, Ar 2 excimer laser; X-ray; Etc. The irradiation light is preferably light having a wavelength of 100 to 600 nm, more preferably light having a distribution in the range of 300 to 500 nm, and particularly preferably i-line (365 nm), h-line (405 nm), and g-line (436 nm). .
　照射装置として、公知の超高圧水銀灯等を用いることができる。露光量は、ｉ線基準で、５～１，０００ｍＪ／ｃｍ２が好ましく、１０～２００ｍＪ／ｃｍ２が特に好ましい。露光量が上記範囲の下限値以上であると、隔壁となるネガ型感光性樹脂組成物の硬化が充分であり、その後の現像で溶解や基板からの剥離が生じにくくなる。上記範囲の上限値以下であると、高い解像度が得られる。 A well-known super high pressure mercury lamp etc. can be used as an irradiation apparatus. Exposure dose, i-line basis, preferably 5 ~ 1,000mJ / cm 2, particularly preferably 10 ~ 200mJ / cm 2. When the exposure amount is at least the lower limit of the above range, the negative photosensitive resin composition serving as the partition is sufficiently cured, and subsequent development does not easily cause dissolution or peeling from the substrate. A high resolution is obtained when it is not more than the upper limit of the above range.
（現像工程）
　現像液により現像し、未露光部分のネガ型感光性樹脂組成物を除去する。現像液としては、無機アルカリ類、アミン類、アルカノールアミン類、第４級アンモニウム塩等のアルカリ類を含むアルカリ水溶液を用いることができる。また現像液には、溶解性の向上や残渣除去のために、界面活性剤やアルコール等の有機溶媒を添加することができる。
　現像時間（現像液に接触させる時間）は、５～１８０秒間が好ましい。また現像方法は液盛り法、ディッピング法、シャワー法等が挙げられる。現像後、高圧水洗や流水洗浄を行い、圧縮空気や圧縮窒素で風乾させることによって、基板表面の水分を除去できる。 (Development process)
It develops with a developing solution and the negative photosensitive resin composition of an unexposed part is removed. As the developer, an aqueous alkali solution containing alkalis such as inorganic alkalis, amines, alkanolamines, and quaternary ammonium salts can be used. Further, an organic solvent such as a surfactant or alcohol can be added to the developer in order to improve solubility and remove residues.
The development time (time for contact with the developer) is preferably 5 to 180 seconds. Examples of the developing method include a liquid piling method, a dipping method, and a shower method. After the development, water on the substrate surface can be removed by washing with high pressure water or running water and drying with compressed air or compressed nitrogen.
（ポスト露光工程）
　次に、必要に応じてポスト露光を行ってもよい。ポスト露光は隔壁が形成されている表面、または隔壁が形成されていない裏面（基板側）のいずれから行ってもよい。また、表裏両面から露光してもよい。露光量は、５０ｍＪ／ｃｍ２以上が好ましく、２００ｍＪ／ｃｍ２以上がより好ましく、１，０００ｍＪ／ｃｍ２以上がさらに好ましく、２，０００ｍＪ／ｃｍ２以上が特に好ましい。 (Post exposure process)
Next, you may perform post exposure as needed. The post-exposure may be performed from either the front surface where the partition walls are formed or the back surface (substrate side) where the partition walls are not formed. Moreover, you may expose from both front and back. Exposure is preferably 50 mJ / cm 2 or more, more preferably 200 mJ / cm 2 or more, more preferably 1,000 mJ / cm 2 or more, 2,000 mJ / cm 2 or more is particularly preferable.
　照射する光としては、紫外線が好ましく、光源として、公知の超高圧水銀灯または高圧水銀灯等を用いることができる。これらの光源は隔壁の硬化に寄与する６００ｎｍ以下の光を発光し、かつ、隔壁の酸化分解の原因となる２００ｎｍ以下の光の発光が少ないため、好ましく用いられる。さらに水銀灯に用いられている石英管ガラスが２００ｎｍ以下の光をカットする光学フィルタ機能を有することが好ましい。 The light to be irradiated is preferably ultraviolet light, and a known ultra-high pressure mercury lamp or high-pressure mercury lamp can be used as the light source. These light sources are preferably used because they emit light having a wavelength of 600 nm or less that contributes to the hardening of the barrier ribs, and emit less light having a wavelength of 200 nm or less that causes oxidative decomposition of the barrier ribs. Furthermore, it is preferable that the quartz tube glass used for the mercury lamp has an optical filter function for cutting light of 200 nm or less.
　光源としては、低圧水銀灯を用いることもできる。ただし、低圧水銀灯は２００ｎｍ以下の波長の発光強度も高く、オゾンの生成により隔壁の酸化分解が起こり易いため、多量の露光を行うことは好ましくない。露光量は５００ｍＪ／ｃｍ２以下であることが好ましく、３００ｍＪ／ｃｍ２以下が特に好ましい。 A low pressure mercury lamp can also be used as the light source. However, a low-pressure mercury lamp has a high emission intensity at a wavelength of 200 nm or less, and oxidative decomposition of the partition walls is likely to occur due to the generation of ozone. The exposure amount is preferably 500 mJ / cm 2 or less, particularly preferably 300 mJ / cm 2 or less.
（ポストベーク工程）
　続いて、隔壁を加熱することが好ましい。ホットプレート、オーブン等の加熱装置により、５～９０分間加熱処理をすることによって、隔壁および隔壁で区分された領域（ドット）とからなるパターンが形成される。
　加熱温度は１５０～２５０℃が好ましく、１８０～２５０℃が特に好ましい。加熱温度が上記範囲の下限値以上であると、隔壁の硬化が充分であり、充分な耐薬品性が得られ、その後の画素を形成する際にインクを塗布した場合に、そのインクに含まれる溶媒により隔壁が膨潤したり、インクが滲んでしまうことがない。上記範囲の上限値以下であると、隔壁の熱分解が生じにくい。 (Post bake process)
Subsequently, it is preferable to heat the partition wall. By performing heat treatment for 5 to 90 minutes with a heating device such as a hot plate or an oven, a pattern composed of partition walls and regions (dots) divided by the partition walls is formed.
The heating temperature is preferably 150 to 250 ° C, particularly preferably 180 to 250 ° C. When the heating temperature is equal to or higher than the lower limit of the above range, the partition walls are sufficiently cured, sufficient chemical resistance is obtained, and is included in the ink when the ink is applied during the subsequent pixel formation. The partition wall does not swell or the ink does not ooze due to the solvent. When it is below the upper limit of the above range, thermal decomposition of the partition wall is difficult to occur.
　本発明のネガ型感光性樹脂組成物から形成されるパターンは、隔壁の幅の平均が、１００μｍ以下であることが好ましく、２０μｍ以下であることが特に好ましい。隣接する隔壁間の距離（ドットの幅）の平均は、３００μｍ以下であることが好ましく、１００μｍ以下であることが特に好ましい。隔壁の高さの平均は、０．０５～５０μｍであることが好ましく、０．２～１０μｍであることが特に好ましい。 The pattern formed from the negative photosensitive resin composition of the present invention preferably has an average partition wall width of 100 μm or less, particularly preferably 20 μm or less. The average distance between adjacent barrier ribs (dot width) is preferably 300 μm or less, and particularly preferably 100 μm or less. The average height of the partition walls is preferably 0.05 to 50 μm, particularly preferably 0.2 to 10 μm.
　本発明の隔壁（ブラックマトリックス）が適用される光学素子としては、カラーフィルタ、有機ＥＬ素子等が挙げられる。 Examples of the optical element to which the partition wall (black matrix) of the present invention is applied include a color filter and an organic EL element.
［カラーフィルタの製造方法］
　上記のように基板表面に隔壁（ブラックマトリックス）を形成した後、この隔壁（ブラックマトリックス）表面に、透明着色感光性樹脂組成物からなるインクを用いて、隔壁と同様な方法（フォトリソグラフィ法）で、隔壁（ブラックマトリックス）間に位置するように画素を形成して、カラーフィルタを製造する。 [Color filter manufacturing method]
After the partition wall (black matrix) is formed on the substrate surface as described above, the same method as that for the partition wall (photolithographic method) is used on the partition wall (black matrix) surface using an ink made of a transparent colored photosensitive resin composition. Thus, pixels are formed so as to be positioned between the barrier ribs (black matrix) to manufacture a color filter.
　フォトリソグラフィ法に用いるインクは、主に着色成分と開始剤とバインダー樹脂成分と溶剤とを含む。着色成分としては、耐熱性、耐光性等に優れた顔料および染料を用いることが好ましい。
　バインダー樹脂成分としては、透明で耐熱性に優れた樹脂が好ましく、アクリル樹脂、メラミン樹脂、ウレタン樹脂等が挙げられる。水性のインクは、溶剤として水および必要に応じて水溶性有機溶媒を含み、バインダー樹脂成分として水溶性樹脂または水分散性樹脂を含み、必要に応じて各種助剤を含む。また、油性のインクは、溶剤として有機溶剤を含み、バインダー樹脂成分として有機溶剤に可溶な樹脂を含み、必要に応じて各種助剤を含む。 The ink used for the photolithography method mainly includes a coloring component, an initiator, a binder resin component, and a solvent. As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like.
As the binder resin component, a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The water-based ink contains water and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary. The oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
　また、隔壁（ブラックマトリックス）で区分された領域内に、インクジェット法によりインクジェット装置を用いてインクを注入して画素を形成することもできる。 In addition, pixels can be formed by injecting ink into an area partitioned by a partition wall (black matrix) by an inkjet method using an inkjet apparatus.
　上記隔壁（ブラックマトリックス）が形成された基板においては、該隔壁（ブラックマトリックス）で仕切られた領域（ドット）内にインクを投入する前に、ドット内に露出した基板表面に、例えば、アルカリ水溶液による洗浄処理、紫外線洗浄処理、紫外線／オゾン洗浄処理、エキシマ洗浄処理、コロナ放電処理、酸素プラズマ処理等の方法で親インク化処理が施されてもよい。 In the substrate on which the partition wall (black matrix) is formed, for example, an alkaline aqueous solution is applied to the surface of the substrate exposed in the dot before the ink is put into the region (dot) partitioned by the partition wall (black matrix). The ink repellency treatment may be performed by a method such as cleaning by UV, UV cleaning, UV / ozone cleaning, excimer cleaning, corona discharge, oxygen plasma.
　インクジェット装置としては、特に限定されるものではないが、帯電したインクを連続的に噴射し磁場によって制御する方法、圧電素子を用いて間欠的にインクを噴射する方法、インクを加熱しその発泡を利用して間欠的に噴射する方法等の各種の方法を用いた装置を用いることができる。
　画素の形状は、ストライプ型、モザイク型、トライアングル型、４画素配置型等の公知のいずれの配列とすることも可能である。 The ink jet device is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, a method in which ink is ejected intermittently using a piezoelectric element, and ink is heated to foam. An apparatus using various methods such as a method of intermittent injection by use can be used.
The pixel shape may be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type.
　インクジェット法に用いるインクは、主に着色成分とバインダー樹脂成分と溶剤とを含む。着色成分としては、耐熱性、耐光性等に優れた顔料および染料を用いることが好ましい。
　バインダー樹脂成分としては、透明で耐熱性に優れた樹脂が好ましく、アクリル樹脂、メラミン樹脂、ウレタン樹脂等が挙げられる。水性のインクは、溶剤として水および必要に応じて水溶性有機溶媒を含み、バインダー樹脂成分として水溶性樹脂または水分散性樹脂を含み、必要に応じて各種助剤を含む。また、油性のインクは、溶剤として有機溶剤を含み、バインダー樹脂成分として有機溶剤に可溶な樹脂を含み、必要に応じて各種助剤を含む。
　なお、インクジェット法においては、上記インクジェット装置でドットにインクを注入した後、ドット内に形成されたインク層に対して、必要に応じて、乾燥、加熱硬化、紫外線硬化等の処理を行うことで画素が形成される。 The ink used for the ink jet method mainly includes a coloring component, a binder resin component, and a solvent. As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like.
As the binder resin component, a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The water-based ink contains water and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary. The oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
In the ink jet method, after ink is injected into the dots by the ink jet device, the ink layer formed in the dots is subjected to treatment such as drying, heat curing, and ultraviolet curing as necessary. Pixels are formed.
　画素形成後、必要に応じて、保護膜層を形成する。保護膜層は表面平坦性を上げる目的と隔壁（ブラックマトリックス）や画素部のインクからの溶出物が液晶層に到達するのを遮断する目的で形成することが好ましい。保護膜層を形成する際に、隔壁（ブラックマトリックス）の撥インク性が強い場合は、事前に隔壁（ブラックマトリックス）の撥インク性を除去することが好ましい。この場合、撥インク性を除去しないと、オーバーコート用塗布液をはじき、均一な膜厚が得られないおそれがある。隔壁（ブラックマトリックス）の撥インク性を除去する方法としては、プラズマアッシング処理や光アッシング処理等が挙げられる。
　さらに必要に応じて、カラーフィルタを用いて製造される液晶パネル等の高品位化のためにフォトスペーサを隔壁（ブラックマトリックス）上に形成することが好ましい。
　本発明のカラーフィルタは、上記本発明による遮光性の高い隔壁をブラックマトリックスとして用いていることから、充分に高いコントラスト性能を有するカラーフィルタである。 After the pixel formation, a protective film layer is formed as necessary. The protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the elution from the partition wall (black matrix) or the pixel portion ink from reaching the liquid crystal layer. When forming the protective film layer, if the ink repellency of the partition wall (black matrix) is strong, it is preferable to remove the ink repellency of the partition wall (black matrix) in advance. In this case, unless the ink repellency is removed, the overcoat coating solution may be repelled and a uniform film thickness may not be obtained. Examples of a method for removing the ink repellency of the partition walls (black matrix) include plasma ashing and light ashing.
Further, if necessary, it is preferable to form a photo spacer on the partition wall (black matrix) in order to improve the quality of a liquid crystal panel or the like manufactured using a color filter.
The color filter of the present invention is a color filter having sufficiently high contrast performance because the partition wall having high light shielding properties according to the present invention is used as a black matrix.
［有機ＥＬ素子の製造方法］
　隔壁を形成する前に、ガラス等の透明基板にスズドープ酸化インジウム錫（ＩＴＯ）等の透明電極をスパッタ法等によって製膜し、必要に応じて所望のパターンに透明電極をエッチングする。次に、本発明のネガ型感光性樹脂組成物を用いて隔壁を形成し、蒸着法、インクジェット法を用いてドットに正孔輸送材料、発光材料の溶液を順次塗布、乾燥して、正孔輸送層、発光層を形成する。その後アルミニウム等の電極を蒸着法等によって形成することによって、有機ＥＬ素子の画素が得られる。インクジェット法を用いて正孔輸送層、発光層を形成する場合、必要に応じて、形成前にドットの親インク化処理を行う。 [Method of manufacturing organic EL element]
Before forming the partition walls, a transparent electrode such as tin-doped indium tin oxide (ITO) is formed on a transparent substrate such as glass by sputtering or the like, and the transparent electrode is etched into a desired pattern as necessary. Next, a barrier rib is formed using the negative photosensitive resin composition of the present invention, and a hole transport material and a light emitting material solution are sequentially applied to the dots using a vapor deposition method and an ink jet method, and dried to form holes. A transport layer and a light emitting layer are formed. Thereafter, an electrode of aluminum or the like is formed by a vapor deposition method or the like, thereby obtaining a pixel of the organic EL element. When forming a positive hole transport layer and a light emitting layer using the inkjet method, if necessary, the ink is made into an ink-philic ink before the formation.
　以下に実施例を用いて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。なお、例１～１１は実施例、例２１～２８が比較例である。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 11 are examples, and examples 21 to 28 are comparative examples.
　合成例および実施例で用いた化合物の略語は以下の通りである。
（アルカリ可溶性樹脂（Ａ））
　ＺＣＲ１６４２：上式（Ａ１－２ａ）で表されるビフェニル骨格を有するエポキシ樹脂にエチレン性二重結合と酸性基とを導入した樹脂（日本化薬社製、商品名：ＺＣＲ－１６４２Ｈ、質量平均分子量（Ｍｗ）：５，８００、酸価：１００ｍｇＫＯＨ／ｇ、固形分：７０質量％、ＰＧＭＥＡ：３０質量％）。 Abbreviations of the compounds used in Synthesis Examples and Examples are as follows.
(Alkali-soluble resin (A))
ZCR1642: Resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the above formula (A1-2a) (trade name: ZCR-1642H, manufactured by Nippon Kayaku Co., Ltd., mass average molecular weight) (Mw): 5,800, acid value: 100 mg KOH / g, solid content: 70% by mass, PGMEA: 30% by mass).
（光重合開始剤（Ｂ））
　ＯＸＥ０２：エタノン,１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）（式（３）で表される化合物において、Ｒ３：メチル基、Ｒ４：メチル基、Ｒ５：エチル基、Ｒ６、Ｒ８、Ｒ９：水素原子、Ｒ７：２－メチルベンゾイル基で示される。ＢＡＳＦ社製、商品名：ＯＸＥ０２。）。
　ＮＣＩ８３１：ＡＤＥＫＡ社製、商品名：アデカクルーズ　ＮＣＩ－８３１。
　Ｎ１９１９：ＡＤＥＫＡ社製、商品名：アデカオプトマー　Ｎ－１９１９。 (Photopolymerization initiator (B))
OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (in the compound represented by formula (3), R 3 : methyl group, R 4 : methyl group, R 5 : ethyl group, R 6 , R 8 , R 9 : hydrogen atom, R 7 : 2-methylbenzoyl group, manufactured by BASF, trade name: OXE02. ).
NCI831: Made by ADEKA, product name: Adeka Cruz NCI-831.
N1919: Made by ADEKA, trade name: Adeka optomer N-1919.
（黒色着色剤（Ｃ）＋高分子分散液）
　ＣＢ：カーボンブラック分散液（平均２次粒径：１２０ｎｍ、カーボンブラック：２０質量％、アミン価１８ｍｇＫＯＨ／ｇのポリウレタン系高分子分散剤：５質量％、ＰＧＭＥＡ：７５質量％。）。
　混合有機顔料：Ｃ．Ｉ．ピグメントブルー１５：６、Ｃ．Ｉ．ピグメントレッド２５４、Ｃ．Ｉ．ピグメントイエロー１３９および高分子分散剤の１０：５：５：５の混合物（固形分：２５質量％、ＰＧＭＥＡ：７５質量％。）。 (Black colorant (C) + polymer dispersion)
CB: carbon black dispersion (average secondary particle size: 120 nm, carbon black: 20% by mass, polyurethane polymer dispersant having an amine value of 18 mgKOH / g: 5% by mass, PGMEA: 75% by mass).
Mixed organic pigment: C.I. I. Pigment blue 15: 6, C.I. I. Pigment red 254, C.I. I. Pigment Yellow 139 and a polymeric dispersant in a 10: 5: 5: 5 mixture (solid content: 25 mass%, PGMEA: 75 mass%).
（溶媒（Ｄ））
（ｉ）溶媒（Ｄ１）
　ＥＤＭ：ジエチレングリコールエチルメチルエーテル（沸点：１７６℃、粘度：１．２ｍＰａ・ｓ）。
　ＩＰＤＭ：ジエチレングリコールイソプロピルメチルエーテル（沸点：１７９℃、粘度：１．３ｍＰａ・ｓ）。
(ii）溶媒（Ｄ２）
　ＣＨＮ：シクロヘキサノン（沸点：１５５℃、粘度：２．１ｍＰａ・ｓ）。
　４－ＢＬ：γ－ブチロラクトン（沸点：２０４℃、粘度：１．８ｍＰａ・ｓ）。
(iii）溶媒（Ｄ３）
　ＭＤＭ：ジエチレングリコールジメチルエーテル（沸点：１６２℃、粘度：１．１ｍＰａ・ｓ）。
　ＰＧＭＥＡ：プロピレングリコール１－モノメチルエーテル２－アセテート（沸点：１４６℃、粘度：１．３ｍＰａ・ｓ）。
　ＥＤＥ：ジエチレングリコールジエチルエーテル（沸点：１８９℃、粘度：１．３ｍＰａ・ｓ）。
　ＢＤＭ：ジエチレングリコールブチルメチルエーテル（沸点：２１２℃、粘度：１．５ｍＰａ・ｓ）。
　ＤＭＭ：ジプロピレングリコールジメチルエーテル（沸点：１７１℃、粘度：１．０ｍＰａ・ｓ）。
　ＣＨＸＡ：酢酸シクロヘキシル（シクロヘキサノールアセテート、沸点：１７３℃、粘度：２．０ｍＰａ・ｓ）。
　ＤＰＭＡ：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（沸点：２１３℃、粘度：２．２ｍＰａ・ｓ）。
　ＩＰＡ：イソプロピルアルコール（２－プロパノール、沸点：８２℃、粘度：１．８ｍＰａ・ｓ）。
　ＢＡ：酢酸ブチル（ｎ－ブチルアセテート、沸点：１２６℃、粘度：０．９ｍＰａ・ｓ）。 (Solvent (D))
(I) Solvent (D1)
EDM: Diethylene glycol ethyl methyl ether (boiling point: 176 ° C., viscosity: 1.2 mPa · s).
IPDM: Diethylene glycol isopropyl methyl ether (boiling point: 179 ° C., viscosity: 1.3 mPa · s).
(ii) Solvent (D2)
CHN: cyclohexanone (boiling point: 155 ° C., viscosity: 2.1 mPa · s).
4-BL: γ-butyrolactone (boiling point: 204 ° C., viscosity: 1.8 mPa · s).
(iii) Solvent (D3)
MDM: Diethylene glycol dimethyl ether (boiling point: 162 ° C., viscosity: 1.1 mPa · s).
PGMEA: Propylene glycol 1-monomethyl ether 2-acetate (boiling point: 146 ° C., viscosity: 1.3 mPa · s).
EDE: Diethylene glycol diethyl ether (boiling point: 189 ° C., viscosity: 1.3 mPa · s).
BDM: Diethylene glycol butyl methyl ether (boiling point: 212 ° C., viscosity: 1.5 mPa · s).
DMM: Dipropylene glycol dimethyl ether (boiling point: 171 ° C., viscosity: 1.0 mPa · s).
CHXA: cyclohexyl acetate (cyclohexanol acetate, boiling point: 173 ° C., viscosity: 2.0 mPa · s).
DPMA: dipropylene glycol monomethyl ether acetate (boiling point: 213 ° C., viscosity: 2.2 mPa · s).
IPA: isopropyl alcohol (2-propanol, boiling point: 82 ° C., viscosity: 1.8 mPa · s).
BA: Butyl acetate (n-butyl acetate, boiling point: 126 ° C., viscosity: 0.9 mPa · s).
（架橋剤（Ｆ））
　ＵＸ５００２：多官能ウレタンアクリレートオリゴマー（日本化薬社製、商品名：ＫＡＹＡＲＡＤ　ＵＸ－５００２Ｄ－Ｐ２０、固形分：８０質量％、ＰＧＭＥＡ：２０質量％）。
（微粒子（Ｇ））
　ＰＭＡ－ＳＴ：商品名（日産化学工業社製。オルガノシリカゾル、固形分：３０質量％、ＰＧＭＥＡ：７０質量％。）。
（シランカップリング剤（Ｈ））
　ＫＢＭ５１０３：商品名（信越化学社製。３－アクリロイルオキシプロピルトリメトキシシラン。）。
（熱硬化剤（Ｉ））
　ＸＤ１０００：多官能エポキシ樹脂（日本化薬社製、商品名：ＸＤ１０００）。
（界面活性剤（Ｋ））
　ＢＹＫ－３０７：商品名（ビックケミー・ジャパン社製。ポリエーテル変性ポリジメチルシロキサン）。 (Crosslinking agent (F))
UX5002: polyfunctional urethane acrylate oligomer (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD UX-5002D-P20, solid content: 80% by mass, PGMEA: 20% by mass).
(Fine particles (G))
PMA-ST: trade name (manufactured by Nissan Chemical Industries, Ltd., organosilica sol, solid content: 30% by mass, PGMEA: 70% by mass).
(Silane coupling agent (H))
KBM5103: Trade name (manufactured by Shin-Etsu Chemical Co., Ltd. 3-acryloyloxypropyltrimethoxysilane).
(Thermosetting agent (I))
XD1000: Multifunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: XD1000).
(Surfactant (K))
BYK-307: trade name (manufactured by Big Chemie Japan, polyether-modified polydimethylsiloxane).
［例１～１１および２１～２８：ネガ型感光性樹脂組成物の調製、隔壁の形成と評価］
（ネガ型感光性樹脂組成物の調製）
　表１および表２に示す割合で、アルカリ可溶性樹脂（Ａ）（溶媒としてＰＧＭＥＡを３０質量％含む。）、光重合開始剤（Ｂ）、黒色着色剤（Ｃ）（溶媒としてＰＧＭＥＡを７５質量％含む。）、溶媒（Ｄ）、架橋剤（Ｆ）（溶媒としてＰＧＭＥＡを２０質量％含む）、微粒子（Ｇ）（溶媒としてＰＧＭＥＡを７０質量％含む。）、シランカップリング剤（Ｈ）、熱硬化剤（Ｉ）および界面活性剤（Ｋ）を配合して、ネガ型感光性樹脂組成物を得た。 [Examples 1 to 11 and 21 to 28: Preparation of negative photosensitive resin composition, formation and evaluation of partition walls]
(Preparation of negative photosensitive resin composition)
In the proportions shown in Table 1 and Table 2, the alkali-soluble resin (A) (containing 30% by mass of PGMEA as a solvent), a photopolymerization initiator (B), and a black colorant (C) (75% by mass of PGMEA as a solvent) ), Solvent (D), crosslinking agent (F) (containing 20% by mass of PGMEA as a solvent), fine particles (G) (containing 70% by mass of PGMEA as a solvent), silane coupling agent (H), heat Curing agent (I) and surfactant (K) were blended to obtain a negative photosensitive resin composition.
（ブラックマトリックスの形成）
　ガラス基板（７５×７５ｍｍ）表面にスピンナーを用いてネガ型感光性樹脂組成物を塗布し、塗膜を形成した（塗膜形成工程）。
　次に、ホットプレート上で１００℃、２分間の乾燥を行い、例１、２および例２１～２７については膜厚１．０μｍ、例３～１０については膜厚２．０μｍ、例１１については膜厚３．０μｍの膜をそれぞれ形成したガラス基板（１）を得た（乾燥工程）。
　次に、１０μｍ×１０ｍｍの線状の開口部を持つフォトマスクを通して、超高圧水銀灯を用いて、露光量がｉ線（３６５ｎｍ）基準で５０ｍＪ／ｃｍ２の光を照射した（露光工程）。 (Formation of black matrix)
A negative photosensitive resin composition was applied to the surface of a glass substrate (75 × 75 mm) using a spinner to form a coating film (coating film forming step).
Next, drying was performed on a hot plate at 100 ° C. for 2 minutes. For Examples 1, 2, and 21 to 27, the film thickness was 1.0 μm, for Examples 3 to 10, the film thickness was 2.0 μm, and for Example 11, Glass substrates (1) each having a film thickness of 3.0 μm were obtained (drying step).
Next, light having an exposure dose of 50 mJ / cm 2 on the basis of i-line (365 nm) was irradiated through a photomask having a linear opening of 10 μm × 10 mm using an ultrahigh pressure mercury lamp (exposure process).
　次いで、未露光部分を無機アルカリタイプ現像液（横浜油脂工業社製、商品名：セミクリーンＤＬ－Ａ４の１０倍希釈水溶液）に浸漬して現像し、未露光部を水により洗い流し、乾燥させた（現像工程）。
　次いで、ホットプレート上、２２０℃で１時間加熱することにより、表面にパターン（ブラックマトリックス）が形成されたガラス基板（２）を得た（ポストベーク工程）。 Next, the unexposed portion was developed by being immersed in an inorganic alkali type developer (Yokohama Yushi Kogyo Co., Ltd., trade name: Semi-clean DL-A4 10-fold diluted aqueous solution), and the unexposed portion was washed away with water and dried. (Development process).
Subsequently, the glass substrate (2) in which the pattern (black matrix) was formed in the surface was obtained by heating on a hotplate at 220 degreeC for 1 hour (post-baking process).
（評価）
　得られたネガ型感光性樹脂組成物の粘度を測定、評価した。また、得られたガラス基板（１）およびガラス基板（２）を用いて、再溶解性および遮光性を以下に示す方法で測定、評価した。評価結果を表１および表２に示す。 (Evaluation)
The viscosity of the obtained negative photosensitive resin composition was measured and evaluated. Moreover, remelting property and light-shielding property were measured and evaluated by the method shown below using the obtained glass substrate (1) and glass substrate (2). The evaluation results are shown in Tables 1 and 2.
（１）粘度
　ネガ型感光性樹脂組成物の粘度は、粘度計校正用標準液ＪＳ２．５（日本グリース社製）で校正したＴＶＥ２５Ｌ形粘度計（東機産業社製）を用いて２５℃の条件下で測定した。なお、溶媒（Ｄ）として用いた各化合物の粘度も同様にして測定したものである。
　得られた測定値をスリットコート法において求められる粘度特性に基づいて以下の基準で評価した。
　３．０ｍＰａ・ｓ未満のものを◎（良好）、３．５ｍＰａ・ｓ未満のものを○（可）、３．５ｍＰａ・ｓ以上のものを×（不良）と評価した。 (1) Viscosity The viscosity of the negative photosensitive resin composition is 25 ° C. using a TVE25L viscometer (manufactured by Toki Sangyo Co., Ltd.) calibrated with a standard solution JS2.5 for viscometer calibration (manufactured by Nippon Grease Co., Ltd.). Measured under conditions. The viscosity of each compound used as the solvent (D) was also measured in the same manner.
The obtained measured values were evaluated according to the following criteria based on the viscosity characteristics obtained in the slit coating method.
Those with less than 3.0 mPa · s were evaluated as ◎ (good), those with less than 3.5 mPa · s were evaluated as ◯ (good), and those with 3.5 mPa · s or higher were evaluated as x (defect).
（２）再溶解性
　上記ガラス基板（１）の表面から剥がした膜（０．１ｍｇ）を、ネガ型感光性樹脂組成物の固形分を除いた溶媒に相当する混合液（４０ｇ）に加えて、室温で１０分間撹拌し、再溶解性液を得た。
　得られた再溶解液の１０ｍＬをポリプロピレン製２．５μｍ孔のメンブレンフィルタでろ過し、目視または光学顕微鏡でメンブレンフィルタに付着した沈殿物を観察した。
　沈殿物が観察されなかったものを◎（良好）、沈殿物が観察されないが、メンブレンフィルタに着色したものを○（可）、沈殿物が観察されたものを×（不良）と評価した。 (2) Re-solubility The film (0.1 mg) peeled from the surface of the glass substrate (1) is added to a mixed liquid (40 g) corresponding to a solvent excluding the solid content of the negative photosensitive resin composition. The mixture was stirred at room temperature for 10 minutes to obtain a re-dissolvable liquid.
10 mL of the obtained redissolved solution was filtered through a polypropylene membrane filter having a pore size of 2.5 μm, and precipitates attached to the membrane filter were observed visually or with an optical microscope.
The case where no precipitate was observed was evaluated as ◎ (good), the case where the precipitate was not observed, but the membrane filter was colored ○ (good), and the case where the precipitate was observed was evaluated as x (bad).
（３）スリットコート特性
　例１および例２２で使用したネガ型感光性樹脂組成物をガラス基板（３７０ｍｍ×４７０ｍｍ）の表面に、以下に説明するスリットコート法にて塗布し、塗膜を形成して塗工性を評価した。
　スリットコートダイスとして、ＳＵＳ３０４製の幅３７０ｍｍ、高さ１００ｍｍ、厚さ６０ｍｍのダイスを用いた。ダイスとガラス基板との間隔は１００μｍとし、ネガ型感光性樹脂組成物をダイスに供給する手法として、ギアポンプを用いた。該条件でガラス基板に対して５０ｍｍ／秒の相対速度でダイスを移動させて、ガラス基板表面にネガ型感光性樹脂組成物の塗膜を形成した。次に、塗膜の乾燥を行い、厚さ１．０μｍの膜を形成した。スリットコートダイスは、塗布後、５分間放置して、再度スリットコート法により塗膜を形成し、乾燥することで膜を形成した。これを１０回繰り返した。得られた膜を目視で観察した。筋や感光性組成物の乾燥固化物による欠陥が観察されなかったものを○（良好）、欠陥が観察されたものを×（不良）と評価した。 (3) Slit coating characteristics The negative photosensitive resin composition used in Examples 1 and 22 was applied to the surface of a glass substrate (370 mm × 470 mm) by the slit coating method described below to form a coating film. The coatability was evaluated.
As the slit coat die, a die made of SUS304 having a width of 370 mm, a height of 100 mm, and a thickness of 60 mm was used. The gap between the die and the glass substrate was 100 μm, and a gear pump was used as a method for supplying the negative photosensitive resin composition to the die. Under these conditions, the die was moved at a relative speed of 50 mm / second with respect to the glass substrate to form a coating film of the negative photosensitive resin composition on the glass substrate surface. Next, the coating film was dried to form a film having a thickness of 1.0 μm. The slit coat die was allowed to stand for 5 minutes after coating, and a coating film was formed again by the slit coat method and dried to form a film. This was repeated 10 times. The obtained film was visually observed. The case where no defects due to the streaks or the dried solidified product of the photosensitive composition were observed was evaluated as ◯ (good), and the case where defects were observed was evaluated as x (defective).
（４）遮光性（光学濃度（ＯＤ））
　上記ガラス基板（２）のパターン（ブラックマトリックス）上の光学濃度（ＯＤ）を白黒透過濃度計Iｈｃａ－Ｔ５（伊原電子工業社製）を用いて測定した。
　光学濃度が２．５以上のものを○（良好）、２．５未満のものを×（不良）と評価した。 (4) Light shielding properties (optical density (OD))
The optical density (OD) on the pattern (black matrix) of the glass substrate (2) was measured using a monochrome transmission densitometer Ihca-T5 (manufactured by Ihara Electronics Co., Ltd.).
An optical density of 2.5 or higher was evaluated as ◯ (good), and an optical density of less than 2.5 was evaluated as x (bad).
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表１より、本発明のネガ型感光性樹脂組成物の再溶解性、粘度、およびネガ型感光性樹脂組成物より形成した隔壁（ブラックマトリックス）の遮光性は良好であった。なかでも、溶媒（Ｄ）として溶媒（Ｄ１）に加えて溶媒（Ｄ２）を用いた例６～１１は、再溶解性が特に良好であった。 From Table 1, the redissolvability and viscosity of the negative photosensitive resin composition of the present invention, and the light shielding properties of the partition (black matrix) formed from the negative photosensitive resin composition were good. In particular, Examples 6 to 11 using the solvent (D2) in addition to the solvent (D1) as the solvent (D) had particularly good resolubility.
　一方、表２において、溶媒（Ｄ１）の含有量が少ない例２１および例２８では再溶解性が不良であった。
　溶媒（Ｄ１）を含まない例２３～２７においても、再溶解性が不良であった。
　式（１）中のＲ１およびＲ２がともにメチル基である溶媒を全溶媒（Ｄ）中に４７質量％含むネガ型感光性樹脂組成物を用いた例２２のスリットコート特性が不良であったことから、Ｒ１およびＲ２がともにメチル基であると沸点が低く、スリットノズルでの乾燥固化が起き、スリットコート特性が不良になったと推定される。 On the other hand, in Table 2, the re-solubility was poor in Examples 21 and 28 where the content of the solvent (D1) was small.
Also in Examples 23 to 27 containing no solvent (D1), the re-solubility was poor.
The slit coat characteristics of Example 22 using a negative photosensitive resin composition containing 47% by mass of the solvent in which R 1 and R 2 in formula (1) are both methyl groups in the total solvent (D) were poor. From these facts, it is presumed that when both R 1 and R 2 are methyl groups, the boiling point is low, and drying and solidification occurs at the slit nozzle, resulting in poor slit coat characteristics.
　式（１）中のＲ１およびＲ２がともにエチル基である溶媒を全溶媒（Ｄ）中に４７質量％含むネガ型感光性樹脂組成物を用いた例２３の再溶解性が不良であったことから、アルキル鎖の炭素原子数が大きくなると疎水性になり、再溶解性が不良になったと推定される。
　さらにＲ１がメチル基で、Ｒ２のアルキル鎖の炭素原子数が４である溶媒を含むネガ型感光性樹脂組成物を用いた例２４でも再溶解性が不良であったことから、例２３と同様な理由で再溶解性が不良になったと推定される。
　先行技術文献に記載の溶媒を全溶媒（Ｄ）中に４７質量％含むネガ型感光性樹脂組成物を用いた例２５～２７でも再溶解性が不良であった。 The re-solubility of Example 23 using a negative photosensitive resin composition containing 47% by mass of the solvent in which R 1 and R 2 in the formula (1) are both ethyl groups in the total solvent (D) was poor. Therefore, it is presumed that when the number of carbon atoms in the alkyl chain is increased, the alkyl chain becomes hydrophobic and the re-solubility becomes poor.
Further, in Example 24 using a negative photosensitive resin composition containing a solvent in which R 1 is a methyl group and the alkyl chain of R 2 has 4 carbon atoms, re-solubility was poor, so that Example 23 It is presumed that the re-solubility became poor for the same reason.
Even in Examples 25 to 27 using a negative photosensitive resin composition containing 47% by mass of the solvent described in the prior art document in the total solvent (D), the re-solubility was poor.
　本発明のネガ型感光性樹脂組成物は、顔料を高濃度に含有する遮光性が高いブラックマトリックスの製造に適する組成物であり、得られるブラックマトリックスを使用して高解像度のカラーフィルタや有機ＥＬ素子が製造される。
　なお、２０１１年８月３０日に出願された日本特許出願２０１１－１８７７６３号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The negative photosensitive resin composition of the present invention is a composition suitable for the production of a black matrix having a high concentration of pigment and a high light-shielding property. Using the resulting black matrix, a high-resolution color filter or organic EL An element is manufactured.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2011-187863 filed on August 30, 2011 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims (12)

  1. 　アルカリ可溶性樹脂（Ａ）、光重合開始剤（Ｂ）、黒色着色剤（Ｃ）および溶媒（Ｄ）を含むネガ型感光性樹脂組成物であって、前記組成物の全固形分に対する前記黒色着色剤（Ｃ）の含有量が２０質量％超であり、前記溶媒（Ｄ）が下式（１）で表される化合物である溶媒（Ｄ１）を前記溶媒（Ｄ）の全量に対して、２０～１００質量％の割合で含むことを特徴とするネガ型感光性樹脂組成物。
    　Ｒ１Ｏ（Ｃ２Ｈ４Ｏ）２Ｒ２　　　（１）
    　式（１）中、Ｒ１はメチル基を示し、Ｒ２は炭素原子数２または３のアルキル基を示す。     A negative photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerization initiator (B), a black colorant (C) and a solvent (D), wherein the black coloration relative to the total solid content of the composition The content of the agent (C) is more than 20% by mass, and the solvent (D1) is a compound represented by the following formula (1) with respect to the total amount of the solvent (D). A negative photosensitive resin composition characterized by containing at a ratio of ˜100 mass%.
    R 1 O (C 2 H 4 O) 2 R 2 (1)
    In formula (1), R 1 represents a methyl group, and R 2 represents an alkyl group having 2 or 3 carbon atoms.
  2. 　前記溶媒（Ｄ１）が、ジエチレングリコールエチルメチルエーテルである、請求項１に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1, wherein the solvent (D1) is diethylene glycol ethyl methyl ether.
  3. 　前記溶媒（Ｄ）が、さらに、環の構成原子として、二重結合を介して酸素原子と結合する炭素原子を１個以上含み、かつエーテル性酸素原子を含んでもよい、脂肪族環式化合物である溶媒（Ｄ２)を、前記溶媒（Ｄ）の全量に対して、１０～４０質量％の割合で含む、請求項１または２に記載のネガ型感光性樹脂組成物。 In the aliphatic cyclic compound, the solvent (D) may further contain at least one carbon atom bonded to an oxygen atom via a double bond as a ring constituent atom, and may contain an etheric oxygen atom. The negative photosensitive resin composition according to claim 1 or 2, wherein the solvent (D2) is contained in a proportion of 10 to 40% by mass with respect to the total amount of the solvent (D).
  4. 　前記脂肪族環式化合物が環状エステルまたは環状ケトンである、請求項３に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 3, wherein the aliphatic cyclic compound is a cyclic ester or a cyclic ketone.
  5. 　前記アルカリ可溶性樹脂（Ａ）が、１分子中に酸性基とエチレン性二重結合とを有する感光性樹脂である、請求項１～４のいずれか一項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin (A) is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. .
  6. 　前記アルカリ可溶性樹脂（Ａ）が、酸性基が導入されたエポキシ(メタ）アクリレート樹脂である、請求項１～５のいずれか一項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (A) is an epoxy (meth) acrylate resin having an acidic group introduced therein.
  7. 　前記光重合開始剤（Ｂ）がＯ－アシルオキシム化合物である、請求項１～６のいずれか一項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 6, wherein the photopolymerization initiator (B) is an O-acyloxime compound.
  8. 　前記光重合開始剤（Ｂ）が、下式（３）で表されるＯ－アシルオキシム化合物である、請求項１～７のいずれか一項に記載のネガ型感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
    　式（３）中、Ｒ３は、水素原子、Ｒ６１またはＯＲ６２を示し、該Ｒ６１およびＲ６２は、それぞれ独立に、炭素原子数１～２０のアルキル基、シクロアルカン環中の水素原子がアルキル基に置換されていてもよい炭素原子数３～８のシクロアルキル基、炭素原子数２～５のアルケニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～３０のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～３０のフェニルアルキル基を示す。
    　Ｒ４は、水素原子、炭素原子数１～２０のアルキル基、炭素原子数３～８のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～３０のフェニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～３０のフェニルアルキル基、炭素原子数２～２０のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンゾイル基、炭素原子数２～１２のアルコキシカルボニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のフェノキシカルボニル基、またはシアノ基を示す。
    　Ｒ５は、炭素原子数１～２０のアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６～３０のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～３０のフェニルアルキル基を示す。
    　Ｒ６、Ｒ７、Ｒ８およびＲ９は、それぞれ独立に、水素原子、シアノ基、ハロゲン原子、ニトロ基、Ｒ６１、ＯＲ６２、炭素原子数２～２０のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンゾイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のベンジルカルボニル基、炭素原子数２～１２のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７～２０のフェノキシカルボニル基、炭素原子数１～２０のアミド基を示す。
    　Ｒ０は、Ｒ６１、ＯＲ６２、シアノ基またはハロゲン原子を示す。ａは０または１～３の整数である。     The negative photosensitive resin composition according to any one of claims 1 to 7, wherein the photopolymerization initiator (B) is an O-acyloxime compound represented by the following formula (3).
    Figure JPOXMLDOC01-appb-C000001
    In formula (3), R 3 represents a hydrogen atom, R 61 or OR 62 , and each of R 61 and R 62 independently represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom in a cycloalkane ring Is a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group A 6-30 phenyl group or a phenylalkyl group having 7-30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group is shown.
    R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 30 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. A phenyl group having 7 to 30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring being an alkyl group A benzoyl group having 7 to 20 carbon atoms which may be substituted, an alkoxycarbonyl group having 2 to 12 carbon atoms or a hydrogen atom in the benzene ring which may be substituted with an alkyl group having 7 to 20 carbon atoms A phenoxycarbonyl group or a cyano group.
    R 5 represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group. An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
    R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R 61 , OR 62 , an alkanoyl group having 2 to 20 carbon atoms, or a hydrogen atom in the benzene ring. A benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an amide group having 1 to 20 carbon atoms.
    R 0 represents R 61 , OR 62 , a cyano group or a halogen atom. a is 0 or an integer of 1 to 3.
  9. 　前記黒色着色剤（Ｃ）がカーボンブラックまたは有機顔料である、請求項１～８のいずれか一項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 8, wherein the black colorant (C) is carbon black or an organic pigment.
  10. 　基板表面を画素形成用の複数の区画に仕切る形に形成された隔壁であって、請求項１～９のいずれか一項に記載のネガ型感光性樹脂組成物の硬化膜からなることを特徴とする隔壁。 A partition formed in a shape that partitions the substrate surface into a plurality of compartments for pixel formation, comprising a cured film of the negative photosensitive resin composition according to any one of claims 1 to 9. A partition wall.
  11. 　請求項１０に記載の隔壁からなる基板表面を複数の区画に仕切ることを特徴とするブラックマトリックス。 A black matrix characterized by partitioning the substrate surface comprising the partition wall according to claim 10 into a plurality of sections.
  12. 　基板表面に複数の画素と隣接する画素間に位置する隔壁とを有する光学素子であって、前記隔壁が請求項１０に記載の隔壁で形成されていることを特徴とする光学素子。 An optical element having a plurality of pixels and a partition located between adjacent pixels on the surface of the substrate, wherein the partition is formed by the partition according to claim 10.
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JP7359559B2 (en) 2019-03-29 2023-10-11 日鉄ケミカル＆マテリアル株式会社 Light-shielding film, photosensitive resin composition for obtaining the same, and method for producing light-shielding film
JP2020170120A (en) * 2019-04-04 2020-10-15 東京応化工業株式会社 Photosensitive resin composition, production method of patterned cured film, and patterned cured film
JP7297499B2 (en) 2019-04-04 2023-06-26 東京応化工業株式会社 Photosensitive resin composition, method for producing patterned cured film, and patterned cured film
CN113149650A (en) * 2021-04-25 2021-07-23 陕西理工大学 SLA-based photosensitive resin for carbon material parts and preparation method of parts
CN113149650B (en) * 2021-04-25 2022-09-23 陕西理工大学 SLA-based photosensitive resin for carbon material parts and preparation method of parts

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